Evaluation of the Ca ion release, pH and surface apatite formation of a prototype tricalcium silicate cement.

Science.gov (United States)

Yamamoto, S; Han, L; Noiri, Y; Okiji, T

2017-12-01

To evaluate the Ca 2+ -releasing, alkalizing and apatite-like surface precipitate-forming abilities of a prototype tricalcium silicate cement, which was mainly composed of synthetically prepared tricalcium silicate and zirconium oxide radiopacifier. The prototype tricalcium silicate cement, white ProRoot MTA (WMTA) and TheraCal LC (a light-cured resin-modified calcium silicate-filled material) were examined. The chemical compositions were analysed with a wavelength-dispersive X-ray spectroscopy electron probe microanalyser with an image observation function (SEM-EPMA). The pH and Ca 2+ concentrations of water in which the set materials had been immersed were measured, and the latter was assessed with the EDTA titration method. The surface precipitates formed on the materials immersed in phosphate-buffered saline (PBS) were analysed with SEM-EPMA and X-ray diffraction (XRD). Kruskal-Wallis tests followed by Mann-Whitney U-test with Bonferroni correction were used for statistical analysis (α = 0.05). The prototype cement contained Ca, Si and Zr as major elemental constituents, whereas it did not contain some metal elements that were detected in the other materials. The Ca 2+ concentrations and pH of the immersion water samples exhibited the following order: WMTA = prototype cement > TheraCal LC (P prototype cement and WMTA. The prototype tricalcium silicate cement exhibited similar Ca 2+ -releasing, alkalizing and apatite-like precipitate-forming abilities to WMTA. The Ca 2+ -releasing, alkalizing and apatite-like precipitate-forming abilities of TheraCal LC were lower than those of the other materials. © 2016 International Endodontic Journal. Published by John Wiley & Sons Ltd.

In vitro bioactivity of a tricalcium silicate cement

Energy Technology Data Exchange (ETDEWEB)

Morejon-Alonso, L.; Bareiro, O.; Santos, L.A. dos, E-mail: loreley.morejon@ufrgs.b [Universidade Federal do Rio Grande do Sul (UFRG), Porto Alegre, RS (Brazil). Escola de Engenharia. Dep. de Materiais; Carrodeguas R, Garcia [Consejo Superior de Investigaciones Cientificas (CSIC), Madrid (Spain). Inst. de Ceramica y Vidrio. Dept. de Ceramica

2009-07-01

Tricalcium silicate is the major constituent of Portland cement and the responsible for their mechanical strength at early stages. In order to be used as and additive of conventional calcium phosphate cement (CPC), in vitro bioactivity of a calcium silicate cement (CSC) after soaking in simulated body fluid (SBF) for 14 days was study. The cement was obtained by mixing Ca{sub 3}SiO{sub 5}, obtained by sol-gel process, and a Na{sub 2}HPO{sub 4} solution. The morphological and structural changes of the material before and after soaking were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results showed the formation of a layer of a Hydroxyapatite (HA) onto the CSC cement after soaking for 1h in SBF that became denser with the increase of soaking time. The study suggests that Ca{sub 3}SiO{sub 5} would be an effective additive to improve the bioactivity and long term strength of conventional CPC. (author)

Origins of saccharide-dependent hydration at aluminate, silicate, and aluminosilicate surfaces.

Science.gov (United States)

Smith, Benjamin J; Rawal, Aditya; Funkhouser, Gary P; Roberts, Lawrence R; Gupta, Vijay; Israelachvili, Jacob N; Chmelka, Bradley F

2011-05-31

Sugar molecules adsorbed at hydrated inorganic oxide surfaces occur ubiquitously in nature and in technologically important materials and processes, including marine biomineralization, cement hydration, corrosion inhibition, bioadhesion, and bone resorption. Among these examples, surprisingly diverse hydration behaviors are observed for oxides in the presence of saccharides with closely related compositions and structures. Glucose, sucrose, and maltodextrin, for example, exhibit significant differences in their adsorption selectivities and alkaline reaction properties on hydrating aluminate, silicate, and aluminosilicate surfaces that are shown to be due to the molecular architectures of the saccharides. Solid-state (1)H, (13)C, (29)Si, and (27)Al nuclear magnetic resonance (NMR) spectroscopy measurements, including at very high magnetic fields (19 T), distinguish and quantify the different molecular species, their chemical transformations, and their site-specific adsorption on different aluminate and silicate moieties. Two-dimensional NMR results establish nonselective adsorption of glucose degradation products containing carboxylic acids on both hydrated silicates and aluminates. In contrast, sucrose adsorbs intact at hydrated silicate sites and selectively at anhydrous, but not hydrated, aluminate moieties. Quantitative surface force measurements establish that sucrose adsorbs strongly as multilayers on hydrated aluminosilicate surfaces. The molecular structures and physicochemical properties of the saccharides and their degradation species correlate well with their adsorption behaviors. The results explain the dramatically different effects that small amounts of different types of sugars have on the rates at which aluminate, silicate, and aluminosilicate species hydrate, with important implications for diverse materials and applications.

Study of cements silicate phases hydrated under high pressure and high temperature; Etude des phases silicatees du ciment hydrate sous haute pression et haute temperature

Energy Technology Data Exchange (ETDEWEB)

Meducin, F.

2001-10-01

This study concerns the durability of oil-well cementing. Indeed, in oil well cementing a cement slurry is pumped down the steel casing of the well up the annular space between it and the surrounding rock to support and protect the casing. The setting conditions of pressure and temperature may be very high (up to 1000 bar and 250 deg C at the bottom of the oil-well). In this research, the hydration of the main constituent of cement, synthetic tri-calcium silicate Ca{sub 3}SiO{sub 2}, often called C{sub 3}S (C = CaO; S = SiO{sub 2} and H H{sub 2}O), is studied. Calcium Silicate hydrates are prepared in high-pressure cells to complete their phase diagram (P,T) and obtain the stability conditions for each species. Indeed, the phases formed in these conditions are unknown and the study consists in the hydration of C{sub 3}S at different temperatures, pressures, and during different times to simulate the oil-well conditions. In a first step (until 120 deg C at ambient pressure) the C-S-H, a not well crystallized and non-stoichiometric phase, is synthesized: it brings adhesion and mechanical properties., Then, when pressure and temperature increase, crystallized phases appear such as jaffeite (Ca{sub 6}(Si{sub 2}O{sub 7})(OH){sub 6}) and hillebrandite (Ca{sub 2}(SiO{sub 3})(OH){sub 2}). Silicon {sup 29}Si Nuclear Magnetic Resonance (using standard sequences MAS, CPMAS) allow us to identify all the silicates hydrates formed. Indeed, {sup 29}Si NMR is a valuable tool to determine the structure of crystallized or not-well crystallized phases of cement. The characterization of the hydrated samples is completed by other techniques: X- Ray Diffraction and Scanning Electron Microscopy. The following results are found: jaffeite is the most stable phase at C/S=3. To simulate the hydration of real cement, hydration of C{sub 3}S with ground quartz and with or without super-plasticizers is done. In those cases, new phases appear: kilchoanite mainly, and xonotlite. A large amount of

Synthesis and stability of α-tricalcium phosphate doped with dicalcium silicate in the system Ca3(PO4)2-Ca2SiO4

International Nuclear Information System (INIS)

Martinez, I.M.; Velasquez, P.A.; De Aza, P.N.

2010-01-01

The aim of this study was to synthesize materials of α-tricalcium phosphate doped with small amounts of dicalcium silicate, by solid state reaction, at high temperature and slow cooling to room temperature. The obtained materials were characterized by X-ray diffraction, Scanning Electron Microscopy and Fourier Transform Infrared Spectroscopy, showing that there is a region between 0.5 and 4.0 wt.% of dicalcium silicate where solid solution α-tricalcium phosphate (α-TCPss) is stable to room temperature.

Hydration behaviors of calcium silicate-based biomaterials.

Science.gov (United States)

Lee, Yuan-Ling; Wang, Wen-Hsi; Lin, Feng-Huie; Lin, Chun-Pin

2017-06-01

Calcium silicate (CS)-based biomaterials, such as mineral trioxide aggregate (MTA), have become the most popular and convincing material used in restorative endodontic treatments. However, the commercially available CS-based biomaterials all contain different minor additives, which may affect their hydration behaviors and material properties. The purpose of this study was to evaluate the hydration behavior of CS-based biomaterials with/without minor additives. A novel CS-based biomaterial with a simplified composition, without mineral oxides as minor additives, was produced. The characteristics of this biomaterial during hydration were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectrometry. The hydration behaviors of commercially available gray and white MTAs with mineral oxide as minor additives were also evaluated for reference. For all three test materials, the XRD analysis revealed similar diffraction patterns after hydration, but MTAs presented a significant decrease in the intensities of Bi 2 O 3 -related peaks. SEM results demonstrated similar porous microstructures with some hexagonal and facetted crystals on the outer surfaces. In addition, compared to CS with a simplified composition, the FTIR plot indicated that hydrated MTAs with mineral oxides were better for the polymerization of calcium silicate hydrate (CSH), presenting Si-O band shifting to higher wave numbers, and contained more water crystals within CSH, presenting sharper bands for O-H bending. Mineral oxides might not result in significant changes in the crystal phases or microstructures during the hydration of CS-based biomaterials, but these compounds affected the hydration behavior at the molecular level. Copyright © 2016. Published by Elsevier B.V.

Observation of microstructure of hydrated Ca3SiO5

International Nuclear Information System (INIS)

Mori, Kazuhiro; Sato, Takashi; Fukunaga, Toshiharu; Oishi, Koji; Kimura, Katsuhiko; Iwase, Kenji; Sugiyama, Masaaki; Itoh, Keiji; Shikanai, Fumihito; Wuernisha, Tuerxun; Yonemura, Masao; Sulistyanintyas, Dyah; Tsukushi, Itaru; Takata, Shinich; Otomo, Toshiya; Kamiyma, Takashi; Kawai, Masayoshi

2006-01-01

Quasi-elastic neutron scattering experiments were carried out to evaluate the hydration rate of tricalcium silicate (Ca 3 SiO 5 ). Furthermore, in the early hydration period, a variation in surface roughness of Ca 3 SiO 5 was observed in nano-scale by the small-angle neutron scattering. From these results, it was found that the hydration rate of Ca 3 SiO 5 is suppressed when the surface of Ca 3 SiO 5 becomes rough through the creation of hydration products C-S-H gel and Ca(OH) 2 , and this roughness is associated with changes in the Ca 3 SiO 5 hydration rate

Calcium and magnesium silicate hydrates

International Nuclear Information System (INIS)

Lothenbach, B.; L'Hopital, E.; Nied, D.; Achiedo, G.; Dauzeres, A.

2015-01-01

Deep geological disposals are planed to discard long-lived intermediate-level and high-level radioactive wastes. Clay-based geological barriers are expected to limit the ingress of groundwater and to reduce the mobility of radioelements. In the interaction zone between the cement and the clay based material alteration can occur. Magnesium silicate hydrates (M-S-H) have been observed due to the reaction of magnesium sulfate containing groundwater with cements or in the interaction zone between low-pH type cement and clays. M-S-H samples synthesized in the laboratory showed that M-S-H has a variable composition within 0.7 ≤ Mg/Si ≤ 1.5. TEM/EDS analyses show an homogeneous gel with no defined structure. IR and 29 Si NMR data reveal a higher polymerization degree of the silica network in M-S-H compared to calcium silicate hydrates (C-S-H). The presence of mainly Q 3 silicate tetrahedrons in M-S-H indicates a sheet like or a triple-chain silica structure while C-S-H is characterised by single chain-structure. The clear difference in the silica structure and the larger ionic radius of Ca 2+ (1.1 Angstrom) compared to Mg 2+ (0.8 Angstrom) make the formation of an extended solid solution between M-S-H and C-S-H gel improbable. In fact, the analyses of synthetic samples containing both magnesium and calcium in various ratios indicate the formation of separate M-S-H and C-S-H gels with no or very little uptake of magnesium in CS-H or calcium in M-S-H

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates

International Nuclear Information System (INIS)

Krishnan, N. M. Anoop; Wang, Bu; Falzone, Gabriel; Le Pape, Yann; Neithalath, Narayanan

2016-01-01

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development, and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C–S–H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C–S–H shows a sudden increase when the CaO/SiO_2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C–S–H’s nanostructure. We identify that confinement is dictated by the topology of the C–S–H’s atomic network. Altogether, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.

Confined Water in Layered Silicates: The Origin of Anomalous Thermal Expansion Behavior in Calcium-Silicate-Hydrates.

Science.gov (United States)

Krishnan, N M Anoop; Wang, Bu; Falzone, Gabriel; Le Pape, Yann; Neithalath, Narayanan; Pilon, Laurent; Bauchy, Mathieu; Sant, Gaurav

2016-12-28

Water, under conditions of nanoscale confinement, exhibits anomalous dynamics, and enhanced thermal deformations, which may be further enhanced when such water is in contact with hydrophilic surfaces. Such heightened thermal deformations of water could control the volume stability of hydrated materials containing nanoconfined structural water. Understanding and predicting the thermal deformation coefficient (TDC, often referred to as the CTE, coefficient of thermal expansion), which represents volume changes induced in materials under conditions of changing temperature, is of critical importance for hydrated solids including: hydrogels, biological tissues, and calcium silicate hydrates, as changes in their volume can result in stress development, and cracking. By pioneering atomistic simulations, we examine the physical origin of thermal expansion in calcium-silicate-hydrates (C-S-H), the binding agent in concrete that is formed by the reaction of cement with water. We report that the TDC of C-S-H shows a sudden increase when the CaO/SiO 2 (molar ratio; abbreviated as Ca/Si) exceeds 1.5. This anomalous behavior arises from a notable increase in the confinement of water contained in the C-S-H's nanostructure. We identify that confinement is dictated by the topology of the C-S-H's atomic network. Taken together, the results suggest that thermal deformations of hydrated silicates can be altered by inducing compositional changes, which in turn alter the atomic topology and the resultant volume stability of the solids.

Dispersion of Silicate in Tricalcium Phosphate Elucidated by Solid-State NMR

Energy Technology Data Exchange (ETDEWEB)

Rewal, A.; Wei, X.; Akinc, M.; Schmidt-Rohr, K.

2008-03-12

The dispersion of silicate in tricalcium phosphate, a resorbable bioceramics for bone replacement, has been investigated by various solid-state nuclear magnetic resonance (NMR) methods. In samples prepared with 5 and 10 mol% of both {sup 29}SiO{sub 2} and ZnO, three types of silicate have been detected: (i) SiO{sub 4}{sup 4-} (Q{sub 0} sites) with long longitudinal (T{sub 1,Si}) relaxation times ({approx} 10,000 s), which substitute for {approx}1% of PO{sub 4}{sup 3-}; (ii) silicate nanoinclusions containing Q{sub 2}, Q{sub 1}, and Q{sub 0} sites with T{sub 1,Si} 100 s, which account for most of the silicon; and (iii) crystalline Q{sub 4} (SiO{sub 2}) with long T{sub 1,Si}. Sensitivity was enhanced >100-fold by {sup 29}Si enrichment and refocused detection. The inclusions in both samples have a diameter of {approx}8 nm, as proved by {sup 29}Si{l_brace}{sup 31}P{r_brace} REDOR dephasing on a 30-ms time scale, which was simulated using a multispin approach specifically suited for nanoparticles. {sup 29}Si CODEX NMR with 30-s {sup 29}Si spin diffusion confirms that an inclusion contains >10 Si (consistent with the REDOR result of >100 Si per inclusion). Overlapping signals of silicate Q{sub 2}, Q{sub 1}, and Q{sub 0} sites were spectrally edited based on their J-couplings, using double-quantum filtering. The large inhomogeneous broadening of the Q{sub 2}, Q{sub 1}, and Q{sub 0} {sup 29}Si subspectra indicates that the nanoinclusions are amorphous.

Why alite stops hydrating below 80% relative humidity

International Nuclear Information System (INIS)

Flatt, Robert J.; Scherer, George W.; Bullard, Jeffrey W.

2011-01-01

It has been observed that the hydration of cement paste stops when the relative humidity drops below about 80%. A thermodynamic analysis shows that the capillary pressure exerted at that RH shifts the solubility of tricalcium silicate, so that it is in equilibrium with water. This is a reflection of the chemical shrinkage in this system: according to Le Chatelier's principle, since the volume of the products is less than that of the reactants, a negative (capillary) pressure opposes the reaction.

Suspension hydration of C3S [tricalcium silicate] at constant pH. II. Effect of previously formed hydrates and of additives

NARCIS (Netherlands)

McCurdy, K.G.; Stein, H.N.

1973-01-01

A retardation shown by the hydration of C3S at pH=11.5 can be prevented if before the addition of C3S there are present hydrate particles in the aqueous medium. These hydrate particles probably have the composition CSHn. This indicates a hydrate CSHn, precipitated from solution, as the retarding

Influence of aluminum hydroxide and lime on the hydration of tricalcium silicate

NARCIS (Netherlands)

de Jong, J.G.M.; Stein, H.N.; Stevels, J.M.

1968-01-01

The influence of amorphorous Al(OH)3 on the hydration of 3CaO.SiO2 in portland cement was studied with an isothermal calorimeter. The reaction mechanism was investigated qual. by x-ray diffraction, D.T.A., ir, and electron microscope methods and the course of Ca(OH)2 concn. was followed quant.

Influence of saline solution on hydration behavior of β-dicalcium silicate in comparison with biphasic calcium phosphate/hydroxyapatite bio-ceramics

Energy Technology Data Exchange (ETDEWEB)

Radwan, M.M., E-mail: mmahmoudradwan@yahoo.com [Ceramics Dept, National Research Centre, Cairo (Egypt); Abd El-Hamid, H.K. [Ceramics Dept, National Research Centre, Cairo (Egypt); Mohamed, A.F. [The Holding Company for Production of Vaccines, Sera and Drugs (EGYVAC) (Egypt)

2015-12-01

The influence of using saline solution as mixing and curing liquid on some characteristics of β-dicalcium silicate (β-C{sub 2}S) and biphasic compound tri-calcium phosphate/hydroxyapatite (TCP/HAp) bio-ceramics was investigated. β-C{sub 2}S (27–30 nm) was prepared by solid state reaction at 1450 °C, while biphasic compound TCP/HAp (7–15 nm) was synthesized from an aqueous solution of Ca(NO{sub 3}){sub 2}·4H{sub 2}O and (NH{sub 4}){sub 2}HPO{sub 4}·12H{sub 2}O by chemical precipitation method. Setting times, compressive strength, pH values, X-ray diffraction analysis, infrared spectroscopy, scanning electron microscopy (SEM) were investigated. The evaluation of cytotoxicity of both calcium silicate and biphasic compounds to human gingival fibroblasts was carried out. The use of saline solution as mixing and immersing liquid shortened the setting time for the two bio-cements. TCP/HAp did not show any mechanical strength but β-C{sub 2}S showed good strength values. Both synthesized compounds showed a moderate cytotoxicity and both materials were effective in a no significant way. - Highlights: • The dissolution and hydration of β-C{sub 2}S and TCP/HAp in distilled water and saline solution were studied. • TCP/HAp did not show mechanical strength, while β-C{sub 2}S showed good mechanical strength. • The use of saline solution did enhances the dissolution & hydration rate. • An increase in pH values was detected when using saline solution. • Both materials showed a moderate cytotoxicity in no significant way.

Hydration water and microstructure in calcium silicate and aluminate hydrates

International Nuclear Information System (INIS)

Fratini, Emiliano; Ridi, Francesca; Chen, Sow-Hsin; Baglioni, Piero

2006-01-01

Understanding the state of the hydration water and the microstructure development in a cement paste is likely to be the key for the improvement of its ultimate strength and durability. In order to distinguish and characterize the reacted and unreacted water, the single-particle dynamics of water molecules in hydrated calcium silicates (C 3 S, C 2 S) and aluminates (C 3 A, C 4 AF) were studied by quasi-elastic neutron scattering, QENS. The time evolution of the immobile fraction represents the hydration kinetics and the mobile fraction follows a non-Debye relaxation. Less sophisticated, but more accessible and cheaper techniques, like differential scanning calorimetry, DSC, and near-infrared spectroscopy, NIR, were validated through QENS results and they allow one to easily and quantitatively follow the cement hydration kinetics and can be widely applied on a laboratory scale to understand the effect of additives (i.e., superplasticizers, cellulosic derivatives, etc) on the thermodynamics of the hydration process. DSC provides information on the free water index and on the activation energy involved in the hydration process while the NIR band at 7000 cm -1 monitors, at a molecular level, the increase of the surface-interacting water. We report as an example the effect of two classes of additives widely used in the cement industry: superplasticizers, SPs, and cellulose derivatives. SPs interact at the solid surface, leading to a consistent increment of the activation energy for the processes of nucleation and growth of the hydrated phases. In contrast, the cellulosic additives do not affect the nucleation and growth activation energy, but cause a significant increment in the water availability: in other words the hydration process is more efficient without any modification of the solid/liquid interaction, as also evidenced by the 1 H-NMR. Additional information is obtained by scanning electron microscopy (SEM), ultra small angle neutron scattering (USANS) and wide

In Vitro Screening of the Apatite-Forming Ability, Biointeractivity and Physical Properties of a Tricalcium Silicate Material for Endodontics and Restorative Dentistry

Directory of Open Access Journals (Sweden)

Maria Giovanna Gandolfi

2013-12-01

Full Text Available Aim: Calcium silicate-based materials are hydraulic self-setting materials with physico-chemical properties suitable for endodontic surgery and good biological/clinical outcomes. The study aim was to evaluate the bio-properties (biointeractivity and apatite-forming ability and selected physical properties (porosity, water sorption, solubility, and setting time of Biodentine, a tricalcium silicate material for endodontics and restorative dentistry, compared to that of ProRoot MTA (Mineral Trioxide Aggregate as gold standard material. Methods: Biodentine and ProRoot MTA pastes were prepared and analyzed for calcium release and alkalinizing activity (3 h–28 days, setting time, water sorption, porosity, solubility, surface microstructure and composition, and apatite-forming ability in simulated body fluid. Results: Biodentine showed higher calcium release, alkalinizing activity, and solubility but higher open and apparent porosity, water sorption, and a markedly shorter setting time. Calcium phosphate (CaP deposits were noted on material surfaces after short ageing times. A CaP coating composed of spherulites was detected after 28 days. The thickness, continuity, and Ca/P ratio of the coating differed markedly between the materials. Biodentine showed a coating composed by denser but smaller spherulites, while ProRoot MTA showed large but less dense aggregates of spherulitic deposits. Conclusions: Biodentine showed a pronounced ability to release calcium and extended alkalinizing activity interlinked with its noticeable porosity, water sorption, and solubility: open porosities provide a broad wet biointeractive surface for the release of the calcium and hydroxyl ions involved in the formation of a CaP mineral. Biodentine is a biointeractive tricalcium silicate material with interesting chemical-physical properties and represents a fast-setting alternative to the conventional calcium silicate MTA-like cements.

Flow perfusion culture of human mesenchymal stem cells on silicate-substituted tricalcium phosphate scaffolds

DEFF Research Database (Denmark)

Bjerre, Lea; Bünger, Cody E; Kassem, Moustapha

2008-01-01

Autologous bone grafts are currently the gold standard for treatment of large bone defects, but their availability is limited due to donor site morbidity. Different substitutes have been suggested to replace these grafts, and this study presents a bone tissue engineered alternative using silicate......-substituted tricalcium phosphate (Si-TCP) scaffolds seeded with human bone marrow-derived mesenchymal stem cells (hMSC). The cells were seeded onto the scaffolds and cultured either statically or in a perfusion bioreactor for up to 21 days and assessed for osteogenic differentiation by alkaline phosphatase activity...... assays and by quantitative real-time RT-PCR on bone markers. During culture, cells from the flow cultured constructs demonstrated improved proliferation and osteogenic differentiation verified by a more pronounced expression of several bone markers, e.g. alkaline phosphatase, osteopontin, Runx2, bone...

Electronic structure calculations of calcium silicate hydrates

International Nuclear Information System (INIS)

Sterne, P.A.; Meike, A.

1995-11-01

Many phases in the calcium-silicate-hydrate system can develop in cement exposed over long periods of time to temperatures above 25 C. As a consequence, chemical reactions involving these phases can affect the relative humidity and water chemistry of a radioactive waste repository that contains significant amounts of cement. In order to predict and simulate these chemical reactions, the authors are developing an internally consistent database of crystalline Ca-Si-hydrate structures. The results of first principles electronic structure calculations on two such phases, wollastonite (CaSiO 3 ) and xonotlite (Ca 6 Si 6 O 17 (OH) 2 ), are reported here. The calculated ground state properties are in very good agreement with experiment, providing equilibrium lattice parameters within about 1--1.4% of the experimentally reported values. The roles of the different types of oxygen atoms, which are fundamental to understanding the energetics of crystalline Ca-Si-hydrates are briefly discussed in terms of their electronic state densities. The good agreement with experiment for the lattice parameters and the consistency of the electronic density of states features for the two structures demonstrate the applicability of these electronic structure methods in calculating the fundamental properties of these phases

Hydration characteristics and environmental friendly performance of a cementitious material composed of calcium silicate slag

Energy Technology Data Exchange (ETDEWEB)

Zhang, Na; Li, Hongxu [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Laboratory of Rare and Precious Metals Green Recycling and Extraction, University of Science and Technology Beijing, Beijing 100083 (China); Zhao, Yazhao [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Liu, Xiaoming, E-mail: liuxm@ustb.edu.cn [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Laboratory of Rare and Precious Metals Green Recycling and Extraction, University of Science and Technology Beijing, Beijing 100083 (China)

2016-04-05

Highlights: • Cementitious material was designed according to [SiO{sub 4}] polymerization degree of raw materials. • The cementitious material composed of calcium silicate slag yields excellent physical and mechanical properties. • Amorphous C–A–S–H gel and rod-like ettringite are predominantly responsible for the strength development. • Leaching toxicity and radioactivity tests show the cementitious material is environmentally acceptable. - Abstract: Calcium silicate slag is an alkali leaching waste generated during the process of extracting Al{sub 2}O{sub 3} from high-alumina fly ash. In this research, a cementitious material composed of calcium silicate slag was developed, and its mechanical and physical properties, hydration characteristics and environmental friendly performance were investigated. The results show that an optimal design for the cementitious material composed of calcium silicate slag was determined by the specimen CFSC7 containing 30% calcium silicate slag, 5% high-alumina fly ash, 24% blast furnace slag, 35% clinker and 6% FGD gypsum. This blended system yields excellent physical and mechanical properties, confirming the usefulness of CFSC7. The hydration products of CFSC7 are mostly amorphous C–A–S–H gel, rod-like ettringite and hexagonal-sheet Ca(OH){sub 2} with small amount of zeolite-like minerals such as CaAl{sub 2}Si{sub 2}O{sub 8}·4H{sub 2}O and Na{sub 2}Al{sub 2}Si{sub 2}O{sub 8}·H{sub 2}O. As the predominant hydration products, rod-like ettringite and amorphous C–A–S–H gel play a positive role in promoting densification of the paste structure, resulting in strength development of CFSC7 in the early hydration process. The leaching toxicity and radioactivity tests results indicate that the developed cementitious material composed of calcium silicate slag is environmentally acceptable. This study points out a promising direction for the proper utilization of calcium silicate slag in large quantities.

Push-out bond strength of different tricalcium silicate-based filling materials to root dentin

Directory of Open Access Journals (Sweden)

Jorge Henrique Stefaneli Marques

2018-03-01

Full Text Available Abstract: The aim of this study was to evaluate the bond strength of different triccalcium silicate cements to retrograde cavity using a push out test. Thirty maxillary central incisors were shaped using #80 hand files and sectioned transversally. Root slices were obtained from the apical 4 mm after eliminating the apical extremity. The specimens were embedded in acrylic resin and positioned at 45° to the horizontal plane for preparation of root-end cavities with a diamond ultrasonic retrotip. The samples were divided into three groups according to the root-end filling material (n = 10: MTA Angelus, ProRoot MTA and Biodentine. A gutta-percha cone (#80 was tugged-back at the limit between the canal and the root-end cavity. The root-end cavity was filled and the gutta-percha cone was removed after complete setting of the materials. The specimens were placed in an Instron machine with the root-end filling turned downwards. The push-out shaft was inserted in the space previously occupied by the gutta-percha cone and push out testing was performed at a crosshead speed of 1.0 mm/min. There was no statistically significant difference in resistance to push out by the materials tested (p > 0.01. MTA Angelus and ProRoot MTA showed predominantly mixed failure while Biodentine exhibited mixed and cohesive failures. The tricalcium silicate-based root-end filling materials showed similar bond strength retrograde cavity.

Push-out bond strength of different tricalcium silicate-based filling materials to root dentin.

Science.gov (United States)

Stefaneli Marques, Jorge Henrique; Silva-Sousa, Yara Teresinha Corrêa; Rached-Júnior, Fuad Jacob Abi; Macedo, Luciana Martins Domingues de; Mazzi-Chaves, Jardel Francisco; Camilleri, Josette; Sousa-Neto, Manoel Damião

2018-03-08

The aim of this study was to evaluate the bond strength of different triccalcium silicate cements to retrograde cavity using a push out test. Thirty maxillary central incisors were shaped using #80 hand files and sectioned transversally. Root slices were obtained from the apical 4 mm after eliminating the apical extremity. The specimens were embedded in acrylic resin and positioned at 45° to the horizontal plane for preparation of root-end cavities with a diamond ultrasonic retrotip. The samples were divided into three groups according to the root-end filling material (n = 10): MTA Angelus, ProRoot MTA and Biodentine. A gutta-percha cone (#80) was tugged-back at the limit between the canal and the root-end cavity. The root-end cavity was filled and the gutta-percha cone was removed after complete setting of the materials. The specimens were placed in an Instron machine with the root-end filling turned downwards. The push-out shaft was inserted in the space previously occupied by the gutta-percha cone and push out testing was performed at a crosshead speed of 1.0 mm/min. There was no statistically significant difference in resistance to push out by the materials tested (p > 0.01). MTA Angelus and ProRoot MTA showed predominantly mixed failure while Biodentine exhibited mixed and cohesive failures. The tricalcium silicate-based root-end filling materials showed similar bond strength retrograde cavity.

Calcium silicate-based sealers: Assessment of physicochemical properties, porosity and hydration.

Science.gov (United States)

Marciano, Marina Angélica; Duarte, Marco Antonio Hungaro; Camilleri, Josette

2016-02-01

Investigation of hydration, chemical, physical properties and porosity of experimental calcium silicate-based sealers. Experimental calcium silicate-based sealers with calcium tungstate and zirconium oxide radio-opacifiers were prepared by mixing 1g of powder to 0.3 mL of 80% distilled water and 20% propylene glycol. MTA and MTA Fillapex were used as controls. The raw materials and set sealers were characterized using a combination of scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Physical properties were analyzed according to ANSI/ADA. The pH and calcium ion release were assessed after 3, 24, 72 and 168 h. The porosity was assessed using mercury intrusion porosimetry. The analysis of hydration of prototype sealers revealed calcium hydroxide as a by-product resulting in alkaline pH and detection of calcium ion release, with high values in initial periods. The radiopacity was similar to MTA for the sealers containing high amounts of radio-opacifiers (p>0.05). Flowability was higher and film thickness was lower for resinous MTA Fillapex sealer (p0.05). The prototype sealers presented adequate hydration, elevated pH and calcium ion release. Regarding physical properties, elevated proportions of radio-opacifiers were necessary to accomplish adequate radiopacity, enhance flowability and reduce film thickness. All the tested sealers presented water sorption and porosity similar to MTA. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effect of temperature on the hydration of Portland cement blended with siliceous fly ash

Energy Technology Data Exchange (ETDEWEB)

Deschner, Florian, E-mail: florian.deschner@gmail.com [Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Concrete and Construction Chemistry, Überlandstrasse 129, 8600 Dübendorf (Switzerland); Lothenbach, Barbara; Winnefeld, Frank [Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Concrete and Construction Chemistry, Überlandstrasse 129, 8600 Dübendorf (Switzerland); Neubauer, Jürgen [GeoZentrum Nordbayern, Mineralogy, University of Erlangen-Nuremberg, 91054 Erlangen (Germany)

2013-10-15

The effect of temperature on the hydration of Portland cement pastes blended with 50 wt.% of siliceous fly ash is investigated within a temperature range of 7 to 80 °C. The elevation of temperature accelerates both the hydration of OPC and fly ash. Due to the enhanced pozzolanic reaction of the fly ash, the change of the composition of the C–S–H and the pore solution towards lower Ca and higher Al and Si concentrations is shifted towards earlier hydration times. Above 50 °C, the reaction of fly ash also contributes to the formation of siliceous hydrogarnet. At 80 °C, ettringite and AFm are destabilised and the released sulphate is partially incorporated into the C–S–H. The observed changes of the phase assemblage in dependence of the temperature are confirmed by thermodynamic modelling. The increasingly heterogeneous microstructure at elevated temperatures shows an increased density of the C–S–H and a higher coarse porosity. -- Highlights: •The reaction of quartz powder at 80 °C strongly enhances the compressive strength. •Almost no strength increase of fly ash blended OPC at 80 °C was found after 2 days. •Siliceous hydrogarnet is formed upon the reaction of fly ash at high temperatures. •Temperature dependent change of the system was simulated by thermodynamic modelling. •Destabilisation of ettringite above 50 °C correlates with sulphate content of C–S–H.

Effect of temperature on the hydration of Portland cement blended with siliceous fly ash

International Nuclear Information System (INIS)

Deschner, Florian; Lothenbach, Barbara; Winnefeld, Frank; Neubauer, Jürgen

2013-01-01

The effect of temperature on the hydration of Portland cement pastes blended with 50 wt.% of siliceous fly ash is investigated within a temperature range of 7 to 80 °C. The elevation of temperature accelerates both the hydration of OPC and fly ash. Due to the enhanced pozzolanic reaction of the fly ash, the change of the composition of the C–S–H and the pore solution towards lower Ca and higher Al and Si concentrations is shifted towards earlier hydration times. Above 50 °C, the reaction of fly ash also contributes to the formation of siliceous hydrogarnet. At 80 °C, ettringite and AFm are destabilised and the released sulphate is partially incorporated into the C–S–H. The observed changes of the phase assemblage in dependence of the temperature are confirmed by thermodynamic modelling. The increasingly heterogeneous microstructure at elevated temperatures shows an increased density of the C–S–H and a higher coarse porosity. -- Highlights: •The reaction of quartz powder at 80 °C strongly enhances the compressive strength. •Almost no strength increase of fly ash blended OPC at 80 °C was found after 2 days. •Siliceous hydrogarnet is formed upon the reaction of fly ash at high temperatures. •Temperature dependent change of the system was simulated by thermodynamic modelling. •Destabilisation of ettringite above 50 °C correlates with sulphate content of C–S–H

Effect of polymers on the nanostructure and on the carbonation of calcium silicate hydrates: a scanning transmission X-ray microscopy study

KAUST Repository

Ha, J.; Chae, S.; Chou, K. W.; Tyliszczak, T.; Monteiro, P. J. M.

2011-01-01

This study investigated the effects of organic polymers (polyethylene glycol and hexadecyltrimethylammonium) on structures of calcium silicate hydrates (C-S-H) which is the major product of Portland cement hydration. Increased surface areas

Discrete element modeling of calcium-silicate-hydrate

International Nuclear Information System (INIS)

Chandler, Mei Qiang; Peters, John F; Pelessone, Daniele

2013-01-01

The discrete element method (DEM) was used to model calcium-silicate-hydrate (C-S-H) at the nanoscale. The C-S-H nanoparticles were modeled as spherical particles with diameters of approximately 5 nm. Interparticle forces included traditional mechanical contact forces, van der Waals forces and ionic correlation forces due to negatively charged C-S-H nanoparticles and ion species in the nanopores. Previous work by the authors demonstrated the DEM method was feasible in studying the properties of the C-S-H nanostructures. In this work, the simulations were performed to look into the effects of nanoparticle packing, nanoparticle morphology, interparticle forces and nanoparticle properties on the deformation mechanisms and mechanical properties of the C-S-H matrix. This work will provide insights into possible ways to improve the properties of the C-S-H matrix. (paper)

Development of Magnesium Silicate Hydrate cement system for nuclear waste encapsulation

International Nuclear Information System (INIS)

Zhang, T.; Vandeperre, L.J.; Cheeseman, C.R.

2012-01-01

A novel low pH cement system for encapsulating nuclear industry wastes containing aluminium has been developed using blends of MgO and silica fume (SF). Identification of the hydrated phases in MgO/silica fume samples showed that brucite formed in early stages of hydration and then reacted with the silica fume to produce a magnesium silicate hydrate (M-S-H) gel phase. When all brucite reacts with silica fume a cement system with an equilibrium pH just below 10 was achieved. Selected mixes have been characterized for hydration reactions, setting time and strength development. Mortar samples with w/s ratios of 0.5 and 50% by weight of sand added achieved compressive strengths in excess of 95 MPa after 28 days. The addition of MgCO 3 buffered the early pH and the addition of fine sand particles eliminated shrinkage cracking. The interaction of the optimised mortar with Al metal has been investigated. Al metal strips were firmly bound into the MgO:SF:sand samples and no H 2 gas detected, and this indicates that the novel systems developed in this work have potential for encapsulating certain types of problematic legacy wastes from the nuclear industry. (authors)

Formation of magnesium silicate hydrate (M-S-H) cement pastes using sodium hexametaphosphate

Energy Technology Data Exchange (ETDEWEB)

Zhang, Tingting [Faculty of Infrastructure Engineering, Dalian University of Technology, Dalian 116024 (China); Department of Materials, Centre for Advanced Structural Ceramics, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Department of Civil and Environmental Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Vandeperre, Luc J. [Department of Materials, Centre for Advanced Structural Ceramics, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom); Cheeseman, Christopher R., E-mail: c.cheeseman@imperial.ac.uk [Department of Civil and Environmental Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ (United Kingdom)

2014-11-15

Magnesium silicate hydrate (M-S-H) gel is formed by the reaction of brucite with amorphous silica during sulphate attack in concrete and M-S-H is therefore regarded as having limited cementing properties. The aim of this work was to form M-S-H pastes, characterise the hydration reactions and assess the resulting properties. It is shown that M-S-H pastes can be prepared by reacting magnesium oxide (MgO) and silica fume (SF) at low water to solid ratio using sodium hexametaphosphate (NaHMP) as a dispersant. Characterisation of the hydration reactions by x-ray diffraction and thermogravimetric analysis shows that brucite and M-S-H gel are formed and that for samples containing 60 wt.% SF and 40 wt.% MgO all of the brucites react with SF to form M-S-H gel. These M-S-H cement pastes were found to have compressive strengths in excess of 70 MPa.

Structural and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from alite hydration in the presence of sodium and potassium hydroxide

International Nuclear Information System (INIS)

Mendoza, Oscar; Giraldo, Carolina; Camargo, Sergio S.; Tobón, Jorge I.

2015-01-01

This research evaluates the effect of sodium and potassium hydroxide on the structure and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from the hydration of pure alite. Monoclinic (MIII) alite was synthesized and hydrated, using water-to-alite ratios of 0.5 and 0.6 and additions of 10% NaOH and KOH by weight of alite. Based on results of X-ray diffraction, isothermal calorimetry, thermogravimetric analysis, Nuclear Magnetic Resonance and nanoindentation, two different effects of the alkaline hydroxides on the hydration reaction of alite, both at early and later ages, can be identified: (i) a differentiated hydration process, attributed to an enhancement in calcium hydroxide (CH) precipitation and a stimulation of the C-S-H nuclei; and (ii) an increase in the elastic modulus of the C-S-H aggregations, attributed to an electrostatic attraction between positive charges from the alkaline cations and negative charges from the C-S-H structure

Structural and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from alite hydration in the presence of sodium and potassium hydroxide

Energy Technology Data Exchange (ETDEWEB)

Mendoza, Oscar, E-mail: oamendoz@unal.edu.co [Grupo del Cemento y Materiales de Construcción (CEMATCO). Universidad Nacional de Colombia, Facultad de Minas, Medellín (Colombia); Giraldo, Carolina [Cementos Argos S.A., Medellín (Colombia); Camargo, Sergio S. [Engenharia Metalúrgica e de Materiais, Universidade Federal do Rio de Janeiro/COPPE, Rio de Janeiro (Brazil); Tobón, Jorge I. [Grupo del Cemento y Materiales de Construcción (CEMATCO). Universidad Nacional de Colombia, Facultad de Minas, Medellín (Colombia)

2015-08-15

This research evaluates the effect of sodium and potassium hydroxide on the structure and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from the hydration of pure alite. Monoclinic (MIII) alite was synthesized and hydrated, using water-to-alite ratios of 0.5 and 0.6 and additions of 10% NaOH and KOH by weight of alite. Based on results of X-ray diffraction, isothermal calorimetry, thermogravimetric analysis, Nuclear Magnetic Resonance and nanoindentation, two different effects of the alkaline hydroxides on the hydration reaction of alite, both at early and later ages, can be identified: (i) a differentiated hydration process, attributed to an enhancement in calcium hydroxide (CH) precipitation and a stimulation of the C-S-H nuclei; and (ii) an increase in the elastic modulus of the C-S-H aggregations, attributed to an electrostatic attraction between positive charges from the alkaline cations and negative charges from the C-S-H structure.

Heavy ion beam measurement of the hydration of cementitious materials

International Nuclear Information System (INIS)

Livingston, R.A.; Schweitzer, J.S.; Spillane, T.; Zickefoose, J.; Rolfs, C.; Becker, H.-W.; Kubsky, S.; Castellote, M.; Viedma, P.G. de; Cheung, J.

2008-01-01

Full text: The setting and development of strength of Portland cement concrete depends upon the reaction of water with various phases in the Portland cement including dicalcium silicate (C 2 S), tricalcium silicate (C 3 S) and tricalcium aluminate (C 3 A). The early age hydration reaction and setting time are determined by surface layers on the cement grains that form a region that is only a few 100 nm thick. This has been difficult to observe with conventional methods. Ion beam techniques have been used to investigate these layers in detail at the Tandem Accelerator facility of the University of the Ruhr in Bochum, Germany. The primary method has been Nuclear Resonance Reaction Analysis (NRRA) involving the 1 H( 15 N,αγ) 12 C reaction to measure the hydrogen depth profile. This technique has an H detection sensitivity of about 10 ppm and an H-depth resolution of a few nm at the surface.. Freshly cleaved mica is used as a calibration standard for conversion of gamma-ray counts to H concentration. The beam energy to depth conversion factor is obtained by numerical simulation using the Monte Carlo code TRIM. NRRA with the 1 H( 19 F, αγ) 16 O reaction has also been used to measure the hydrogen depth profile. Some samples were implanted with a 131 Xe layer in order to measure the depth profile of other significant elements such as calcium with Rutherford Backscattering (RBS), and also to measure the erosion of the surface layers

Zinc incorporation improves biological activity of beta-tricalcium silicate resin-based cement.

Science.gov (United States)

Osorio, Raquel; Yamauti, Monica; Sauro, Salvatore; Watson, Tim F; Toledano, Manuel

2014-11-01

Matrix metalloproteinase (MMP) inhibition may improve endodontic treatment prognosis. The purpose of this study was to determine if zinc incorporation into experimental resin cements containing bioactive fillers may modulate MMP-mediated collagen degradation of dentin. Human dentin samples untreated and demineralized using 10% phosphoric acid or 0.5 mol/L EDTA were infiltrated with the following experimental resins: (1) unfilled resin, (2) resin with Bioglass 45S5 particles (OSspray, London, UK), (3) resin with beta-tricalcium silicate particles (βTCS), (4) resin with zinc-doped Bioglass 45S5, and (5) resin with zinc-doped βTCS particles. The specimens were stored in artificial saliva (for 24 hours, 1 week, and 4 weeks) and submitted to radioimmunoassay to quantify C-terminal telopeptide. Scanning electron microscopy analysis was also undertaken on dentin samples after 4 weeks of storage. Collagen degradation was prominent both in phosphoric acid and EDTA-treated dentin. Resin infiltration strongly reduced MMP activity in demineralized dentin. Resin containing Bioglass 45S5 particles exerted higher and stable protection of collagen. The presence of zinc in βTCS particles increases MMP inhibition. Different mineral precipitation was attained in dentin infiltrated with the resin cements containing bioactive fillers. MMP degradation of dentin collagen is strongly reduced after resin infiltration of dentin. Zinc incorporation in βTCS particles exerted an additional protection against MMP-mediated collagen degradation. However, it did not occur in resin containing Bioglass 45S5 particles, probably because of the formation of phosphate-zinc compounds. Copyright © 2014 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

The effect of mixing method on tricalcium silicate-based cement.

Science.gov (United States)

Duque, J A; Fernandes, S L; Bubola, J P; Duarte, M A H; Camilleri, J; Marciano, M A

2018-01-01

To evaluate the effect of three methods of mixing on the physical and chemical properties of tricalcium silicate-based cements. The materials evaluated were MTA Angelus and Portland cement with 20% zirconium oxide (PC-20-Zr). The cements were mixed using a 3 : 1 powder-to-liquid ratio. The mixing methods were manual (m), trituration (tr) and ultrasonic (us) activation. The materials were characterized by means of scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy. Flowability was analysed according to ANSI/ADA 57/2012. Initial and final setting times were assessed following ASTM C266/08. Volume change was evaluated using a micro-CT volumetric method. Solubility was analysed according to ADA 57/2012. pH and calcium ion release were measured after 3, 24, 72 and 168 h. Statistical analysis was performed using two-way analysis of variance. The level of significance was set at P = 0.05. The SEM analysis revealed that ultrasonic activation was associated with a homogeneous distribution of particles. Flowability, volume change and initial setting time were not influenced by the mixing method (P > 0.05). Solubility was influenced by the mixing method (P < 0.05). For pH, at 168 h, significant differences were found between MTA-m and PC-20-Zr-m (P < 0.05). For calcium ion release, PC-20-Zr-tr had higher values than MTA-m at 3 h, and MTA-tr had higher values than PC-20-Zr-m at 168 h (P < 0.05). The ultrasonic and trituration methods led to higher calcium ion release and pH compared with manual mixing for all cements, whilst the ultrasonic method produced smaller particles for the PC-20-Zr cement. Flow, setting times and volume change were not influenced by the mixing method used; however, it did have an impact on solubility. © 2017 International Endodontic Journal. Published by John Wiley & Sons Ltd.

Swelling behavior of ion exchange resins incorporated in tri-calcium silicate cement matrix: I. Chemical analysis

International Nuclear Information System (INIS)

Neji, M.; Bary, B.; Le Bescop, P.; Burlion, N.

2015-01-01

This paper presents the first part of a theoretical and experimental work aiming at modeling the chemo-mechanical behavior of composites made up of ion exchange resins (IER) solidified in a tri-calcium silicate cement paste (C_3S). Because of ion exchange processes, the volume change of the IER may cause internal pressures leading to the degradation of the material. In this study, a predictive modeling is developed for describing the chemical behavior of such material. It is based on thermodynamic equilibria to determine the evolution of the ion exchange processes, and the potential precipitation of portlandite in the composite. In parallel, a phenomenological study has been set up to understand chemical phenomena related to the swelling mechanisms. The model created has been finally implemented in a finite elements software; the simulation of a laboratory test has been performed and the results compared to experimental data. - Highlights: • Ion exchange theory to model the swelling behavior of Ion exchange resin. • Experimental phenomenon analysis about Chemo-mechanical interaction between IER and cement paste matrix. • Chemo-Transport modeling on a composite material made with IER embedded into cement paste matrix.

Swelling behavior of ion exchange resins incorporated in tri-calcium silicate cement matrix: II. Mechanical analysis

International Nuclear Information System (INIS)

Neji, M.; Bary, B.; Le Bescop, P.; Burlion, N.

2015-01-01

This paper presents the second part of a study aiming at modelling the mechanical behavior of composites made up of ion exchange resins (IER) solidified in a tri-calcium silicate cement paste (C_3S). Such composites may be subjected to internal pressures due to ion exchange processes between ionic species which are in IER and interstitial solution of the cement paste. The reactive transport model developed in the companion paper is coupled in this study to a multi-scale approach describing the mechanical behavior of the material. It is based on an analogy with thermomechanics for taking in account the IER internal pressures, and on Eshelby-based homogenization techniques to estimate both mechanical and coupling parameters. A laboratory test has been set up to measure the macroscopic strain caused by the swelling phenomenon. The model has been finally implemented in a finite elements software. The simulation of the laboratory tests has been performed and the results have been analyzed and compared to experimental data. - Highlights: • Experimental analysis about mechanical behavior of a composite material. • Chemo-Mechanical-Transport modeling on a composite material made up with IER embedded into cement paste matrix. • Multi-scale modeling.

Synthesis of pure Portland cement phases

DEFF Research Database (Denmark)

Wesselsky, Andreas; Jensen, Ole Mejlhede

2009-01-01

Pure phases commonly found in Portland cement clinkers are often used to test cement hydration behaviour in simplified experimental conditions. The synthesis of these phases is covered in this paper, starting with a description of phase relations and possible polymorphs of the four main phases...... in Portland cement, i.e. tricalcium silicate, dicalcium silicate, tricalcium aluminate and tetracalcium alumino ferrite. Details of the The process of solid state synthesis are is described in general including practical advice on equipment and techniques. Finally In addition, some exemplary mix compositions...

Portland cement hydration and early setting of cement stone intended for efficient paving materials

Science.gov (United States)

Grishina, A.

2017-10-01

Due to the growth of load on automotive roads, modern transportation engineering is in need of efficient paving materials. Runways and most advanced highways require Portland cement concretes. This makes important the studies directed to improvement of binders for such concretes. In the present work some peculiarities of the process of Portland cement hydration and early setting of cement stone with barium hydrosilicate sol were examined. It was found that the admixture of said sol leads to a shift in the induction period to later times without significant change in its duration. The admixture of a modifier with nanoscale barium hydrosilicates increases the degree of hydration of the cement clinker minerals and changes the phase composition of the hydration products; in particular, the content of portlandite and tricalcium silicate decreases, while the amount of ettringite increases. Changes in the hydration processes of Portland cement and early setting of cement stone that are caused by the nanoscale barium hydrosilicates, allow to forecast positive technological effects both at the stage of manufacturing and at the stage of operation. In particular, the formwork age can be reduced, turnover of molds can be increased, formation of secondary ettringite and corrosion of the first type can be eliminated.

Activation of Ca(OH){sub 2} using different siliceous materials

Energy Technology Data Exchange (ETDEWEB)

Karatepe, N.; Ersoy-Mericboyu, A.; Kucukbayrak, S. [Istanbul Technical University, Istanbul (Turkey)

1999-04-01

Siliceous materials such as silica fume, bentonite and diatomite were mixed with Ca(OH){sub 2} and hydrated at different conditions to produce reactive SO{sub 2} sorbents. Two different hydration methods were used, namely atmospheric and pressure hydration. The effects of the hydration temperature, time and siliceous material/Ca(OH){sub 2} weight ratio on the physical properties of the activated sorbents wereinvestigated. A statistical design technique was applied by use of a two-level factorial design matrix to interpret experimental results. In atmospheric hydration, it was found that increasing the temperature and hydration time caused an increase in the total surface area of the sorbents. But, increasing the siliceous material/Ca(OH){sub 2} weight ratio caused a decrease in the total surface area of the sorbents. In pressure hydration, mathematical analysis showed that the surface area of the activated sorbents was positively affected by the hydration variables. Thermogravimetric measurements showed that increasing the amount of reacted Ca(OH){sub 2} during hydration caused an increase in the surface area of the sorbent. X-ray diffraction studies also indicated that calcium silicate hydrates were the principal Ca-containing species formed during hydration.

Total allowable concentrations of monomeric inorganic aluminum and hydrated aluminum silicates in drinking water.

Science.gov (United States)

Willhite, Calvin C; Ball, Gwendolyn L; McLellan, Clifton J

2012-05-01

Maximum contaminant levels are used to control potential health hazards posed by chemicals in drinking water, but no primary national or international limits for aluminum (Al) have been adopted. Given the differences in toxicological profiles, the present evaluation derives total allowable concentrations for certain water-soluble inorganic Al compounds (including chloride, hydroxide, oxide, phosphate and sulfate) and for the hydrated Al silicates (including attapulgite, bentonite/montmorillonite, illite, kaolinite) in drinking water. The chemistry, toxicology and clinical experience with Al materials are extensive and depend upon the particular physical and chemical form. In general, the water solubility of the monomeric Al materials depends on pH and their water solubility and gastrointestinal bioavailability are much greater than that of the hydrated Al silicates. Other than Al-containing antacids and buffered aspirin, food is the primary source of Al exposure for most healthy people. Systemic uptake of Al after ingestion of the monomeric salts is somewhat greater from drinking water (0.28%) than from food (0.1%). Once absorbed, Al accumulates in bone, brain, liver and kidney, with bone as the major site for Al deposition in humans. Oral Al hydroxide is used routinely to bind phosphate salts in the gut to control hyperphosphatemia in people with compromised renal function. Signs of chronic Al toxicity in the musculoskeletal system include a vitamin D-resistant osteomalacia (deranged membranous bone formation characterized by accumulation of the osteoid matrix and reduced mineralization, reduced numbers of osteoblasts and osteoclasts, decreased lamellar and osteoid bands with elevated Al concentrations) presenting as bone pain and proximal myopathy. Aluminum-induced bone disease can progress to stress fractures of the ribs, femur, vertebrae, humerus and metatarsals. Serum Al ≥100 µg/L has a 75-88% positive predictive value for Al bone disease. Chronic Al

NON-AUTOCLAVE SILICATE BRICK

Directory of Open Access Journals (Sweden)

V. N. Yaglov

2015-01-01

Full Text Available The paper proposes a technology for obtaining bricks on the basis of lime-silica mixtures where chemical interactions are practically completely realized in dispersive state at the stage of preparation of binding contact maturing and raw mixture as a whole. The role of forming operation (moulding is changed in principle because in this case conversion of dispersive system into a rock-like solid occurs and due to this the solid obtains complete water-resistance in contact with water immediately after forming operation. Theoretical basis for the developed technology is capability of silicate dispersive substances (hydrated calcium silicate to transit in non-stable state, to form a rock-like water-resistant solid in the moment of mechanical load application during forming process. Specific feature of the proposed method is an exclusion of additional operations for autoclaving of products from the process of obtaining a silicate brick.Synthetic hydrated calcium silicate in contrast to natural ones are more uniform in composition and structure, they contain less impurities and they are characterized by dispersive composition and due to the mentioned advantages they find wider practical application. Contact-condensation binders permit to manipulate product properties on their basis and ensure maximum correspondence to the requirements of the concrete application. Raw material sources for obtaining synthetic hydrated calcium silicates are practically un-limited because calcium-silicon containing substances are found as in various technogenic wastes so in natural compounds as well. So the problem for obtaining hydrated calcium silicates having contact-condensation ability for structure formation becomes more and more actual one. This transition is considered as dependent principally on arrangement rate of substance particles which determined the level of its instability.

Pore solution in alkali-activated slag cement pastes. Relation to the composition and structure of calcium silicate hydrate

International Nuclear Information System (INIS)

Puertas, F.; Fernandez-Jimenez, A.; Blanco-Varela, M.T.

2004-01-01

In this work, the relationship between the composition of pore solution in alkali-activated slag cement (AAS) pastes activated with different alkaline activator, and the composition and structure of the main reaction products, has been studied. Pore solution was extracted from hardened AAS pastes. The analysis of the liquids was performed through different techniques: Na, Mg and Al by atomic absorption (AA), Ca ions by ionic chromatography (IC) and Si by colorimetry; pH was also determined. The solid phases were analysed by XRD, FTIR, solid-state 29 Si and 27 Al NMR and BSE/EDX. The most significant changes in the ionic composition of the pore solution of the AAS pastes activated with waterglass take place between 3 and 24 h of reaction. These changes are due to the decrease of the Na content and mainly to the Si content. Results of 29 Si MAS NMR and FTIR confirm that the activation process takes place with more intensity after 3 h (although at this age, Q 2 units already exist). The pore solution of the AAS pastes activated with NaOH shows a different evolution to this of pastes activated with waterglass. The decrease of Na and Si contents progresses with time. The nature of the alkaline activator influences the structure and composition of the calcium silicate hydrate formed as a consequence of the alkaline activation of the slag. The characteristic of calcium silicate hydrate in AAS pastes activated with waterglass is characterised by a low structural order with a low Ca/Si ratio. Besides, in this paste, Q 3 units are detected. The calcium silicate hydrate formed in the pastes activated with NaOH has a higher structural order (higher crystallinity) and contains more Al in its structure and a higher Ca/Si ratio than those obtained with waterglass

X-ray spectra and theoretical elastic properties of crystalline calcium silicate hydrates: comparison with cement hydrated gels

Directory of Open Access Journals (Sweden)

Ayuela, A.

2010-09-01

Full Text Available For 22 crystalline Calcium Silicates Hydrates, we have calculated their structure and their elastic properties by atomistic force field methods as well as simulate their Xray diffraction patterns. From the computed Young moduli, it can be suggested that the key parameters to determine the elastic properties of crystalline Calcium Silicate Hydrates are densities and water content. We have compared these trends with those of cementitious C-S-H gel and synthetic C-S-H type I as a function of their C/S ratios and nominal water content. Our comparison show that the experimentally suggested values of density and Young moduli for C-S-H gel lie in the range of the calculated CSH crystals. However, we conclude that a detailed correspondence might require investigating structurally within CSH gels the role of water and especially of Ca and Si sites through their C/S ratio.

En este trabajo se han calculado para 22 Silicatos Cálcicos Hidratados cristalinos, su estructura y sus propiedades elásticas mediante métodos atomísticos “force field”, así como simulado sus espectros de difracción de rayos X. De los módulos de Young calculados se puede deducir, que los parámetros clave que determinan las propiedades elásticas de los Silicatos Cálcicos Hidratados cristalinos son la densidad y el contenido en agua. Nuestros resultados muestran que los valores experimentales de la densidad y de los módulos de Young para el gel C-S-H están dentro del rango de los cristales de CSH calculados. Sin embargo, podemos concluir que para establecer una correlación más directa sería necesario investigar el papel que juegan el agua y sobre todo el Ca y Si, mediante la relación C/S, en la estructura del gel CSH.

Densification of the interlayer spacing governs the nanomechanical properties of calcium-silicate-hydrate.

Science.gov (United States)

Geng, Guoqing; Myers, Rupert J; Qomi, Mohammad Javad Abdolhosseini; Monteiro, Paulo J M

2017-09-08

Calciuam-silicate-hydrate (C-S-H) is the principal binding phase in modern concrete. Molecular simulations imply that its nanoscale stiffness is 'defect-driven', i.e., dominated by crystallographic defects such as bridging site vacancies in its silicate chains. However, experimental validation of this result is difficult due to the hierarchically porous nature of C-S-H down to nanometers. Here, we integrate high pressure X-ray diffraction and atomistic simulations to correlate the anisotropic deformation of nanocrystalline C-S-H to its atomic-scale structure, which is changed by varying the Ca-to-Si molar ratio. Contrary to the 'defect-driven' hypothesis, we clearly observe stiffening of C-S-H with increasing Ca/Si in the range 0.8 ≤ Ca/Si ≤ 1.3, despite increasing numbers of vacancies in its silicate chains. The deformation of these chains along the b-axis occurs mainly through tilting of the Si-O-Si dihedral angle rather than shortening of the Si-O bond, and consequently there is no correlation between the incompressibilities of the a- and b-axes and the Ca/Si. On the contrary, the intrinsic stiffness of C-S-H solid is inversely correlated with the thickness of its interlayer space. This work provides direct experimental evidence to conduct more realistic modelling of C-S-H-based cementitious material.

A novel sol-gel-derived calcium silicate cement with short setting time for application in endodontic repair of perforations.

Science.gov (United States)

Lee, Bor-Shiunn; Lin, Hong-Ping; Chan, Jerry Chun-Chung; Wang, Wei-Chuan; Hung, Ping-Hsuan; Tsai, Yu-Hsin; Lee, Yuan-Ling

2018-01-01

Mineral trioxide aggregate (MTA) is the most frequently used repair material in endodontics, but the long setting time and reduced mechanical strength in acidic environments are major shortcomings. In this study, a novel sol-gel-derived calcium silicate cement (sCSC) was developed using an initial Ca/Si molar ratio of 3, with the most effective mixing orders of reactants and optimal HNO 3 catalyst volumes. A Fourier transform infrared spectrometer, scanning electron microscope with energy-dispersive X-ray spectroscopy, and X-ray powder diffractometer were used for material characterization. The setting time, compressive strength, and microhardness of sCSC after hydration in neutral and pH 5 environments were compared with that of MTA. Results showed that sCSC demonstrated porous microstructures with a setting time of ~30 min, and the major components of sCSC were tricalcium silicate, dicalcium silicate, and calcium oxide. The optimal formula of sCSC was sn200, which exhibited significantly higher compressive strength and microhardness than MTA, irrespective of neutral or pH 5 environments. In addition, both sn200 and MTA demonstrated good biocompatibility because cell viability was similar to that of the control. These findings suggest that sn200 merits further clinical study for potential application in endodontic repair of perforations.

Effect of sodium carbonate solution on self-setting properties of tricalcium silicate bone cement.

Science.gov (United States)

Zhiguang Huan; Jiang Chang

2008-11-01

In this study, the effects of sodium carbonate (Na(2)CO(3) ) solution with different concentrations (10, 15, 20, and 25 wt%) as liquid phase on the setting time and compressive strength of tricalcium silicate bone cements are investigated. The in vitro bioactivity and degradability of the resultant Ca(3)SiO(5)-Na(2)CO(3) solution paste was also studied. The results indicate that as the concentration of Na(2)CO(3) solution varies from 0 to 25 wt%, the initial and final setting time of the cement decrease significantly from 90 to 20 min and from 180 to 45 min, respectively. After setting for 24 h, the compressive strength of Ca(3)SiO(5)-Na(2)CO(3) solution paste reaches 5.1 MPa, which is significantly higher than that of Ca( 3)SiO(5)-water cement system. The in vitro bioactivity of the cements is investigated by soaking in simulated body fluid (SBF) for 7 days. The results show that the Ca(3)SiO(5)-Na(2)CO( 3) solution bone cement has a good bioactivity and can degrade in Ringer's solution. The results indicate that Na(2)CO(3) solution as a liquid phase significantly improves the self-setting properties of Ca( 3)SiO(5) cement as compared to water. The Ca(3)SiO( 5) cement paste prepared using Na(2)CO(3) solution shows good bioactivity and moderate degradability, and the Ca(3)SiO( 5)-Na(2)CO(3) solution system may be used as degradable and bioactive bone defect filling materials.

Fractionation and solubility of cadmium in paddy soils amended with porous hydrated calcium silicate.

Science.gov (United States)

Zhao, Xiu-Lan; Masaihiko, Saigusa

2007-01-01

Previous studies have shown that porous hydrated calcium silicate (PS) is very effective in decreasing cadmium (Cd) content in brown rice. However, it is unclear whether the PS influences cadmium transformation in soil. The present study examined the effect of PS on pH, cadmium transformation and cadmium solubility in Andosol and Alluvial soil, and also compared its effects with CaCO3, acidic porous hydrated calcium silicate (APS) and silica gel. Soil cadmium was operationally fractionationed into exchangeable (Exch), bound to carbonates (Carb), bound to iron and manganese oxides (FeMnO(x)), bound to organic matters (OM) and residual (Res) fraction. Application of PS and CaCO3 at hig rates enhanced soil pH, while APS and silica gel did not obviously change soil pH. PS and CaCO3 also increased the FeMnO(x)-Cd in Andosol and Carb-Cd in Alluvial soil, thus reducing the Exch-Cd in the tested soils. However, PS was less effective than CaCO3 at the same application rate. Cadmium fractions in the two soils were not changed by the treatments of APS and silica gel. There were no obvious differences in the solubility of cadmium in soils treated with PS, APS, silica gel and CaCO3 except Andosol treated 2.0% CaCO3 at the same pH of soil-CaCl2 suspensions. These findings suggested that the decrease of cadmium availability in soil was mainly attributed to the increase of soil pH caused by PS.

Structural study and crystallography of the major compound of anhydrous cement: tri-calcium silicate; Etude structurale et cristallographie du compose majoritaire du ciment anhydre: le silicate tricalcique

Energy Technology Data Exchange (ETDEWEB)

Noirfontaine, M.N. de

2000-01-01

Anhydrous (Portland) cement is mainly composed of a synthetic material, the clinker, whose major compound is tri-calcium silicate (Ca{sub 3}SiO{sub 5}), often referred as C{sub 3}S with the compact oxides notations, C = CaO et S = SiO{sub 2}. The polymorphism of C{sub 3}S, still not well known, is the main subject of the thesis. Various crystal structures (rhombohedral R, monoclinic M1, M2, M3 and triclinic T1, T2, T3) can be found, depending on temperature and impurities. The only known structures are T1, M1 and M3, involving large unit cells with an orientational disorder of silicate tetrahedra. The single crystal studies exhibit no clear relation between the various polymorphs. Starting from known results from literature single crystal experiments, we establish the metric and structural relations between the different structures. Averaged structures for the T1, M1 and M3 polymorphs are proposed, together with all the matrices of transformation between the unit cells. We also introduce new 1-D, 2-D, and 3-D structural units, which make easier the understanding of the structures of C{sub 3}S, with the result of a better description of the orientational disorder. The effects of impurities on the structure are discussed. In industrial clinkers, impurities stabilize mainly M1 and M3 monoclinic forms. We propose a space group (Pc) and two structural models (a superstructure and an approximate averaged structure) for the M1 form. All the models are validated on synthetic compounds (M3, M2, M1 et T1) and industrial clinkers analysed by X-Ray powder diffraction with Rietveld analysis. (author)

Mechanical behavior of a composite interface: Calcium-silicate-hydrates

Energy Technology Data Exchange (ETDEWEB)

Palkovic, Steven D.; Moeini, Sina; Büyüköztürk, Oral, E-mail: obuyuk@mit.edu [Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Yip, Sidney [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

2015-07-21

The generalized stacking fault (GSF) is a conceptual procedure historically used to assess shear behavior of defect-free crystalline structures through molecular dynamics or density functional theory simulations. We apply the GSF technique to the spatially and chemically complex quasi-layered structure of calcium-silicate-hydrates (C-S-H), the fundamental nanoscale binder within cementitious materials. A failure plane is enforced to calculate the shear traction-displacement response along a composite interface containing highly confined water molecules, hydroxyl groups, and calcium ions. GSF simulations are compared with affine (homogeneous) shear simulations, which allow strain to localize naturally in response to the local atomic environment. Comparison of strength and deformation behavior for the two loading methods shows the composite interface controls bulk shear deformation. Both models indicate the maximum shear strength of C-S-H exhibits a normal-stress dependency typical of cohesive-frictional materials. These findings suggest the applicability of GSF techniques to inhomogeneous structures and bonding environments, including other layered systems such as biological materials containing organic and inorganic interfaces.

Hydration of dicalcium silicate and diffusion through neo-formed calcium-silicate-hydrates at weathered surfaces control the long-term leaching behaviour of basic oxygen furnace (BOF) steelmaking slag.

Science.gov (United States)

Stewart, Douglas I; Bray, Andrew W; Udoma, Gideon; Hobson, Andrew J; Mayes, William M; Rogerson, Mike; Burke, Ian T

2018-04-01

Alkalinity generation and toxic trace metal (such as vanadium) leaching from basic oxygen furnace (BOF) steel slag particles must be properly understood and managed by pre-conditioning if beneficial reuse of slag is to be maximised. Water leaching under aerated conditions was investigated using fresh BOF slag at three different particle sizes (0.5-1.0, 2-5 and 10 × 10 × 20 mm blocks) and a 6-month pre-weathered block. There were several distinct leaching stages observed over time associated with different phases controlling the solution chemistry: (1) free-lime (CaO) dissolution (days 0-2); (2) dicalcium silicate (Ca 2 SiO 4 ) dissolution (days 2-14) and (3) Ca-Si-H and CaCO 3 formation and subsequent dissolution (days 14-73). Experiments with the smallest size fraction resulted in the highest Ca, Si and V concentrations, highlighting the role of surface area in controlling initial leaching. After ~2 weeks, the solution Ca/Si ratio (0.7-0.9) evolved to equal those found within a Ca-Si-H phase that replaced dicalcium silicate and free-lime phases in a 30- to 150-μm altered surface region. V release was a two-stage process; initially, V was released by dicalcium silicate dissolution, but V also isomorphically substituted for Si into the neo-formed Ca-Si-H in the alteration zone. Therefore, on longer timescales, the release of V to solution was primarily controlled by considerably slower Ca-Si-H dissolution rates, which decreased the rate of V release by an order of magnitude. Overall, the results indicate that the BOF slag leaching mechanism evolves from a situation initially dominated by rapid hydration and dissolution of primary dicalcium silicate/free-lime phases, to a slow diffusion limited process controlled by the solubility of secondary Ca-Si-H and CaCO 3 phases that replace and cover more reactive primary slag phases at particle surfaces.

Characterization of the Bonds Developed between Calcium Silicate Hydrate and Polycarboxylate-Based Superplasticizers with Silyl Functionalities

KAUST Repository

Orozco, Carlos A.

2017-03-24

Major developments in concrete technology have been achieved with the use of polycarboxylate-based superplasticizers (PCEs) to improve the concrete rheology without increasing the mix water content. Currently, it is possible to control the fluidity of the fresh concrete and obtain stronger and more durable structures. Therefore, there is a strong incentive to understand the interactions between PCEs and cement hydrates at the atomic scale to design new customized functional PCEs according to the ever-increasing requirements of the concrete industry. Here, the bonding types generated between a PCE with silyl functionalities (PCE-Sil) and a synthetic calcium silicate hydrate (C-S-H) are analyzed using XRD, 29Si NMR spectroscopy, and synchrotron-based techniques, such as NEXAFS and EXAFS. The results indicated that the carboxylic groups present in PCE-Sil interact by a ligand-type bond with calcium, which modified not only the symmetry and coordination number of the calcium located at the surface of C-S-H but also the neighboring silicon atoms of the C-S-H. In addition, the silyl functionalities of the PCE-Sil generated covalent bonds through siloxane bridges between the silanol groups of PCE-Sil and the nonbonding oxygen located at the dimeric sites in C-S-H, forming new bridging silicon sites and subsequently increasing the silicate polymerization.

Characterization of the Bonds Developed between Calcium Silicate Hydrate and Polycarboxylate-Based Superplasticizers with Silyl Functionalities.

Science.gov (United States)

Orozco, Carlos A; Chun, Byong W; Geng, Guoqing; Emwas, Abdul H; Monteiro, Paulo J M

2017-04-11

Major developments in concrete technology have been achieved with the use of polycarboxylate-based superplasticizers (PCEs) to improve the concrete rheology without increasing the mix water content. Currently, it is possible to control the fluidity of the fresh concrete and obtain stronger and more durable structures. Therefore, there is a strong incentive to understand the interactions between PCEs and cement hydrates at the atomic scale to design new customized functional PCEs according to the ever-increasing requirements of the concrete industry. Here, the bonding types generated between a PCE with silyl functionalities (PCE-Sil) and a synthetic calcium silicate hydrate (C-S-H) are analyzed using XRD, 29 Si NMR spectroscopy, and synchrotron-based techniques, such as NEXAFS and EXAFS. The results indicated that the carboxylic groups present in PCE-Sil interact by a ligand-type bond with calcium, which modified not only the symmetry and coordination number of the calcium located at the surface of C-S-H but also the neighboring silicon atoms of the C-S-H. In addition, the silyl functionalities of the PCE-Sil generated covalent bonds through siloxane bridges between the silanol groups of PCE-Sil and the nonbonding oxygen located at the dimeric sites in C-S-H, forming new bridging silicon sites and subsequently increasing the silicate polymerization.

Characterization of the Bonds Developed between Calcium Silicate Hydrate and Polycarboxylate-Based Superplasticizers with Silyl Functionalities

KAUST Repository

Orozco, Carlos A.; Chun, Byong W.; Geng, Guoqing; Emwas, Abdul-Hamid M.; Monteiro, Paulo J. M.

2017-01-01

Major developments in concrete technology have been achieved with the use of polycarboxylate-based superplasticizers (PCEs) to improve the concrete rheology without increasing the mix water content. Currently, it is possible to control the fluidity of the fresh concrete and obtain stronger and more durable structures. Therefore, there is a strong incentive to understand the interactions between PCEs and cement hydrates at the atomic scale to design new customized functional PCEs according to the ever-increasing requirements of the concrete industry. Here, the bonding types generated between a PCE with silyl functionalities (PCE-Sil) and a synthetic calcium silicate hydrate (C-S-H) are analyzed using XRD, 29Si NMR spectroscopy, and synchrotron-based techniques, such as NEXAFS and EXAFS. The results indicated that the carboxylic groups present in PCE-Sil interact by a ligand-type bond with calcium, which modified not only the symmetry and coordination number of the calcium located at the surface of C-S-H but also the neighboring silicon atoms of the C-S-H. In addition, the silyl functionalities of the PCE-Sil generated covalent bonds through siloxane bridges between the silanol groups of PCE-Sil and the nonbonding oxygen located at the dimeric sites in C-S-H, forming new bridging silicon sites and subsequently increasing the silicate polymerization.

A Study of Calcium-Silicate-Hydrate/Polymer Nanocomposites Fabricated Using the Layer-By-Layer Method

Directory of Open Access Journals (Sweden)

Mahsa Kamali

2018-03-01

Full Text Available Calcium-silicate-hydrate (CSH/polymer nanocomposites were synthesized with the layer-by-layer (LBL method, and their morphology and mechanical properties were investigated using atomic force microscopy (AFM imaging and AFM nanoindentation. Different sets of polymers were used to produce CSH/polymer nanocomposites. The effect of different factors including dipping time, calcium to silicate ratios (C/S ratios and pH on morphology was investigated. CSH/polymer nanocomposites made with different sets of polymers showed variation in morphologies. However, the Young’s modulus did not seem to reveal significant differences between the nanocomposites studied here. In nanocomposites containing graphene oxide (GO nanosheet, an increase in the density of CSH particles was observed on the GO nanosheet compared to areas away from the GO nanosheet, providing evidence for improved nucleation of CSH in the presence of GO nanosheets. An increase in roughness and a reduction in the packing density in nanocomposites containing GO nanosheets was observed.

On crystallochemistry of uranil silicates

International Nuclear Information System (INIS)

Sidorenko, G.A.; Moroz, I.Kh.; Zhil'tsova, I.G.

1975-01-01

A crystallochemical analysis has been made of uranil silicates. It is shown that on crystallochemical grounds it is justified to distinguish among them uranophane-kasolite, soddyite and viksite groups differing in the uranil-anion [SiO 4 ] -4 ratio and, as a consequence, in their crystallochemical structures. Widespread silicates of the uranophane-kasolite group is the formation of polytype modifications where, depending on the interlaminar cation, crystalline structures are formed with various packing of single-type uranil-anion layers. It has been shown experimentally that silicates of the uranophanekasolite group contain no oxonium ion in their crystalline structures. Minerals of the viksite group belong to a group of isostructural (homeotypic) laminated formation apt to form phases of different degrees of hydration. Phases with a smaller interlaminar cation form hydrates with a greater number of water molecules in the formulas unit

Apatite formation on bioactive calcium-silicate cements for dentistry affects surface topography and human marrow stromal cells proliferation.

Science.gov (United States)

Gandolfi, Maria Giovanna; Ciapetti, Gabriela; Taddei, Paola; Perut, Francesca; Tinti, Anna; Cardoso, Marcio Vivan; Van Meerbeek, Bart; Prati, Carlo

2010-10-01

The effect of ageing in phosphate-containing solution of bioactive calcium-silicate cements on the chemistry, morphology and topography of the surface, as well as on in vitro human marrow stromal cells viability and proliferation was investigated. A calcium-silicate cement (wTC) mainly based on dicalcium-silicate and tricalcium-silicate was prepared. Alpha-TCP was added to wTC to obtain wTC-TCP. Bismuth oxide was inserted in wTC to prepare a radiopaque cement (wTC-Bi). A commercial calcium-silicate cement (ProRoot MTA) was tested as control. Cement disks were aged in DPBS for 5 h ('fresh samples'), 14 and 28 days, and analyzed by ESEM/EDX, SEM/EDX, ATR-FTIR, micro-Raman techniques and scanning white-light interferometry. Proliferation, LDH release, ALP activity and collagen production of human marrow stromal cells (MSC) seeded for 1-28 days on the cements were evaluated. Fresh samples exposed a surface mainly composed of calcium-silicate hydrates CSH (from the hydration of belite and alite), calcium hydroxide, calcium carbonate, and ettringite. Apatite nano-spherulites rapidly precipitated on cement surfaces within 5 h. On wTC-TCP the Ca-P deposits appeared thicker than on the other cements. Aged cements showed an irregular porous calcium-phosphate (Ca-P) coating, formed by aggregated apatite spherulites with interspersed calcite crystals. All the experimental cements exerted no acute toxicity in the cell assay system and allowed cell growth. Using biochemical results, the scores were: fresh cements>aged cements for cell proliferation and ALP activity (except for wTC-Bi), whereas fresh cements

Electron radiation damages to dicalcium (Ca{sub 2}SiO{sub 4}) and tricalcium (Ca{sub 3}SiO{sub 5}) orthosilicates

Energy Technology Data Exchange (ETDEWEB)

Noirfontaine, Marie-Noëlle de; Dunstetter, Frédéric [Laboratoire des Solides Irradiés, UMR CNRS 7642, Ecole Polytechnique, Université Paris-Saclay, F-91128 Palaiseau Cedex (France); Courtial, Mireille [Laboratoire des Solides Irradiés, UMR CNRS 7642, Ecole Polytechnique, Université Paris-Saclay, F-91128 Palaiseau Cedex (France); Université d’Artois, 1230 Rue de l’Université, CS 20819, F-62408 Béthune (France); Signes-Frehel, Marcel [Laboratoire des Solides Irradiés, UMR CNRS 7642, Ecole Polytechnique, Université Paris-Saclay, F-91128 Palaiseau Cedex (France); Wang, Guillaume [Laboratoire Matériaux et Phénomènes Quantiques, UMR CNRS 7162, Université Paris Diderot, F-75205 Paris Cedex 13 (France); Gorse - Pomonti, Dominique [Laboratoire des Solides Irradiés, UMR CNRS 7642, Ecole Polytechnique, Université Paris-Saclay, F-91128 Palaiseau Cedex (France)

2016-05-01

Electron radiation damages to dicalcium silicate (Ca{sub 2}SiO{sub 4}) and tricalcium silicate (Ca{sub 3}SiO{sub 5}) are reported for the first time in this paper. With increasing flux, between 2.7 × 10{sup 17} and 2.2 × 10{sup 22} e{sup −} cm{sup −2} s{sup −1}, decomposition into nanodomains of crystalline CaO plus an amorphous silica rich phase is first observed for both silicates, then amorphization at higher flux always for both silicates, and finally hole drilling but only for Ca{sub 3}SiO{sub 5}. These structural modifications are accompanied by a net reduction of Ca content under the electron beam depending on the silicate species. These radiation effects occur for values of flux and dose larger than in previously studied orthosilicates (like olivines), and much larger than in all tectosilicates.

Effect of temperature on the microstructure of calcium silicate hydrate (C-S-H)

Energy Technology Data Exchange (ETDEWEB)

Gallucci, E., E-mail: gallucci.emmanuel@ch.sika.com; Zhang, X.; Scrivener, K.L.

2013-11-15

Temperature affects the properties of concrete through its effect on the hydration of cement and its associated microstructural development. This paper focuses on the modifications to C-S-H induced by isothermal curing between 5 and 60 °C. The results show that as the temperature increases (within the range studied) the C/S ratio of C-S-H changes only slightly, with a higher degree of polymerisation of silicate chains, but there is a significant decrease in its bound water content and an increase of apparent density of 25%. This increase seems to come from a different packing of C-S-H at the nanoscale. As a consequence of these changes, the microstructure of the cement paste is much coarser and porous, which explains the lower final strengths obtained by curing at elevated temperatures. -- Highlights: •C-S-H structure studied at the atomic level •Multiple analytical techniques used •Studies conducted at temperatures above and below normal temperatures.

The effect of powder properties on sintering, microstructure, mechanical strength and degradability of beta-tricalcium phosphate/calcium silicate composite bioceramics

Energy Technology Data Exchange (ETDEWEB)

Lin Kaili; Chang Jiang; Shen Ruxiang, E-mail: jchang@mail.sic.ac.c [State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China)

2009-12-15

The effect of powder properties on sintering, microstructure, mechanical strength and degradability of beta-tricalcium phosphate/Calcium silicate (beta-Ca{sub 3}(PO{sub 4}){sub 2}/CaSiO{sub 3}, beta-TCP/CS) composite bioceramics was investigated. beta-TCP/CS composite powders with a weight ratio of 50:50 were prepared by three different methods: mechanical milling method (TW-A), two-step chemical precipitation method (TW-B) and in situ chemical co-precipitation method (TW-C), and then the three composite powders were uniaxially compacted at 30 MPa, followed by cold isostatic pressing into rectangular-prism-shaped specimens under a pressure of 200 MPa for 15 min, and then sintered at 1150 deg. C for 5 h. The TW-B powders with less agglomerative morphologies and uniform nano-size particles attained 96.14% relative density (RD). A uniform microstructure with about 120 nm grains was observed. Whereas, the samples obtained from TW-A and TW-C powders only reached a RD of 63.08% and 78.86%, respectively. The bending strength of the samples fabricated from TW-B reached 125 MPa, which was more than 3.7 and 1.5 times higher as compared with that of samples obtained from TW-A and TW-C powders, respectively. Furthermore, the degradability of the samples fabricated from TW-B powders was obviously lower than that of the samples fabricated from TW-A and TW-C powders.

Preparation of iron-modified portland cement adsorbent and the investigation of its decolorization performance

Science.gov (United States)

Jiang, Bo; Wang, Huifeng; Li, Yang; Li, Zhen

2018-02-01

The ordinary portland cement was modified by ferric salt impregnation method. Through the technologies of x-ray diffraction, scanning electron microscope and energy dispersive spectroscopy, the physicochemical properties of modified cement were detected and analyzed. It was found that after the modification, the main constituents of raw cement, tricalcium silicate and dicalcium silicate had been depleted, and the new crystal mineral of antarcticite replaced them. The iron precipitates and cement hydration products calcium silicate hydrate gel mainly existed in the form of amorphous on modified cement. The results of BET specific surface determination showed that the modified cement particles had mesoporous distribution. The results of adsorption experiment revealed modified cement exhibited excellent adsorption performance on reactive brilliant blue KNR. The combination mechanism between modified cement and adsorbate was mainly electrostatic interaction. The adsorption process satisfied with the pseudo-second order kinetics model, and the adsorption reaction was a spontaneous endothermic process.

Mechanistic study and modeling of radionuclides retention by the hydrated calcium silicates (HCS) of cements; Etude mecanistique et modelisation de la retention de radionucleides par les silicates de calcium hydrates (CSH) des ciments

Energy Technology Data Exchange (ETDEWEB)

Pointeau, I

2000-09-01

This work attempts to investigate the modelling of radioisotopes (Cs{sup +}, Pb{sup 2+}, Eu{sup 3+}) immobilization in cement matrix, in the frame of the design of engineered barrier of a deep radwaste repository. The model development concept consists of three major steps: - surface chemistry modelling of the calcium silicate hydrate CSH, used to simulate hydrated cement behaviour; - solid analysis of the batch sorption experiments: identification of the uptake mechanism; - both previous steps are used, with isotherm data, in the modelling of the radioisotopes immobilization in the CSH matrix. Final results: (all modelling are available for all the range of studied Ca/Si ratios and have been validated with predictive calculations). - A thermodynamic modelling of the CSH surface chemistry has been developed. The labile calcium and proton sorption constants on silanol sites (>SiOH) have been extracted. - Cs{sup +} is sorbed on two sites. The silanol site (weak site) has a high site density (10 sites.nm{sup -2}), which accounts for the CSH unsaturation in high [CS{sup +}]. A strong site is also identified. - Pb{sup 2+} immobilization in CSH matrix is modelled with surface equilibria and solubility equilibrium. - Eu{sup 3+} fixation has been investigated with solid analysis: Site-Selective anti Time-Resolved Luminescence Spectroscopy, XPS and SEM-EDS. Eu{sup 3+} thus does not precipitate in CSH water but is sorbed on the CSH surface (high hydroxylated environment). Europium is also (minority site) inserted in the CSH framework. (author)

Hydration of a low-alkali CEM III/B–SiO2 cement (LAC)

International Nuclear Information System (INIS)

Lothenbach, Barbara; Le Saout, Gwenn; Ben Haha, Mohsen; Figi, Renato; Wieland, Erich

2012-01-01

The hydration of a low-alkali cement based on CEM III/B blended with 10 wt.% of nanosilica has been studied. The nanosilica reacted within the first days and 90% of the slag reacted within 3.5 years. C-S-H (Ca/Si ∼ 1.2, Al/Si ∼ 0.12), calcite, hydrotalcite, ettringite and possibly strätlingite were the main hydrates. The pore water composition revealed ten times lower alkali concentrations than in Portland cements. Reducing conditions (HS − ) and a pH value of 12.2 were observed. Between 1 month and 3.5 years of hydration more hydrates were formed due to the ongoing slag reaction but no significant differences in the composition of the pore solution or solid phase assemblage were observed. On the basis of thermodynamic calculations it is predicted that siliceous hydrogarnet could form in the long-term and, in the presence of siliceous hydrogarnet, also thaumasite. Nevertheless, even after 3.5 year hydration, neither siliceous hydrogarnet nor thaumasite have been observed.

Microstructure of hydrated cement pastes as determined by SANS

International Nuclear Information System (INIS)

Sabine, T.; Bertram, W.; Aldridge, L.

1999-01-01

Full text: Technologists have known how to make concrete for over 2000 years but despite painstaking research no one has been able to show how and why concrete sets. Part of the problem is that the calcium silicate hydrate (the gel produced by hydrating cement) is amorphous and cannot be characterised by x-ray crystallographic techniques. Small angle neutron scattering on instrument V12a at BENSC was used to characterise the hydration reactions and show the growth of the calcium silicate hydrates during initial hydration and the substantial differences in the rate of growth and structure as different additives are used. SANS spectra were measured as a function of the hydration from three different types of cement paste: 1) Ordinary Portland Cement made with a water to cement ratio of about 0.4; 2) A blend of Ordinary Portland Cement(25%) and Ground Granulated Blast Furnace Slag (75%) with a water to cement ration of about 0.4; 3) A dense paste made from silica fume(24%), Ordinary Portland Cement (76%) at a water to powder ratio of 0.18. The differences in the spectra are interpreted in terms of differences between the microstructure of the pastes

Mechanistic study and modeling of radionuclides retention by the hydrated calcium silicates (HCS) of cements

International Nuclear Information System (INIS)

Pointeau, I.

2000-09-01

This work attempts to investigate the modelling of radioisotopes (Cs + , Pb 2+ , Eu 3+ ) immobilization in cement matrix, in the frame of the design of engineered barrier of a deep radwaste repository. The model development concept consists of three major steps: - surface chemistry modelling of the calcium silicate hydrate CSH, used to simulate hydrated cement behaviour; - solid analysis of the batch sorption experiments: identification of the uptake mechanism; - both previous steps are used, with isotherm data, in the modelling of the radioisotopes immobilization in the CSH matrix. Final results: (all modelling are available for all the range of studied Ca/Si ratios and have been validated with predictive calculations). - A thermodynamic modelling of the CSH surface chemistry has been developed. The labile calcium and proton sorption constants on silanol sites (>SiOH) have been extracted. - Cs + is sorbed on two sites. The silanol site (weak site) has a high site density (10 sites.nm -2 ), which accounts for the CSH unsaturation in high [CS + ]. A strong site is also identified. - Pb 2+ immobilization in CSH matrix is modelled with surface equilibria and solubility equilibrium. - Eu 3+ fixation has been investigated with solid analysis: Site-Selective anti Time-Resolved Luminescence Spectroscopy, XPS and SEM-EDS. Eu 3+ thus does not precipitate in CSH water but is sorbed on the CSH surface (high hydroxylated environment). Europium is also (minority site) inserted in the CSH framework. (author)

Uranium-thorium silicates, with specific reference to the species in the Witwatersrand reefs

International Nuclear Information System (INIS)

Smits, G.

1987-01-01

(U,Th)-silicates form two complete series of anhydrous and hydrated species with general formulae (U,Th)SiO 4 and (U,Th)SiO 4 .nH 2 O respectively. The end-members of the anhydrous series are anhydrous coffinite and thorite, and those of the hydrated series, coffinite and thorogummite. Although the silicates are relatively rare in nature, coffinite is a common ore mineral in uranium deposits of the sandstone type. In the Witwatersrand reefs, (U,Th)-silicates are extremely rare in most reefs, except for the Elsburg Reefs on the West Rand Goldfield and the Dominion Reef. In these reefs detrital uraninite has been partly or entirely transformed to (U,Th)-silicates of coffinite composition, but thorite and thorogummite of detrital origin are also found in the Dominion Reef. In leaching tests on polished sections of rock samples containing (U,Th)-silicates, a dilute sulphuric acid solution, to which ferric iron had been added, was used as the lixiviant. It appeared that the dissolution of coffinite is less rapid than that of uraninite and uraniferous leucoxene. However, the reaction of silicates of high thorium content is much slower, and was not completed during the tests

On the nature of structural disorder in calcium silicate hydrates with a calcium/silicon ratio similar to tobermorite

Energy Technology Data Exchange (ETDEWEB)

Grangeon, Sylvain, E-mail: S.Grangeon@brgm.fr [BRGM, 3, Avenue Claude Guillemin, 45060 Orléans Cedex 2 (France); Claret, Francis; Lerouge, Catherine [BRGM, 3, Avenue Claude Guillemin, 45060 Orléans Cedex 2 (France); Warmont, Fabienne [CRMD, UMR 6619 – CNRS, 1b rue de la férollerie, 45071 Orléans Cedex 2 (France); Sato, Tsutomu; Anraku, Sohtaro [Laboratory of Environmental Geology, Research Group of Geoenvironmental/Engineering Division of Solid Waste, Resources and Geoenvironmental/Engineering Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Sapporo 060-8628 (Japan); Numako, Chiya [Faculty of Integrated Arts and Sciences, The University of Tokushima, 1-1, Minami-Josanjima, Tokushima, 770-8502 (Japan); Linard, Yannick [ANDRA, Centre de Meuse/Haute Marne, 55290 Bure (France); Lanson, Bruno [ISTerre, Grenoble University, CNRS, F-38041 Grenoble (France)

2013-10-15

Four calcium silicate hydrates (C-S-H) with structural calcium/silicon (Ca/Si) ratios ranging from 0.82 ± 0.02 to 0.87 ± 0.02 were synthesized at room temperature, 50, 80, and 110 °C. Their structure was elucidated by collating information from electron probe micro-analysis, transmission electron microscopy, extended X-ray absorption fine structure spectroscopy, and powder X-ray diffraction (XRD). A modeling approach specific to defective minerals was used because sample turbostratism prevented analysis using usual XRD refinement techniques (e.g. Rietveld analysis). It is shown that C-S-H with Ca/Si ratio of ∼ 0.8 are structurally similar to nano-crystalline turbostratic tobermorite, a naturally occurring mineral. Their structure thus consists of sheets of calcium atoms in 7-fold coordination, covered by ribbons of silicon tetrahedra with a dreierketten (wollastonite-like) organization. In these silicate ribbons, 0.42 Si per bridging tetrahedron are missing. Random stacking faults occur systematically between successive layers (turbostratic stacking). Layer-to-layer distance is equal to 11.34 Å. Crystallites have a mean size of 10 nm in the a–b plane, and a mean number of 2.6–2.9 layers stacked coherently along the c* axis.

NMR study of hydrated calcium silicates; Etude par RMN de la structure des silicates de calcium hydrates

Energy Technology Data Exchange (ETDEWEB)

Klur, I

1996-02-26

Radioactive wastes storage methods are developed by the CEA. As cements are important materials as well for hours living radioisotopes than for years living radioisotopes, a better knowledge of this material will allow to anticipate its behaviour and to obtain safer storage methods. The structure of calcium silicates (C-S-H) (main constituent of cements) have then been determined in this thesis by nuclear magnetic resonance. This method has allow to explain in structural terms, the different calcium rates that can be measured in the C-S-H too. (O.M.) 101 refs.

Class H cement hydration at 180 deg. C and high pressure in the presence of added silica

International Nuclear Information System (INIS)

Jupe, Andrew C.; Wilkinson, Angus P.; Luke, Karen; Funkhouser, Gary P.

2008-01-01

Under deep oil-well conditions of elevated temperature and pressure, crystalline calcium silicate hydrates are formed during Portland cement hydration. The use of silica rich mineral additives leads to the formation of crystalline hydrates with better mechanical properties than those formed without the additive. The effects of silica flour, silica fume (amorphous silica), and a natural zeolite mixture on the hydration of Class H cement slurries at 180 deg. C under externally applied pressures of 7 and 52 MPa are examined in real time using in-situ synchrotron X-ray diffraction. For some compositions examined, but not all, pressure was found to have a large effect on the kinetics of crystalline hydrate formation. The use of silica fume delayed both C 3 S hydration and the formation of crystalline silicate hydrates compared to what was seen with other silica sources

Nanostructural Deformation Analysis of Calcium Silicate Hydrate in Portland Cement Paste by Atomic Pair Distribution Function

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Hiroshi Suzuki

2016-01-01

Full Text Available The deformation of nanostructure of calcium silicate hydrate (C-S-H in Portland cement (PC paste under compression was characterized by the atomic pair distribution function (PDF, measured using synchrotron X-ray diffraction. The PDF of the PC paste exhibited a unique deformation behavior for a short-range order below 2.0 nm, close to the size of the C-S-H globule, while the deformation for a long-range order was similar to that of a calcium hydroxide phase measured by Bragg peak shift. The compressive deformation of the C-S-H nanostructure was comprised of three stages with different interactions between globules. This behavior would originate from the granular nature of C-S-H, which deforms with increasing packing density by slipping the interfaces between globules, rearranging the overall C-S-H nanostructure. This new approach will lead to increasing applications of the PDF technique to understand the deformation mechanism of C-S-H in PC-based materials.

The synergistic effects of Chinese herb and injectable calcium silicate/β-tricalcium phosphate composite on an osteogenic accelerator in vitro.

Science.gov (United States)

Huang, Ming-Hsien; Kao, Chia-Tze; Chen, Yi-Wen; Hsu, Tuan-Ti; Shieh, Den-En; Huang, Tsui-Hsien; Shie, Ming-You

2015-04-01

This study investigates the physicochemical and biological effects of traditional Chinese medicines on the β-tricalcium phosphate (β-TCP)/calcium silicate (CS) composites of bone cells using human dental pulp cell. CS is an osteoconductive and bioactive material. For this research we have combined β-TCP and CS and check its effectiveness, a series of β-TCP/CS composites with different ratios of Xu Duan (XD) were prepared to make new bioactive and biodegradable biocomposites for bone repair. XD has been used in Traditional Chinese Medicine for hundreds of years as an antiosteoporosis, tonic and antiaging agent for the therapy of low back pain, traumatic hematoma, threatened abortion and bone fractures. Formation of bone-like apatite, the diametral tensile strength, and weight loss of composites were considered before and after immersion in simulated body fluid (SBF). In addition, we also examined the effects of XD released from β-TCP/CS composites and in vitro human dental pulp cell (hDPCs) and studied its behavior. The results show the XD-contained paste did not give any demixing when the weight ratio of XD increased to 5-10 % due to the filter-pressing effect during extrusion through the syringe. After immersion in SBF, the microstructure image showed a dense bone-like apatite layer covered on the β-TCP/CS/XD composites. In vitro cell experiments shows that the XD-rich composites promote human dental pulp cells (hDPCs) proliferation and differentiation. However, when the XD quantity in the composite is more than 5 %, the amount of cells and osteogenesis protein of hDPCs were stimulated by XD released from β-TCP/CS composites. The combination of XD in degradation of β-TCP and osteogenesis of CS gives strong reason to believe that these calcium-based composite cements may prove to be promising bone repair materials.

Modeling Nanomechanical Behavior of Calcium-Silicate-Hydrate

Science.gov (United States)

2012-08-01

coefficient is effective in making the C-S-H matrix stronger. However, increasing packing density also makes the material response more brittle ...16102-16107 Pellenq, R.J. –M and Van Damme, Henri., 2004, Why Does Concrete set?: The nature of Cohesion Forces in hardened Cement-Based...Hydrated Nanocomposites: Concrete, Bone , and Shale. J. Am. Ceram. Soc., 90(9): 2677-2692. Wu, Jianzhong. and John M. Prausnitz. 2002. Generalizations for

Sintering and mechanical properties of the alumina–tricalcium phosphate–titania composites

Energy Technology Data Exchange (ETDEWEB)

Sakka, Siwar, E-mail: sakka.siwar@yahoo.fr; Bouaziz, Jamel; Ben Ayed, Foued

2014-07-01

The objective of this study was to determine the effect of the content of titania and the sintering process on the transformation phase, the densification, the rupture strength and the microstructures of the alumina–10 wt.% tricalcium phosphate composites. After the sintering process, the samples were examined by using {sup 31}P and {sup 27}Al magic angle scanning nuclear magnetic resonance, X-ray powder diffraction and scanning electron microscopy analysis. The Brazilian test was used to measure the rupture strength of the samples. The present results provide new information about solid-state reactivity in the ternary system α-alumina-β-tricalcium phosphate–anatase–titania. The differential thermal analysis of the α-alumina-β-tricalcium phosphate–titania composites shows two endothermic peaks, at 1360 °C and at 1405 °C, which are caused by the reactions between titania/alumina and titania/tricalcium phosphate, respectively. Thus, the presence of titania in the alumina–10 wt.% tricalcium phosphate leads to the formation of β-Al{sub 2}TiO{sub 5} at 1360 °C. At 1600 °C, the alumina–10 wt.% tricalcium phosphate–5 wt.% titania composites displayed the highest rupture strength (74 MPa), compared to the alumina–10 wt.% tricalcium phosphate composites (13.5 MPa). Accordingly, the increase of the rupture strength is due to the formation of the new β-Al{sub 2}TiO{sub 5} phase. - Highlights: • We examine the mechanical properties of bioceramics. • We measure the rupture strength by the Brazilian test. • We characterize the alumina–10 wt.% tricalcium phosphate–titania composites.

Using calcium silicate to regulate the physicochemical and biological properties when using β-tricalcium phosphate as bone cement

Energy Technology Data Exchange (ETDEWEB)

Kao, Chia-Tze; Huang, Tsui-Hsien [School of Dentistry, Chung Shan Medical University, Taichung, Taiwan (China); Department of Dentistry, Chung Shan Medical University Hospital, Taichung, Taiwan (China); Chen, Yi-Jyun [School of Dentistry, Chung Shan Medical University, Taichung, Taiwan (China); Department of Dentistry, Chung Shan Medical University Hospital, Taichung, Taiwan (China); Dental Department, Taichung Hospital, Ministry of Health and Welfare, Taichung City, Taiwan (China); Hung, Chi-Jr [School of Dentistry, Chung Shan Medical University, Taichung, Taiwan (China); Department of Dentistry, Chung Shan Medical University Hospital, Taichung, Taiwan (China); Lin, Chi-Chang, E-mail: chichang31@gmail.com [Department of Chemical and Materials Engineering, Tunghai University, Taichung, Taiwan (China); Shie, Ming-You, E-mail: eviltacasi@gmail.com [Department of Chemical and Materials Engineering, Tunghai University, Taichung, Taiwan (China)

2014-10-01

β-Tricalcium phosphate (β-TCP) is an osteoconductive material. For this research we have combined it with a low degradation calcium silicate (CS) to enhance its bioactive and osteostimulative properties. To check its effectiveness, a series of β-TCP/CS composites with different ratios were prepared to make new bioactive and biodegradable biocomposites for bone repair. Regarding the formation of bone-like apatite, the diametral tensile strength as well as the ion release and weight loss of composites were compared both before and after immersions in simulated body fluid (SBF). In addition, we also examined the behavior of human dental pulp cells (hDPCs) cultured on β-TCP/CS composites. The results show that the apatite deposition ability of the β-TCP/CS composites improves as the CS content is increased. For composites with more than a 60% CS content, the samples become completely covered by a dense bone-like apatite layer. At the end of the immersion period, weight losses of 24%, 32%, 34%, 38%, 41%, and 45% were observed for the composites containing 0%, 20%, 40%, 80%, 80% and 100% β-TCP cements, respectively. In addition, the antibacterial activity of CS/β-TCP composite improves as the CS-content is increased. In vitro cell experiments show that the CS-rich composites promote human dental pulp cell (hDPC) proliferation and differentiation. However, when the CS quantity in the composite is less than 60%, the quantity of cells and osteogenesis protein of hDPCs is stimulated by Si released from the β-TCP/CS composites. The degradation of β-TCP and the osteogenesis of CS give strong reason to believe that these calcium-based composite cements will prove to be effective bone repair materials. - Highlights: • CS improved the physicochemical properties and osteogenic activity of β-TCP. • Higher CS in the composite, the shorter setting time and the higher DTS was found. • With a CS more than 40%, the osteogenesis and angiogenesis proteins were promoted by

Copper Silicate Hydrate Hollow Spheres Constructed by Nanotubes Encapsulated in Reduced Graphene Oxide as Long-Life Lithium-Ion Battery Anode.

Science.gov (United States)

Wei, Xiujuan; Tang, Chunjuan; Wang, Xuanpeng; Zhou, Liang; Wei, Qiulong; Yan, Mengyu; Sheng, Jinzhi; Hu, Ping; Wang, Bolun; Mai, Liqiang

2015-12-09

Hierarchical copper silicate hydrate hollow spheres-reduced graphene oxide (RGO) composite is successfully fabricated by a facile hydrothermal method using silica as in situ sacrificing template. The electrochemical performance of the composite as lithium-ion battery anode was studied for the first time. Benefiting from the synergistic effect of the hierarchical hollow structure and conductive RGO matrix, the composite exhibits excellent long-life performance and rate capability. A capacity of 890 mAh/g is achieved after 200 cycles at 200 mA/g and a capacity of 429 mAh/g is retained after 800 cycles at 1000 mA/g. The results indicate that the strategy of combining hierarchical hollow structures with conductive RGO holds the potential in addressing the volume expansion issue of high capacity anode materials.

Influence of alkali, silicate, and sulfate content of carbonated concrete pore solution on mild steel corrosion behavior

International Nuclear Information System (INIS)

L'Hostis, V.; Huet, B.; Tricheux, L.; Idrissi, H.

2010-01-01

The increase in the rebar corrosion rate due to the concrete carbonation is the major cause of reinforced concrete degradation. The aim of this study was to investigate the corrosion behavior of mild steel rebars in simulated carbonated concrete solution. For this purpose, thermodynamic calculations, electrochemical techniques, gravimetric measurements, and surface analyses were used. Thermodynamic investigations of the nature of the interstitial solution provides an estimation of the influence of sulfate (SO 4 2- ) and alkali (Na + , K + ) content on carbonate alkalinity of the CO 2 /H 2 O open system (pCO 2 =0. 3 mbar). in this system, calcium-silicate hydrates (C-S-H) remain thermodynamically unstable and amorphous silica controls silicate aqueous content at 100 ppm. Electrochemical results highlight a decrease in the corrosion rate with increasing carbonate alkalinity and the introduction of silicate. The introduction of sulfate at fixed carbonate alkalinity shows a dual effect: at high carbonate alkalinity, the corrosion rate is increased whereas at low carbonate alkalinity, corrosion rate is decreased. Those results are supported by surface analysis. Authors conclude that silicate and sulfate release from cement hydrates and fixation of alkali on carbonated hydrates are key parameters to estimate mild steel corrosion in carbonated concrete. (authors)

Interaction of calcium silicate hydrates (C-S-H), the main components of cement, with alkaline chlorides, analogy with clays; Interaction des silicates de calcium hydrates, principaux constituants du ciment, avec les chlorures d'alcalins. Analogie avec les argiles

Energy Technology Data Exchange (ETDEWEB)

Viallis-Terrisse, H

2000-10-06

This work, belonging to a more general study on the structure and reactivity of cement, deals with the experimental and theoretical analysis of the interaction of alkaline chlorides with calcium silicate hydrates (C-S-H), the main components of cement paste. The interaction of alkaline cations with C-S-H is interfacial, involving both electrostatic and surface complexation mechanisms. The C-S-H surface is constituted of silanol sites, partially dissociated due to the high pH of the interstitial solution. The calcium ions, present in large amounts in the equilibrium solution of C-S-H, constitute potential determining ions for the C-S-H surface. The alkaline ions seem to compete with calcium for the same surface sites. The adsorption isotherms show that caesium presents a better affinity than sodium and lithium for the C-S-H surface. Moreover, solid-state NMR suggests that caesium forms with the surface sites inner-sphere complexes, whereas sodium seems to keep its hydration sphere. These results are in agreement with zeta potential measurements, which let suppose a specific adsorption of caesium ions, and an indifferent behaviour of both other alkaline ions. A model for the C-S-H surface was proposed, from the electric double layer model, and mass action laws expressing the complexation of the different ionic species with the silanol sites. The whole study relies on a structural analogy with smectites, some clays presenting well-known cationic adsorption properties. The structural similarity between both minerals is enhanced by some similarities of reactivity, though significant behaviour differences could also be noted. (author)

Biological and therapeutic effects of ortho-silicic acid and some ortho-silicic acid-releasing compounds: New perspectives for therapy

Directory of Open Access Journals (Sweden)

Jurkić Lela Munjas

2013-01-01

Full Text Available Abstract Silicon (Si is the most abundant element present in the Earth's crust besides oxygen. However, the exact biological roles of silicon remain unknown. Moreover, the ortho-silicic acid (H4SiO4, as a major form of bioavailable silicon for both humans and animals, has not been given adequate attention so far. Silicon has already been associated with bone mineralization, collagen synthesis, skin, hair and nails health atherosclerosis, Alzheimer disease, immune system enhancement, and with some other disorders or pharmacological effects. Beside the ortho-silicic acid and its stabilized formulations such as choline chloride-stabilized ortho-silicic acid and sodium or potassium silicates (e.g. M2SiO3; M= Na,K, the most important sources that release ortho-silicic acid as a bioavailable form of silicon are: colloidal silicic acid (hydrated silica gel, silica gel (amorphous silicon dioxide, and zeolites. Although all these compounds are characterized by substantial water insolubility, they release small, but significant, equilibrium concentration of ortho-silicic acid (H4SiO4 in contact with water and physiological fluids. Even though certain pharmacological effects of these compounds might be attributed to specific structural characteristics that result in profound adsorption and absorption properties, they all exhibit similar pharmacological profiles readily comparable to ortho-silicic acid effects. The most unusual ortho-silicic acid-releasing agents are certain types of zeolites, a class of aluminosilicates with well described ion(cation-exchange properties. Numerous biological activities of some types of zeolites documented so far might probably be attributable to the ortho-silicic acid-releasing property. In this review, we therefore discuss biological and potential therapeutic effects of ortho-silicic acid and ortho-silicic acid -releasing silicon compounds as its major natural sources.

Analysis of cubic and orthorhombic C3A hydration in presence of gypsum and lime

KAUST Repository

Kirchheim, A. P.; Fernà ndez-Altable, V.; Monteiro, P. J. M.; Dal Molin, D. C. C.; Casanova, I.

2009-01-01

Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) have been used to study the microstructural changes and phase development that take place during the hydration of cubic (pure) and orthorhombic (Na-doped) tricalcium aluminate (C3A) and gypsum in the absence and presence of lime. The results demonstrate that important differences occur in the hydration of each C3A polymorph and gypsum when no lime is added; orthorhombic C3A reacts faster with gypsum than the cubic phase, forming longer ettringite needles; however, the presence of lime slows down the formation of ettringite in the orthorhombic sample. Additional rheometric tests showed the possible effects on the setting time in these cementitious mixes.

Analysis of cubic and orthorhombic C3A hydration in presence of gypsum and lime

KAUST Repository

Kirchheim, A. P.

2009-02-26

Field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) have been used to study the microstructural changes and phase development that take place during the hydration of cubic (pure) and orthorhombic (Na-doped) tricalcium aluminate (C3A) and gypsum in the absence and presence of lime. The results demonstrate that important differences occur in the hydration of each C3A polymorph and gypsum when no lime is added; orthorhombic C3A reacts faster with gypsum than the cubic phase, forming longer ettringite needles; however, the presence of lime slows down the formation of ettringite in the orthorhombic sample. Additional rheometric tests showed the possible effects on the setting time in these cementitious mixes.

Hydration Properties of Ground Granulated Blast-Furnace Slag (GGBS Under Different Hydration Environments

Directory of Open Access Journals (Sweden)

Shuhua LIU

2017-02-01

Full Text Available The hydration properties of various cementitious materials containing Ground Granulated Blast-furnace Slag (GGBS, two alkali-activated slag cements (AAS-1 and AAS-2 in which sodium silicate and sodium hydroxide act as alkaline activators respectively, supersulfated cement (SSC and slag Portland cement(PSC, are compared with ordinary Portland cement (OPC to investigate the effect of activating environment on the hydration properties in this study by determining the compressive strength of the pastes, the hydration heat of binders within 96 hours, and the hydration products at age of 28 days. The results show that C-S-H gels are the main hydrated products for all cementitious systems containing GGBS. Ca(OH2 is the hydration products of OPC and PSC paste. However, ettringite and gypsum crystals instead of Ca(OH2 are detected in SSC paste. Additionally, tobermorite, a crystalline C-S-H, and calcite are hydrated products in AAS-1. Tobermorite, cowlesite and calcite are hydrated products of AAS-2 as well. Based on strength results, AAS-1 paste exhibits the highest compressive strength followed by POC, PSC, SSC in order at all testing ages and AAS-2 give the lowest compressive strength except for the early age at 3 days, which is higher than SSC but still lower than PSC. From hydration heat analysis, alkalinity in the reaction solution is a vital factor influencing the initial hydration rate and the initial hydration rate from higher to lower is AAS-2, AAS-1, OPC, PSC and SSC. Although AAS possesses a faster reaction rate in the initial hours, cumulative hydration heat of AAS is comparably lower than that of OPC, but higher than those of PSC and SSC in turn, which indicates that the hydration heat of clinkers is much higher than that of slag.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14934

Properties and hydration of blended cements with steelmaking slag

International Nuclear Information System (INIS)

Kourounis, S.; Tsivilis, S.; Tsakiridis, P.E.; Papadimitriou, G.D.; Tsibouki, Z.

2007-01-01

The present research study investigates the properties and hydration of blended cements with steelmaking slag, a by-product of the conversion process of iron to steel. For this purpose, a reference sample and three cements containing up to 45% w/w steel slag were tested. The steel slag fraction used was the '0-5 mm', due to its high content in calcium silicate phases. Initial and final setting time, standard consistency, flow of normal mortar, autoclave expansion and compressive strength at 2, 7, 28 and 90 days were measured. The hydrated products were identified by X-ray diffraction while the non-evaporable water was determined by TGA. The microstructure of the hardened cement pastes and their morphological characteristics were examined by scanning electron microscopy. It is concluded that slag can be used in the production of composite cements of the strength classes 42.5 and 32.5 of EN 197-1. In addition, the slag cements present satisfactory physical properties. The steel slag slows down the hydration of the blended cements, due to the morphology of contained C 2 S and its low content in calcium silicates

Resorption Rate Tunable Bioceramic: Si, Zn-Modified Tricalcium Phosphate

Energy Technology Data Exchange (ETDEWEB)

Wei, Xiang [Iowa State Univ., Ames, IA (United States)

2006-01-01

This dissertation is organized in an alternate format. Several manuscripts which have already been published or are to be submitted for publication have been included as separate chapters. Chapter 1 is a general introduction which describes the dissertation organization and introduces the human bone and ceramic materials as bone substitute. Chapter 2 is the background and literature review on dissolution behavior of calcium phosphate, and discussion of motivation for this research. Chapter 3 is a manuscript entitled ''Si,Zn-modified tricalcium phosphate: a phase composition and crystal structure study'', which was published in ''Key Engineering Materials'' [1]. Chapter 4 gives more crystal structure details by neutron powder diffraction, which identifies the position for Si and Zn substitution and explains the stabilization mechanism of the structure. A manuscript entitled ''Crystal structure analysis of Si, Zn-modified Tricalcium phosphate by Neutron Powder Diffraction'' will be submitted to Biomaterials [2]. Chapter 5 is a manuscript, entitled ''Dissolution behavior and cytotoxicity test of Si, Zn-modified tricalcium phosphate'', which is to be submitted to Biomaterials [3]. This paper discusses the additives effect on the dissolution behavior of TCP, and cytotoxicity test result is also included. Chapter 6 is the study of hydrolysis process of {alpha}-tricalcium phosphate in the simulated body fluid, and the phase development during drying process is discussed. A manuscript entitled ''Hydrolysis of {alpha}-tricalcium phosphate in simulated body fluid and phase transformation during drying process'' is to be submitted to Biomaterials [4]. Ozan Ugurlu is included as co-authors in these two papers due to his TEM contributions. Appendix A is the general introduction of the materials synthesis, crystal structure and preliminary dissolution result. A manuscript entitled

Vibrational investigation of calcium-silicate cements for endodontics in simulated body fluids

Science.gov (United States)

Taddei, Paola; Modena, Enrico; Tinti, Anna; Siboni, Francesco; Prati, Carlo; Gandolfi, Maria Giovanna

2011-05-01

Calcium-silicate MTA (Mineral Trioxide Aggregate) cements have been recently developed for oral and endodontic surgery. This study was aimed at investigating commercial (White ProRoot MTA, White and Grey MTA-Angelus) and experimental (wTC-Bi) accelerated calcium-silicate cements with regards to composition, hydration products and bioactivity upon incubation for 1-28 days at 37 °C, in Dulbecco's Phosphate Buffered Saline (DPBS). Deposits on the surface of the cements and the composition changes during incubation were investigated by micro-Raman and ATR/FT-IR spectroscopy, and pH measurements. Vibrational techniques disclosed significant differences in composition among the unhydrated cements, which significantly affected the bioactivity as well as pH, and hydration products of the cements. After one day in DPBS, all the cements were covered by a more or less homogeneous layer of B-type carbonated apatite. The experimental cement maintained a high bioactivity, only slightly lower than the other cements and appears a valid alternative to commercial cements, in view of its adequate setting time properties. The bioactivity represents an essential property to favour bone healing and makes the calcium-silicate cements the gold standard materials for root-apical endodontic surgery.

Thermogravimetric study on the hydration of reactive magnesia and silica mixture at room temperature

International Nuclear Information System (INIS)

Jin, Fei; Al-Tabbaa, Abir

2013-01-01

Highlights: • The characteristics of reactive MgO vary significantly in terms of their impurity content and reactivity depending on their sources and calcination conditions. • The synthesis of magnesium silicate hydrate (MSH) is affected by the characteristics of the precursors, i.e., MgO and silica. • The reaction process in the MgO–SiO 2 –H 2 O system can be followed by TGA, and is essential to develop MSH-based materials. - Abstract: The synthesis of magnesium silicate hydrate (MSH), which has wide applications in both construction and environmental fields, has been studied for decades. However, it is known that the characteristics of magnesia (MgO) vary significantly depending on their calcination conditions, which is expected to affect their performance in the MgO–SiO 2 –H 2 O system. This paper investigated the effect of different MgO and silica sources on the formation of magnesium silicate hydrate (MSH) at room temperature. The hydration process was studied by mixing commercial reactive MgO and silica powders with water and curing for 1, 7 and 28 days. The hydration products were analysed with the help of X-ray diffraction (XRD) and thermogravimatric analysis (TGA). The results showed the continuous consumption of MgO and the existence of MSH and brucite and other minor phases such as magnesite and calcite. It is found that the Mg and Si sources have significant effect on the hydration process of MgO–SiO 2 –H 2 O system. The reaction degree is controlled by the availability of dissolved Mg and Si in the solution. The former is determined by the reactivity of MgO and the latter is related to the reactivity of the silica as well as the pH of the system

Structural Investigations of Portland Cement Components, Hydration, and Effects of Admixtures by Solid-State NMR Spectroscopy

DEFF Research Database (Denmark)

Skibsted, Jørgen Bengaard; Andersen, Morten D.; Jakobsen, Hans Jørgen

2006-01-01

for the C-S-H phase formed during hydration. It will be demonstrated that Al3+ and flouride guest-ions in the anhydrous and hydrated calcium silicates can be studied in detail by 27Al and 19F MAS NMR, thereby providing information on the local structure and the mechanisms for incorporation of these ions......Solid-state, magic-angle spinning (MAS) NMR spectroscopy represents a valuable tool for structural investigations on the nanoscale of the most important phases in anhydrous and hydrated Portland cements and of various admixtures. This is primarily due to the fact that the method reflects the first......- and second-coordination spheres of the spin nucleus under investigation while it is less sensitive to long-range order. Thus, crystalline as well as amorphous phases can be detected in a quantitative manner by solid-state NMR. In particular the structure of the calcium-silicate-hydrate (C-S-H) phase have...

Hydration and leaching characteristics of cement pastes made from electroplating sludge.

Science.gov (United States)

Chen, Ying-Liang; Ko, Ming-Sheng; Lai, Yi-Chieh; Chang, Juu-En

2011-06-01

The purpose of this study was to investigate the hydration and leaching characteristics of the pastes of belite-rich cements made from electroplating sludge. The compressive strength of the pastes cured for 1, 3, 7, 28, and 90 days was determined, and the condensation of silicate anions in hydrates was examined with the (29)Si nuclear magnetic resonance (NMR) technology. The leachabilities of the electroplating sludge and the hardened pastes were studied with the multiple toxicity characteristic leaching procedure (MTCLP) and the tank leaching test (NEN 7345), respectively. The results showed that the electroplating sludge continued to leach heavy metals, including nickel, copper, and zinc, and posed a serious threat to the environment. The belite-rich cement made from the electroplating sludge was abundant in hydraulic β-dicalcium silicate, and it performed well with regard to compressive-strength development when properly blended with ordinary Portland cements. The blended cement containing up to 40% the belite-rich cement can still satisfy the compressive-strength requirements of ASTM standards, and the pastes cured for 90 days had comparable compressive strength to an ordinary Portland cement paste. It was also found that the later hydration reaction of the blended cements was relatively more active, and high fractions of belite-rich cement increased the chain length of silicate hydrates. In addition, by converting the sludge into belite-rich cements, the heavy metals became stable in the hardened cement pastes. This study thus indicates a viable alternative approach to dealing with heavy metal bearing wastes, and the resulting products show good compressive strength and heavy-metal stability. Copyright © 2011 Elsevier Ltd. All rights reserved.

Role of Adsorption Phenomena in Cubic Tricalcium Aluminate Dissolution.

Science.gov (United States)

Myers, Rupert J; Geng, Guoqing; Li, Jiaqi; Rodríguez, Erich D; Ha, Juyoung; Kidkhunthod, Pinit; Sposito, Garrison; Lammers, Laura N; Kirchheim, Ana Paula; Monteiro, Paulo J M

2017-01-10

The workability of fresh Portland cement (PC) concrete critically depends on the reaction of the cubic tricalcium aluminate (C 3 A) phase in Ca- and S-rich pH >12 aqueous solution, yet its rate-controlling mechanism is poorly understood. In this article, the role of adsorption phenomena in C 3 A dissolution in aqueous Ca-, S-, and polynaphthalene sulfonate (PNS)-containing solutions is analyzed. The zeta potential and pH results are consistent with the isoelectric point of C 3 A occurring at pH ∼12 and do not show an inversion of its electric double layer potential as a function of S or Ca concentration, and PNS adsorbs onto C 3 A, reducing its zeta potential to negative values at pH >12. The S and Ca K-edge X-ray absorption spectroscopy (XAS) data obtained do not indicate the structural incorporation or specific adsorption of SO 4 2- on the partially dissolved C 3 A solids analyzed. Together with supporting X-ray ptychography and scanning electron microscopy results, a model for C 3 A dissolution inhibition in hydrated PC systems is proposed whereby the formation of an Al-rich leached layer and the complexation of Ca-S ion pairs onto this leached layer provide the key inhibiting effect(s). This model reconciles the results obtained here with the existing literature, including the inhibiting action of macromolecules such as PNS and polyphosphonic acids upon C 3 A dissolution. Therefore, this article advances the understanding of the rate-controlling mechanism in hydrated C 3 A and thus PC systems, which is important to better controlling the workability of fresh PC concrete.

Interaction of calcium silicate hydrates (C-S-H), the main components of cement, with alkaline chlorides, analogy with clays

International Nuclear Information System (INIS)

Viallis-Terrisse, H.

2000-01-01

This work, belonging to a more general study on the structure and reactivity of cement, deals with the experimental and theoretical analysis of the interaction of alkaline chlorides with calcium silicate hydrates (C-S-H), the main components of cement paste. The interaction of alkaline cations with C-S-H is interfacial, involving both electrostatic and surface complexation mechanisms. The C-S-H surface is constituted of silanol sites, partially dissociated due to the high pH of the interstitial solution. The calcium ions, present in large amounts in the equilibrium solution of C-S-H, constitute potential determining ions for the C-S-H surface. The alkaline ions seem to compete with calcium for the same surface sites. The adsorption isotherms show that caesium presents a better affinity than sodium and lithium for the C-S-H surface. Moreover, solid-state NMR suggests that caesium forms with the surface sites inner-sphere complexes, whereas sodium seems to keep its hydration sphere. These results are in agreement with zeta potential measurements, which let suppose a specific adsorption of caesium ions, and an indifferent behaviour of both other alkaline ions. A model for the C-S-H surface was proposed, from the electric double layer model, and mass action laws expressing the complexation of the different ionic species with the silanol sites. The whole study relies on a structural analogy with smectites, some clays presenting well-known cationic adsorption properties. The structural similarity between both minerals is enhanced by some similarities of reactivity, though significant behaviour differences could also be noted. (author)

A new aluminium-hydrate species in hydrated Portland cements characterized by 27Al and 29Si MAS NMR spectroscopy

International Nuclear Information System (INIS)

Andersen, Morten Daugaard; Jakobsen, Hans J.; Skibsted, Jorgen

2006-01-01

Recent 27 Al MAS NMR studies of hydrated Portland cements and calcium-silicate-hydrate (C-S-H) phases have shown a resonance from Al in octahedral coordination, which cannot be assigned to the well-known aluminate species in hydrated Portland cements. This resonance, which exhibits the isotropic chemical shift δ iso = 5.0 ppm and the quadrupole product parameter P Q = 1.2 MHz, has been characterized in detail by 27 Al MAS and 27 Al{ 1 H} CP/MAS NMR for different hydrated white Portland cements and C-S-H phases. These experiments demonstrate that the resonance originates from an amorphous or disordered aluminate hydrate which contains Al(OH) 6 3- or O x Al(OH) 6-x (3+x)- units. The formation of the new aluminate hydrate is related to the formation of C-S-H at ambient temperatures, however, it decomposes by thermal treatment at temperatures of 70-90 o C. From the experiments in this work it is proposed that the new aluminate hydrate is either an amorphous/disordered aluminate hydroxide or a calcium aluminate hydrate, produced as a separate phase or as a nanostructured surface precipitate on the C-S-H phase. Finally, the possibilities of Al 3+ for Ca 2+ substitution in the principal layers and interlayers of the C-S-H structure are discussed

The Internal Recycle Reactor Enhances Porous Calcium Silicate Hydrates to Recover Phosphorus from Aqueous Solutions

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Wei Guan

2017-01-01

Full Text Available In this experiment, the porous calcium silicate hydrates (P-CSHs were prepared via a hydrothermal method and then modified by polyethylene glycol (PEG. The modified P-CSHs combined with an internal recycle reactor could successfully recover the phosphorus from electroplating wastewater. The modified P-CSHs were characterized by X-ray diffraction (XRD, N2 adsorption-desorption isotherms, and Fourier transform infrared spectroscopy (FT-IR. After compared with different samples, the modified P-CSHs-PEG2000 sample had larger specific surface area of 87.48 m2/g and higher pore volume of 0.33 cm3/g, indicating a high capacity for phosphorus recovery. In the process of phosphorus recovery, the pH value of solution was increased to 9.5, which would enhance the recovery efficiency of phosphorus. The dissolution rate of Ca2+ from P-CSH-PEG2000 was fast, which was favorable for phosphorus precipitation and phosphorus recovery. The effects of initial concentration of phosphorus, P-CSHs-PEG2000 dosage, and stirring speed on phosphorus recovery were analyzed, so the optimal operation conditions for phosphorus recovery were obtained. The deposition was analyzed by XRD, N2 adsorption-desorption, and SEM techniques; it was indicated that the pore volume and surface area of the P-CSHs-PEG2000 were significantly reduced, and the deposition on the surface of P-CSHs-PEG2000 was hydroxyapatite.

Physico-chemical and thermochemical studies of the hydrolytic conversion of amorphous tricalcium phosphate into apatite

International Nuclear Information System (INIS)

Somrani, Saida; Banu, Mihai; Jemal, Mohamed; Rey, Christian

2005-01-01

The conversion of amorphous tricalcium phosphate with different hydration ratio into apatite in water at 25 deg. C has been studied by microcalorimetry and several physical-chemical methods. The hydrolytic transformation was dominated by two strong exothermic events. A fast, relatively weak, wetting process and a very slow but strong heat release assigned to a slow internal rehydration and the crystallization of the amorphous phase into an apatite. The exothermic phenomenon related to the rehydration exceeded the crystalline transformation enthalpy. Rehydration occurred before the conversion of the amorphous phase into apatite and determined the advancement of the hydrolytic reaction. The apatitic phases formed evolved slightly with time after their formation. The crystallinity increased whereas the amount of HPO 4 2- ion decreased. These data allow a better understanding of the behavior of biomaterials involving amorphous phases such as hydroxyapatite plasma-sprayed coatings

Bone regeneration of calvarial defect using marine calcareous-derived beta-tricalcium phosphate macrospheres

Directory of Open Access Journals (Sweden)

Joshua Chou

2014-02-01

Full Text Available The aim of this study was to examine the bone regeneration properties of beta-tricalcium phosphate hydrothermally converted from foraminifera carbonate exoskeleton in the repair of rat calvarial defect. These natural materials possess unique interconnected porous network with uniform pore size distribution, which can be potentially advantageous. In total, 20 adult male Wistar rats received full-thickness calvarial defect with a diameter of 5 mm. The rate of newly formed bone was measured radiologically by X-ray and micro-computed tomography and by histologic examination. After 2 weeks, the beta-tricalcium phosphate group exhibited full closure of the defect site, while control group remained unrestored at the end of the 6-week experimentation. It was observed that the newly regenerated bone thickened over the course of the experiment in the beta-tricalcium phosphate group. No soft tissue reaction was observed around the beta-tricalcium phosphate implant and the rats remained healthy. These results showed that repair of the calvarial defect can be achieved by biomimetic beta-tricalcium phosphate macrospheres, which hold potential for application as bone grafts for bone augmentation surgeries.

Regulation of physicochemical properties, osteogenesis activity, and fibroblast growth factor-2 release ability of β-tricalcium phosphate for bone cement by calcium silicate

International Nuclear Information System (INIS)

Su, Ching-Chuan; Kao, Chia-Tze; Hung, Chi-Jr; Chen, Yi-Jyun; Huang, Tsui-Hsien; Shie, Ming-You

2014-01-01

β-Tricalcium phosphate (β-TCP) is an osteoconductive material. For this research we have combined it with a low degradation calcium silicate (CS) to enhance its bioactive and osteostimulative properties. To check its effectiveness, a series of β-TCP/CS composites with different ratios were prepared to make new bioactive and biodegradable biocomposites for bone repair. Formation of bone-like apatite, the diametral tensile strength, and weight loss of composites were considered before and after immersion in simulated body fluid (SBF). In addition, we also examined the effects of fibroblast growth factor-2 (FGF-2) released from β-TCP/CS composites and in vitro human dental pulp cell (hDPC) and studied its behavior. The results showed that the apatite deposition ability of the β-TCP/CS composites was enhanced as the CS content was increased. For composites with more than 50% CS contents, the samples were completely covered by a dense bone-like apatite layer. At the end of the immersion point, weight losses of 19%, 24%, 33%, 42%, and 51% were observed for the composites containing 0%, 30%, 50%, 70% and 100% β-TCP cements, respectively. In vitro cell experiments show that the CS-rich composites promote human dental pulp cell (hDPC) proliferation and differentiation. However, when the CS quantity in the composite is less than 70%, the amount of cells and osteogenesis protein of hDPCs was stimulated by FGF-2 released from β-TCP/CS composites. The combination of FGF-2 in degradation of β-TCP and osteogenesis of CS gives a strong reason to believe that these calcium-based composite cements may prove to be promising bone repair materials. - Highlights: • CS improved physicochemical properties and osteogenic activity of β-TCP. • The higher the CS in the cement, the shorter the setting time and the higher the DTS. • The cell behavior was stimulated by FGF-2 released from composite containing 50% CS. • β-TCP/CS composite with FGF-2 has optimal properties for

Immobilisation of heavy metal in cement-based solidification/stabilisation: A review

International Nuclear Information System (INIS)

Chen, Q.Y.; Tyrer, M.; Hills, C.D.; Yang, X.M.; Carey, P.

2009-01-01

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C 3 S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H + attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition of C 3 S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of 29 Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research on the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique

Hydration products of lime-metakaolin pastes at ambient temperature with ageing

Energy Technology Data Exchange (ETDEWEB)

Gameiro, A., E-mail: agameiro@lnec.pt [National Laboratory of Civil Engineering, Materials Department, Av. do Brasil, 101, 1700 Lisbon (Portugal); Santos Silva, A., E-mail: ssilva@lnec.pt [National Laboratory of Civil Engineering, Materials Department, Av. do Brasil, 101, 1700 Lisbon (Portugal); Veiga, R., E-mail: rveiga@lnec.pt [National Laboratory of Civil Engineering, Buildings Department, Av. do Brasil, 101, 1700 Lisbon (Portugal); Velosa, A., E-mail: avelosa@ua.pt [Department of Civil Engineering, Geobiotec, University of Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro (Portugal)

2012-05-10

Highlights: Black-Right-Pointing-Pointer We study the compounds formed in lime/MK blended pastes and their stability over time. Black-Right-Pointing-Pointer Different mixes of lime/MK pastes show different reaction kinetics during curing time, being the pozzolanic compounds formed directly proportional to the lime by MK replacement. Black-Right-Pointing-Pointer Some pozzolanic products are found to be unstable during the hydration reaction employed in our study. - Abstract: Mortars constituted of lime mixtures with pozzolanic additions have been extensively used in the past for the construction of historic and traditional buildings. This paper presents the results of blended pastes of lime and metakaolin (MK), namely compounds formed and their stability over time. This research is part of an extensive study aiming at the formulation of lime based mortars for restoration purposes. It has been shown for several years that MK has been applied in inorganic binders due to its capacity to react vigorously with calcium hydroxide (CH). In the presence of water originating a series of major hydrated phases, namely tetra calcium aluminate hydrate (C{sub 4}AH{sub 13}), calcium silicates hydrates (CSH) and calcium aluminium silicate hydrates (stratlingite - C{sub 2}ASH{sub 8}). Several blended pastes of lime and MK, with different substitution rates of lime by MK (wt%) were prepared and cured at a temperature of 20 Degree-Sign C and relative humidity RH > 95%. The phase composition of the formed hydrated phases was determined by X-ray diffraction (XRD) and simultaneous thermal analysis (TG-DTA). The obtained results showed that lime/MK pastes compositions displayed different reaction kinetics during curing time, being the pozzolanic products content directly proportional to the substitution rate of lime by MK. Also, a relationship between the increase stratlingite content and the MK substitution rate of lime by MK was found.

Preparation of micro-porous bioceramic containing silicon-substituted hydroxyapatite and beta-tricalcium phosphate.

Science.gov (United States)

Fuh, Lih-Jyh; Huang, Ya-Jing; Chen, Wen-Cheng; Lin, Dan-Jae

2017-06-01

Dimensional instability caused by sintering shrinkage is an inevitable drawback for conventional processing of hydroxyapatite (HA). A new preparation method for biphasic calcium phosphates was developed to increase micro pores and biodegradation without significant dimensional change. Powder pressed HA discs, under 100MPa, were immersed in a colloidal mixture of tetraethoxysilane (TEOS) and ammonium hydroxide for 10min, followed by drying, and then were sintered at 900°C, 1050°C, and 1200°C, respectively. Comparing with pure HA discs, the newly prepared product sintered up to 1200°C contained silicon substituted HA, beta-tricalcium phosphate, and calcium silicate with better micro-porosity, high specific surface area, less sintering shrinkage and the strength maintained. The cytocompatibility test demonstrated a better viability for D1 mice stem cells cultured on TEOS treated HA for 14days compared to the pure HA. This simple TEOS sol-gel pretreatment has the potential to be applied to any existing manufacturing process of HA scaffold for better control of sintering shrinkage, create micropores, and increase biodegradation. Copyright © 2017 Elsevier B.V. All rights reserved.

Topotactic conversion of β-helix-layered silicate into AST-type zeolite through successive interlayer modifications.

Science.gov (United States)

Asakura, Yusuke; Takayama, Ryosuke; Shibue, Toshimichi; Kuroda, Kazuyuki

2014-02-10

AST-type zeolite with a plate morphology can be synthesized by topotactic conversion of a layered silicate (β-helix-layered silicate; HLS) by using N,N-dimethylpropionamide (DPA) to control the layer stacking of silicate layers and the subsequent interlayer condensation. Treatment of HLS twice with 1) hydrochloric acid/ethanol and 2) dimethylsulfoxide (DMSO) are needed to remove interlayer hydrated Na ions and tetramethylammonium (TMA) ions in intralayer cup-like cavities (intracavity TMA ions), both of which are introduced during the preparation of HLS. The utilization of an amide molecule is effective for the control of the stacking sequence of silicate layers. This method could be applicable to various layered silicates that cannot be topotactically converted into three-dimensional networks by simple interlayer condensation by judicious choice of amide molecules. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructure engineering of Portland cement pastes and mortars through addition of ultrafine layer silicates

DEFF Research Database (Denmark)

Lindgreen, Holger; Geiker, Mette; Krøyer, Hanne

2008-01-01

Pozzolanic submicron-sized silica fume and the non-pozzolanic micron- and nano-sized layer silicates (clay minerals) kaolinite, smectite and palygorskite have been used as additives in Portland cement pastes and mortars. These layer silicates have different particle shape (needles and plates......), surface charge, and size (micron and nano). The structure of the resulting cement pastes and mortars has been investigated by atomic force microscopy (AFM), helium porosimetry, nitrogen adsorption (specific surface area and porosity), low-temperature calorimetry (LTC) and thermal analysis. The main result...... is that the cement paste structure and porosity can be engineered by addition of selected layer silicates having specific particle shapes and surface properties (e.g., charge and specific surface area). This seems to be due to the growth of calcium-silicate hydrates (C-S-H) on the clay particle surfaces...

Uptake of CrO42- ions by Fe-treated tri-calcium phosphate

International Nuclear Information System (INIS)

Serrano G, J.; Ramirez S, J. L.; Bonifacio M, J.; Granados C, F.; Badillo A, V. E.

2010-01-01

CrO 4 2- ion adsorption of Fe-treated tri-calcium phosphate was studied by batch experiments as a function of contact time, initial concentration of metal ion and temperature. Adsorption results showed that at ph 5.5 and 1.0 x 10 -4 M chromium concentration the adsorption capacity of Fe-treated tri-calcium phosphate for CrO 4 2- ions was 7.10 x 10 -3 mmol/g. Chromium adsorption data on Fe-treated tri-calcium phosphate at various initial concentration fitted the Freundlich isotherm. By temperature studies the thermodynamic parameters ΔH 0 , ΔG 0 and ΔS 0 were estimated and the obtained results showed that the adsorption reaction was endothermic and spontaneous. (Author)

Strength, leachability and microstructure characteristics of cement-based solidified plating sludge

International Nuclear Information System (INIS)

Asavapisit, Suwimol; Naksrichum, Siripat; Harnwajanawong, Naraporn

2005-01-01

The solidification of the stabilized zinc-cyanide plating sludge was carried out using ordinary Portland cement (OPC) and pulverized fuel ash (PFA) as solidification binders. The plating sludge were used at the level of 0%, 10%, 20% and 30% dry weight, and PFA was used to replace OPC at 0%, 10%, 20% and 30% dry weight, respectively. Experimental results showed that a significant reduction in strength was observed when the plating sludge was added to both the OPC and OPC/PFA binders, but the negative effect was minimized when PFA was used as part substitute for OPC. SEM observation reveals that the deposition of the plating sludge on the surface of the clinkers and PFA could be the cause for hydration retardation. In addition, calcium zinc hydroxide hydrate complex and the unreacted di- and tricalcium silicates were the major phases in X-ray diffraction (XRD) patterns of the solidified plating waste hydrated for 28 days, although the retardation effect on hydration reactions but Cr concentration in toxicity characteristic leaching procedure (TCLP) leachates was lower than the U.S. EPA regulatory limit

Hydration kinetics of cement composites with varying water-cement ratio using terahertz spectroscopy

Science.gov (United States)

Ray, Shaumik; Dash, Jyotirmayee; Devi, Nirmala; Sasmal, Saptarshi; Pesala, Bala

2015-03-01

Cement is mixed with water in an optimum ratio to form concrete with desirable mechanical strength and durability. The ability to track the consumption of major cement constituents, viz., Tri- and Dicalcium Silicates (C3S, C2S) reacting with water along with the formation of key hydration products, viz., Calcium-Silicate-Hydrate (C-S-H) which gives the overall strength to the concrete and Calcium Hydroxide (Ca(OH)2), a hydration product which reduces the strength and durability, using an efficient technique is highly desirable. Optimizing the amount of water to be mixed with cement is one of the main parameters which determine the strength of concrete. In this work, THz spectroscopy has been employed to track the variation in hydration kinetics for concrete samples with different water-cement ratios, viz., 0.3, 0.4, 0.5 and 0.6. Results show that for the sample with water-cement ratio of 0.3, significant amount of the C3S and C2S remain unreacted even after the initial hydration period of 28 days while for the cement with water-cement ratio of 0.6, most of the constituents get consumed during this stage. Analysis of the formation of Ca(OH)2 has been done which shows that the concrete sample with water-cement ratio of 0.6 produces the highest amount of Ca(OH)2 due to higher consumption of C3S/C2S in presence of excess water which is not desirable. Samples with water-cement ratio of 0.4 and 0.5 show more controlled reaction during the hydration which can imply formation of an optimized level of desired hydration products resulting in a more mechanically strong and durable concrete.

Real-time high-resolution X-ray imaging and nuclear magnetic resonance study of the hydration of pure and Na-doped C3A in the presence of sulfates

KAUST Repository

Kirchheim, A. P.

2011-02-21

This study details the differences in real-time hydration between pure tricalcium aluminate (cubic C3A or 3CaO·Al2O 3) and Na-doped tricalcium aluminate (orthorhombic C3A or Na2Ca8Al6O18), in aqueous solutions containing sulfate ions. Pure phases were synthesized in the laboratory to develop an independent benchmark for the reactions, meaning that their reactions during hydration in a simulated early age cement pore solution (saturated with respect to gypsum and lime) were able to be isolated. Because the rate of this reaction is extremely rapid, most microscopy methods are not adequate to study the early phases of the reactions in the early stages. Here, a high-resolution full-field soft X-ray imaging technique operating in the X-ray water window, combined with solution analysis by 27Al nuclear magnetic resonance (NMR) spectroscopy, was used to capture information regarding the mechanism of C3A hydration during the early stages. There are differences in the hydration mechanism between the two types of C3A, which are also dependent on the concentration of sulfate ions in the solution. The reactions with cubic C3A (pure) seem to be more influenced by higher concentrations of sulfate ions, forming smaller ettringite needles at a slower pace than the orthorhombic C3A (Na-doped) sample. The rate of release of aluminate species into the solution phase is also accelerated by Na doping. © 2011 American Chemical Society.

Synthesis and characterization of silica gel from siliceous sands of southern Tunisia

Directory of Open Access Journals (Sweden)

Ali Sdiri

2014-09-01

Full Text Available The present work aimed to achieve valorization of Albian sands for the preparation of sodium silicates that are commonly used as a precursor to prepare silica gel. A siliceous sand sample was mixed with sodium carbonate and heated at a high temperature (1060 °C to prepare sodium silicates. The sodium silicates were dissolved in distilled water to obtain high quality sodium silicate solution. Hydrochloric acid was then slowly added to the hydrated sodium silicates to obtain silica gel. The collected raw siliceous sands, as well as the prepared silica gels, were characterized by different techniques, such as X-ray fluorescence (XRF, X-ray diffraction (XRD, scanning electron microscopy (SEM and thermal analysis (DSC. XRF confirmed that the detrital sand deposits of southern Tunisia contain high amounts of silica, with content ranging from 88.8% to 97.5%. The internal porosity varied between 17% and 22%, and the specific surface area was less than 5 m2/g. After the treatment described above, it was observed that the porosity of the obtained silica gel reached 57% and the specific surface area exceeded 340 m2/g. Nitrogen adsorption isotherms showed that the prepared silica gels are microporous and mesoporous materials with high adsorption capacities. These results suggest that the obtained silica gels are promising materials for numerous environmental applications.

The composition of cement hydrating at 60 deg C from synchrotron radiation

International Nuclear Information System (INIS)

Auld, J.; Turner, K.; Thorogood, G.J.; Ball, C.J.; Aldridge, L.P.; Taylor, J.C.

2002-01-01

Full text: Cement consists of 5 phases C3S, C2S, C3A, C4AF (where C denotes CaO, S denotes SiO 2 , A denotes AI 2 O 3 and F denotes Fe 2 O 3 ) and gypsum. When cement hydrates it forms an amorphous calcium silicate hydrate (C-S-H) as well as the crystalline ettringite and calcium hydroxide. The x-ray diffraction pattern of the hydrated cement is difficult to interpret because of its complexity. In addition, the overlapping lines from the remaining cement compounds make it difficult to quantify the amount of the crystalline components present. Using Rietveld analysis we have been able to interpret the patterns obtained from synchrotron x-ray diffraction patterns obtained at the Photon Factory at the Australian National Beamline Facility using BIGDIF. The changes in the composition of the hydrated cement paste were determined as a function of time during hydration at 60 deg C. Copyright (2002) Australian X-ray Analytical Association Inc

Effect of polymers on the nanostructure and on the carbonation of calcium silicate hydrates: a scanning transmission X-ray microscopy study

KAUST Repository

Ha, J.

2011-09-07

This study investigated the effects of organic polymers (polyethylene glycol and hexadecyltrimethylammonium) on structures of calcium silicate hydrates (C-S-H) which is the major product of Portland cement hydration. Increased surface areas and expansion of layers were observed for all organic polymer modified C-S-H. The results from attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopic measurements also suggest lowered water contents in the layered structures for the C-S-H samples that are modified by organic polymers. Scanning transmission X-ray microscopy (STXM) results further supports this observation. We also observed difference in the extent of C-S-H carbonation due to the presence of organic polymers. No calcite formed in the presence of HDTMA whereas formation of calcite was observed with C-S-H sample modified with PEG. We suggest that the difference in the carbonation reaction is possibly due to the ease of penetration and diffusion of the CO 2. This observation suggests that CO 2 reaction strongly depends on the presence of organic polymers and the types of organic polymers incorporated within the C-S-H structure. This is the first comprehensive study using STXM to quantitatively characterize the level of heterogeneity in cementitious materials at high spatial and spectral resolutions. The results from BET, XRD, ATR-FTIR, and STXM measurements are consistent and suggest that C-S-H layer structures are significantly modified due to the presence of organic polymers, and that the chemical composition and structural differences among the organic polymers determine the extent of the changes in the C-S-H nanostructures as well as the extent of carbonation reaction. © 2011 Springer Science+Business Media, LLC.

Superplasticizer function and sorption in high performance cement based grouts

International Nuclear Information System (INIS)

Onofrei, M.; Gray, M.N.; Roe, L.H.

1991-08-01

This report describes laboratory studies undertaken to determine interactions between the main components of high-performance cement-based grout. These interactions were studied with the grouts in both their unset and hardened states with the specific intention of determining the following: the mechanistic function of superplasticizer; the phase of residence of the superplasticizer in hardened materials; and the permanence of the superplasticizer in hardened grouts. In unset pastes attempts were made to extract superplasticizer by mechanical processes. In hardened grout the superplasticizer was leached from the grouts. A microautoradiographic method was developed to investigate the phases of residence of superplasticizer in hardened grouts and confirm the inferences from the leaching studies. In hardened grout the superplasticizer was located on the hydrated phases formed during the early stages of cement hydration. These include tricalcium aluminate hydrates and tricalcium silicate phases. There is some tendency for the superplasticizer to sorb on ettringite. The presence of superplasticizer did not coincide with the locations of unreacted silica fume and high silica content phases such as C 2 S-H. The observations explain the findings of the studies of unset pastes which also showed that the sorption of superplasticizer is likely to be enhanced with increased mixing water content and, hence, distribution in and exposure to the hydration reaction surfaces in the grout. Superplasticizer can be leached in very small quantities from the hardened grouts. Rapid release takes place from the unsorbed superplasticizer contained in the accessible pore space. Subsequent release likely occurs with dissolution of the cement phases and the exposure of isolated pores to groundwater. (au) (37 refs.)

Sorption of caesium and strontium onto calcium silicate hydrate in saline groundwater

International Nuclear Information System (INIS)

Sugiyama, D.; Fujita, T.

2005-01-01

Full text of publication follows: In the concept for radioactive waste disposal in Japan, cement is a potential waste packaging and backfilling material and is expected to provide chemical containment. The sorption of radionuclides onto cement materials, which controls the aqueous concentrations of elements in the pore-water, is a very important parameter when considering the release of radionuclides from the near field of a cementitious radioactive waste repository. Many safety assessment calculations currently assume radionuclide retardation as linear sorption equilibrium and describe it with a distribution ratio (R d value). In this study, the sorption mechanism is discussed by measuring the sorption isotherm of caesium, strontium (10 -5 ∼ 10 -2 mol dm -3 ) and sodium (10 -4 ∼ 10 -1 mol dm -3 ) onto Calcium Silicate Hydrate (C-S-H gel, Ca/Si 0.65 ∼ 1.2) at a liquid:solid ratio of 100:1, to support the assumption. In addition, the competitive sorption between caesium or strontium, and sodium is studied by sorption measurements using a range of sodium chloride concentration to simulate different ionic strengths in saline groundwater. The initial and equilibrated aqueous compositions were measured in the sorption experiments and it was found that caesium, strontium and sodium were sorbed by substitution for Ca in C-S-H phases by examining the mass balance. Based on the experimental results, we propose a modelling approach in which the ion-exchange model is employed and the presence of some calcium sites with different ion-exchange log K values in C-S-H is assumed by considering the composition and the structure of C-S-H. The modelling calculation results predict the measured Rd values well and also describe the competition of sorption of caesium or strontium, and sodium in the experiments. The log K values for sorption of each cation element decreased as Ca/Si ratio of C-S-H gel increased. This agrees with the trend that C-S-H gel is negatively charged at low

A thermodynamic approach to the hydration of sulphate-resisting Portland cement

International Nuclear Information System (INIS)

Lothenbach, Barbara; Wieland, Erich

2006-01-01

A thermodynamic approach is used to model changes in the hydrate assemblage and the composition of the pore solution during the hydration of calcite-free and calcite-containing sulphate-resisting Portland cement CEM I 52.5 N HTS. Modelling is based on thermodynamic data for the hydration products and calculated hydration rates for the individual clinker phases, which are used as time-dependent input parameters. Model predictions compare well with the composition of the hydrate assemblage as observed by TGA and semi-quantitative XRD and with the experimentally determined compositions of the pore solutions. The calculations show that in the presence of small amounts of calcite typically associated with Portland cement, C-S-H, portlandite, ettringite and calcium monocarbonate are the main hydration products. In the absence of calcite in the cement, however, siliceous hydrogarnet instead of calcium monocarbonate is observed to precipitate. The use of a higher water-to-cement ratio for the preparation of a calcite-containing cement paste has a minor effect on the composition of the hydrate assemblage, while it significantly changes the composition of the pore solution. In particular, lower pH value and higher Ca concentrations appear that could potentially influence the solubility and uptake of heavy metals and anions by cementitious materials

Influence of pozzolana on C4AF hydratio n and the effects of chloride and sulfate io ns on the hydrates formed

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RIMVYDAS KAMINSKAS

2011-09-01

Full Text Available This study investigated the influence of natural pozzolana additive on the hydration of C4AF (aluminoferrite and the effects of chloride and sulfate ions on the hydrates formed. In the samples, 25% (by weight of the C4AF was replaced with pozzolana. The mixture was then hardened for 28 days in water, soaked in a saturated NaCl solution for 3 months, and then soaked in a 5% Na2SO4 solution for 3 months at 20°C. It is estimated that under normal conditions, pozzolana additive accelerates the formation of CO32-–AFm (monocarboaluminate and gibbsite, however, impede the formation of cubic aluminum hydrates. Also, part of the amorphous SiO2 penetrates into the structure of hydrates of C4AF and initiates the formation of hydrated alumino-silicate (gismondine. Monocarboaluminate affected by NaCl becomes unstable and takes part in reactions producing Ca2Al(OH6Cl·2H2O (hydrocalumite-M. After samples were transferred from a saturated NaCl solution to a 5% Na2SO4 solution, hydrocalumite-M was the source of aluminates for the formation of ettringite. In samples with pozzolana additive, the hydrated alumino-silicate and gibbsite compounds that were formed remained stable in an environment containing chloride and sulfate ions and retarded the corrosion reaction of C4AF hydrates.

A transmission electron microscopy study of radiation damages to β-dicalcium (Ca{sub 2}SiO{sub 4}) and M3-tricalcium (Ca{sub 3}SiO{sub 5}) orthosilicates

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Noirfontaine, Marie-Noëlle de; Dunstetter, Frédéric [Laboratoire des Solides Irradiés, Ecole Polytechnique, CNRS UMR 7642, CEA-DSM-IRAMIS, Université Paris Saclay, F-91128 Palaiseau Cedex (France); Courtial, Mireille [Laboratoire des Solides Irradiés, Ecole Polytechnique, CNRS UMR 7642, CEA-DSM-IRAMIS, Université Paris Saclay, F-91128 Palaiseau Cedex (France); Université d' Artois, 1230 Rue de l' Université, CS 20819, F-62408 Béthune (France); Signes-Frehel, Marcel [Laboratoire des Solides Irradiés, Ecole Polytechnique, CNRS UMR 7642, CEA-DSM-IRAMIS, Université Paris Saclay, F-91128 Palaiseau Cedex (France); Wang, Guillaume [Laboratoire Matériaux et Phénomènes Quantiques, CNRS UMR 7162, Université Paris Diderot, F-75205 Paris Cedex 13 (France); Gorse-Pomonti, Dominique, E-mail: dominique.gorse-pomonti@polytechnique.edu [Laboratoire des Solides Irradiés, Ecole Polytechnique, CNRS UMR 7642, CEA-DSM-IRAMIS, Université Paris Saclay, F-91128 Palaiseau Cedex (France)

2016-01-15

In this paper, we present results of a first study of electron radiation damages to β-dicalcium silicate (Ca{sub 2}SiO{sub 4}:C{sub 2}S) and M3-tricalcium silicate (Ca{sub 3}SiO{sub 5}:C{sub 3}S) in a Transmission Electron Microscope. Electron irradiation is used here as a means to bring to light a difference of reactivity under the electron beam between these two complex ceramic oxides, keeping in mind that C{sub 3}S reacts faster with water than C{sub 2}S and that this property remains unexplained, owing to the complex structural characteristics of these ceramics which have not yet been fully elucidated. The following results were obtained by coupling TEM imaging and EDS analysis: i) Rapid decomposition of both silicate particles into CaO nano-crystals separated by (presumably SiO{sub 2}-rich) amorphous areas at low flux for both silicates; ii) once reached a threshold electron flux, formation of an amorphous crater in both silicates, fully calcium-depleted in C{sub 3}S but never in C{sub 2}S; iii) significant post-mortem structural evolution of the craters that at least partially recrystallize in C{sub 2}S, to be compared to the quasi frozen damaged area in C{sub 3}S; iv) hole drilling at high flux but only in C{sub 3}S once reached a threshold flux, ϕ{sub th} ∼ 7.9 × 10{sup 21} e{sup −} cm{sup −2} s{sup −1}, of the same order of magnitude than previously estimated in a number of ceramic materials, whereas C{sub 2}S still amorphizes under the electron beam for a flux as high as 2.2 × 10{sup 22} e{sup −} cm{sup −2} s{sup −1}. The radiation damages and their post–mortem evolution differ largely between C{sub 2}S and C{sub 3}S. We attempted to relate the obtained results, and especially the evolution of the Ca content in the damaged areas under the electron beam to the available structural characteristics of these two orthosilicates. - Highlights: • TEM study of electron damages in β-dicalcium (C{sub 2}S), M3-tricalcium silicates

A Scanning Transmission X-ray Microscopy Study of Cubic and Orthorhombic C3A and Their Hydration Products in the Presence of Gypsum

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Vanessa Rheinheimer

2016-08-01

Full Text Available This paper shows the microstructural differences and phase characterization of pure phases and hydrated products of the cubic and orthorhombic (Na-doped polymorphs of tricalcium aluminate (C3A, which are commonly found in traditional Portland cements. Pure, anhydrous samples were characterized using scanning transmission X-ray microscopy (STXM, X-ray photoelectron spectroscopy (XPS and X-ray diffraction (XRD and demonstrated differences in the chemical and mineralogical composition as well as the morphology on a micro/nano-scale. C3A/gypsum blends with mass ratios of 0.2 and 1.9 were hydrated using a water/C3A ratio of 1.2, and the products obtained after three days were assessed using STXM. The hydration process and subsequent formation of calcium sulfate in the C3A/gypsum systems were identified through the changes in the LIII edge fine structure for Calcium. The results also show greater Ca LII binding energies between hydrated samples with different gypsum contents. Conversely, the hydrated samples from the cubic and orthorhombic C3A at the same amount of gypsum exhibited strong morphological differences but similar chemical environments.

Investigation of the swelling behavior of cationic exchange resins saturated with Na{sup +} ions in a C{sub 3}S paste

Energy Technology Data Exchange (ETDEWEB)

Lafond, E. [CEA, DEN, DTCD, SPDE, F-30207 Bagnols-sur-Cèze cedex (France); Cau Dit Coumes, C., E-mail: celine.cau-dit-coumes@cea.fr [CEA, DEN, DTCD, SPDE, F-30207 Bagnols-sur-Cèze cedex (France); Gauffinet, S. [UMR5209 Institut Carnot de Bourgogne, Université de Bourgogne Dijon, Faculté des Sciences Mirande, 9 Avenue Alain Savary, BP 47870, 21078 Dijon cedex (France); Chartier, D. [CEA, DEN, DTCD, SPDE, F-30207 Bagnols-sur-Cèze cedex (France); Le Bescop, P. [CEA, DEN, DPC, SECR, F-91192 Gif-sur-Yvette (France); Stefan, L. [AREVA, Back End Business Group, Dismantling & Services, 1 place Jean Millier, 92084 Paris La Défense (France); Nonat, A. [UMR5209 Institut Carnot de Bourgogne, Université de Bourgogne Dijon, Faculté des Sciences Mirande, 9 Avenue Alain Savary, BP 47870, 21078 Dijon cedex (France)

2015-03-15

Ion exchange resins (IERs) are widely used by the nuclear industry to decontaminate radioactive effluents. Spent products are usually encapsulated in cementitious materials. However, the solidified waste form can exhibit strong expansion, possibly leading to cracking, if the appropriate binder is not used. In this work, the interactions between cationic resins in the Na{sup +} form and tricalcium silicate are investigated during the early stages of hydration in order to gain a better understanding of the expansion process. It is shown that the IERs exhibit a transient swelling of small magnitude due to the decrease in the osmotic pressure of the external solution. This expansion, which occurs just after setting, is sufficient to damage the material which is poorly consolidated for several reasons: low degree of hydration, precipitation of poorly cohesive sodium-bearing C–S–H, and very heterogeneous microstructure with zones of high porosity.

On the swelling behavior of cationic exchange resins saturated with Na+ ions in a C3S paste

International Nuclear Information System (INIS)

Lafond, E.; Cau Dit Coumes, C.; Chartier, D.; Gauffinet, S.; Le Bescop, P.; Stefan, L.

2015-01-01

Ion exchange resins (IERs) are widely used in the nuclear industry to decontaminate radioactive effluents. Spent resins are usually encapsulated in cementitious materials. However, the solidified waste form can exhibit strong expansion, possibly leading to cracking, if the appropriate binder is not used. In this work, the interactions between cationic resins in the Na + form and tricalcium silicate are investigated during the early stages of hydration in order to gain a better understanding of the expansion process. It is shown that the IERs exhibit a transient swelling of small magnitude due to the decrease in the osmotic pressure of the external solution. This expansion, which occurs just after setting, is sufficient to damage the material which is poorly consolidated for several reasons: low degree of hydration, precipitation of poorly cohesive sodium-bearing C-S-H, and very heterogeneous microstructure with zones of high porosity. (authors)

Rietveld analysis, powder diffraction and cement

International Nuclear Information System (INIS)

Peterson, V.

2002-01-01

Full text: Phase quantification of cement is essential in its industrial use, however many methods are inaccurate and/or time consuming. Powder diffraction is one of the more accurate techniques used for quantitative phase analysis of cement. There has been an increase in the use of Rietveld refinement and powder diffraction for the analysis and phase quantification of cement and its components in recent years. The complex nature of cement components, existence of solid solutions, polymorphic variation of phases and overlapping phase peaks in diffraction patterns makes phase quantification of cements by powder diffraction difficult. The main phase in cement is alite, a solid solution of tricalcium silicate. Tricalcium silicate has been found to exist in seven modifications in three crystal systems, including triclinic, monoclinic, and rhombohedral structures. Hence, phase quantification of cements using Rietveld methods usually involves the simultaneous modelling of several tricalcium silicate structures to fit the complex alite phase. An industry ordinary Portland cement, industry and standard clinker, and a synthetic tricalcium silicate were characterised using neutron, laboratory x-ray and synchrotron powder diffraction. Diffraction patterns were analysed using full-profile Rietveld refinement. This enabled comparison of x-ray, neutron and synchrotron data for phase quantification of the cement and examination of the tricalcium silicate. Excellent Rietveld fits were achieved, however the results showed that the quantitative phase analysis results differed for some phases in the same clinker sample between various data sources. This presentation will give a short introduction about cement components including polymorphism, followed by the presentation of some problems in phase quantification of cements and the role of Rietveld refinement in solving these problems. Copyright (2002) Australian X-ray Analytical Association Inc

Characterization and chemical activity of Portland cement and two experimental cements with potential for use in dentistry.

Science.gov (United States)

Camilleri, J

2008-09-01

To evaluate the chemical activity of Portland cement and two other cement types with similar chemical composition to mineral trioxide aggregate with the aim of developing these cements for further applications in dentistry. The chemical composition of the three cement types namely Portland cement, calcium sulpho-aluminate cement and calcium fluoro-aluminate cement was evaluated by elemental analysis using energy dispersive analysis with X-ray under the scanning electron microscope and by X-ray diffraction analysis (XRD) to determine the phases. The constituents of the hydration reaction by-products were evaluated by XRD analysis of the set cements at 1, 7, 28 and 56 days and by analysis of the leachate by ion chromatography. The pH of both cements and leachate was determined at different time intervals. Cements admixed with micro-silica were also tested to determine the effect of micro-silica on the reaction by-products. All three cement types were composed of tricalcium silicate as the main constituent phase. The hydration reaction of Portland cement produced calcium hydroxide. However, this was not present in the other cements tested at all ages. Admixed micro-silica had little or no effect on the cements with regard to reaction by-products. The pH of all cements tested was alkaline. Both the experimental calcium sulpho-aluminate cement and calcium fluoro-aluminate cement had different hydration reactions to that of Portland cement even though calcium silicate was the major constituent element of both cement types. No calcium hydroxide was produced as a by-product to cement hydration. Micro-silica addition to the cement had no effect on the hydration reaction.

Post-extraction application of beta-tricalcium phosphate in alveolar socket

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M. Muñoz-Corcuera

2015-03-01

Full Text Available Aim The objective of this study was to assess the capacity of beta-tricalcium phosphate to facilitate bone formation in the socket and prevent post-extraction alveolar resorption. Materials and methods After premolar extraction in 16 patients, the sockets were filled with beta-tricalcium phosphate. Six months later, during the implant placement surgery, a trephine was used to harvest the bone samples which were processed for histological and histomorphometrical analyses. Data were gathered on patient, clinical, histological and histomorphometric variables at the extraction and implant placement sessions, using data collection forms and pathological reports. Results Clinical outcomes were satisfactory, the biomaterial was radio-opaque on X-ray. Histological study showed: partial filling with alveolar bone of appropriate maturation and mineralization for the healing time, osteoblastic activity and bone lacunae containing osteocytes. The biomaterial was not completely resorbed at six months. Conclusion Beta-tricalcium phosphate is a material capable of achieving preservation of the alveolar bone when it is positioned in the immediate post-extraction socket followed by suture; it also helps the formation of new bone in the socket. Further studies are needed comparing this technique with other available biomaterials, with growth factors and with sites where no alveolar preservation techniques are performed.

Incorporation of zinc into calcium silicate hydrates, Part I: formation of C-S-H(I) with C/S=2/3 and its isochemical counterpart gyrolite

International Nuclear Information System (INIS)

Stumm, Andreas; Garbev, Krassimir; Beuchle, Guenter; Black, Leon; Stemmermann, Peter; Nueesch, Rolf

2005-01-01

We have investigated the incorporation of zinc into both nanocrystalline and crystalline calcium silicate hydrates with starting C/S ratios of 2/3 (0.66). Zinc was added replacing calcium in the starting mixtures [Zn/(Zn+Ca)=0-1/4; 0-10 wt.% Zn], and the resultant phases were characterised using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), differential thermal analysis-thermogravimetry (DTA-TG) and environmental scanning electron microscopy (ESEM). In both groups of samples, increasing zinc content led to gradual structural changes, until eventually a second phase was formed. Zinc was incorporated to similar limits in both sets of samples. The thermal stability of the structures increased to a certain zinc content, beyond which there was structural destabilisation. Zinc incorporation is possible up to ∼6 wt.%. Our observations strongly indicate similar zinc incorporation mechanisms in both sample series, namely incorporation of zinc into the interlayer of C-S-H(I) and the X-sheet of gyrolite for nanocrystalline and crystalline samples, respectively

Interaction of dispersed polyvynil acetate with silicate in finishing materials

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Runova, R. F.

1996-12-01

Full Text Available This article focuses on the processes of interaction between calcium silicate hydrates and dispersed polyvinyl acetate in tight films with the aim of developing compounds meant for restoration and finishing works. The basis of this development relies on the concept concerning the determining role of the crystal-chemical factor of the silicate phase in the formation of organic-mineral compounds of increased durability. The characteristics of dispersed calcium silicate hydrates are portrayed. The preparation conditions, accounting for the synthesis of the product of submicrocrystalline structure, conforming with the stoichiometry CaO∙SiO₂ =0.8-2.0 have been determined. The interaction has been studied for compounds achieved by mixing ingredients in a rapid whirling mixer, and subjected to hardening at T=20+2 T. With the aid of XRD, DTA and Infra-Red Spectrometry methods the formation process of the sophisticated polymer silicate phase in the material was observed for a period of 90 days. The properties of the film were investigated and its high resistance against the influence of external factors was established. On this basis a conclusion concerning the quite high effectiveness of substituting portland cement with dispersed calcium silicate hydrate in polymer cement compounds has been made. White colour and other various special properties determine the suitability for repair and finishing works on facades of buildings.

Este artículo está orientado a estudiar los procesos de interacción entre los silicatos cálcicos hidratados y el acetato de polivinilo disperso en capas impermeables, con el objeto de desarrollar compuestos destinados para la restauración. El fundamento de estos estudios es determinar el papel que los factores cristaloquímicos de las fases silicato tienen en la formación de compuestos órganominerales de elevada durabilidad. Se han descrito las características de los silicatos cálcicos hidratados

Low-δD hydration rinds in Yellowstone perlites record rapid syneruptive hydration during glacial and interglacial conditions

Science.gov (United States)

Bindeman, Ilya N.; Lowenstern, Jacob B.

2016-01-01

Hydration of silicic volcanic glass forms perlite, a dusky, porous form of altered glass characterized by abundant “onion-skin” fractures. The timing and temperature of perlite formation are enigmatic and could plausibly occur during eruption, during post-eruptive cooling, or much later at ambient temperatures. To learn more about the origin of natural perlite, and to fingerprint the hydration waters, we investigated perlitic glass from several synglacial and interglacial rhyolitic lavas and tuffs from the Yellowstone volcanic system. Perlitic cores are surrounded by a series of conchoidal cracks that separate 30- to 100-µm-thick slivers, likely formed in response to hydration-induced stress. H2O and D/H profiles confirm that most D/H exchange happens together with rapid H2O addition but some smoother D/H variations may suggest separate minor exchange by deuterium atom interdiffusion following hydration. The hydrated rinds (2–3 wt% H2O) transition rapidly (within 30 µm, or by 1 wt% H2O per 10 µm) to unhydrated glass cores. This is consistent with quenched “hydration fronts” where H2O diffusion coefficients are strongly dependent on H2O concentrations. The chemical, δ18O, and δD systematics of bulk glass records last equilibrium between ~110 and 60 °C without chemical exchange but with some δ18O exchange. Similarly, the δ18O of water extracted from glass by rapid heating suggests that water was added to the glass during cooling at higher rates of diffusion at 60–110 °C temperatures, compared with values expected from extrapolation of high-temperature (>400 °C) experimental data. The thick hydration rinds in perlites, measuring hundreds of microns, preserve the original D/H values of hydrating water as a recorder of paleoclimate conditions. Measured δD values in perlitic lavas are −150 to −191 or 20–40 ‰ lower than glass hydrated by modern Yellowstone waters. This suggests that Yellowstone perlites record the low-δD signature

Effect of Graphene Oxide (GO on the Morphology and Microstructure of Cement Hydration Products

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Liguo Wang

2017-12-01

Full Text Available In this study, the effects of graphene oxide (GO on the microstructure of cement mortars were studied using scanning electron microscopy (SEM, thermogravimetric (TG, and X-ray diffraction (XRD techniques. Cement mortar samples with different proportions of GO (0.02, 0.04, 0.06, and 0.08 wt % based on the weight of cement were prepared. The test results showed that GO affected the crystallization of cement hydration products, C–S–H (calcium silicate hydrate is the main hydrate product and CH (calcium hydroxide. The morphology of hydration products changed with the increase of GO content. Furthermore, the results of XRD analyses showed that the diffraction peak intensity and the crystal grain size of CH (001, (100, (101, and (102 for GO samples increased considerably compared with the control sample. Based on the results, it can be understood that GO can modify the crystal surface of CH, leading to the formation of larger crystals.

Uptake of CrO{sub 4}{sup 2-} ions by Fe-treated tri-calcium phosphate

Energy Technology Data Exchange (ETDEWEB)

Serrano G, J.; Ramirez S, J. L.; Bonifacio M, J.; Granados C, F.; Badillo A, V. E., E-mail: juan.serrano@inin.gob.m [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

2010-07-01

CrO{sub 4}{sup 2-} ion adsorption of Fe-treated tri-calcium phosphate was studied by batch experiments as a function of contact time, initial concentration of metal ion and temperature. Adsorption results showed that at ph 5.5 and 1.0 x 10{sup -4} M chromium concentration the adsorption capacity of Fe-treated tri-calcium phosphate for CrO{sub 4}{sup 2-} ions was 7.10 x 10{sup -3} mmol/g. Chromium adsorption data on Fe-treated tri-calcium phosphate at various initial concentration fitted the Freundlich isotherm. By temperature studies the thermodynamic parameters {Delta}H{sup 0}, {Delta}G{sup 0} and {Delta}S{sup 0} were estimated and the obtained results showed that the adsorption reaction was endothermic and spontaneous. (Author)

Individual and combined effects of chloride, sulfate, and magnesium ions on hydrated Portland-cement paste

International Nuclear Information System (INIS)

Poole, T.S.; Wakeley, L.D.; Young, C.L.

1994-03-01

Ground water with a high concentration of magnesium ion is known to cause deterioration to portland cement concretes. A proposed mechanism for this deterioration process published previously involves an approximate 1:1 replacement of Ca ions by Mg ions in the crystalline phases of hydrated cement. The current study was undertaken to determine which ions, among magnesium, chloride, and sulfate, cause deterioration; whether their deleterious action is individual or interdependent; and to relate this mechanism of deterioration to the outlook for a 100-yr service life of concretes used in mass placements at the Waste Isolation Pilot Plant. Loss of Ca ion by cement pastes was found to be strongly related to the concentration of Mg ion in simulated ground-water solutions in which the paste samples were aged. This was true of both salt- containing and conventional cement pastes. No other ion in the solutions exerted a strong effect on Ca loss. Ca ion left first from calcium hydroxide in the pastes, depleting all calcium hydroxide by 60 days. Some calcium silicate hydrate remained even after 90 days in the solutions with the highest concentration of Mg ion, while the paste samples deteriorated noticeably. The results indicated a mechanism that involves dissolution of Ca phases and transport of Ca ions to the surface of the sample, followed by formation of Mg-bearing phases at this reaction surface rather than directly by substitution within the microstructure of hydrated cement. Given that calcium hydroxide and calcium silicate hydrate are the principal strength-giving phases of hydrated cement, this mechanism indicates the likelihood of significant loss of integrity of a concrete exposed to Mg-bearing ground water at the WIPP. The rate of deterioration ultimately will depend on Mg-ion concentration, the microstructure materials of the concrete exposed to that groundwater, and the availability of brine

XANES analysis of calcium and sodium phosphates and silicates and hydroxyapatite-Bioglass (registered) 45S5 co-sintered bioceramics

Energy Technology Data Exchange (ETDEWEB)

Demirkiran, Hande [Graduate Student, Materials Science and Engineering Department, University of Texas at Arlington, Arlington, TX (United States); Hu Yongfeng; Zuin, Lucia [Beamline Scientist, Canadian Light Source, Saskatoon, SK (Canada); Appathurai, Narayana [Beamline Scientist, Synchrotron Radiation Center, Madison, WI (United States); Aswath, Pranesh B., E-mail: aswath@uta.edu [Materials Science and Engineering Department, University of Texas at Arlington, Arlington, TX (United States)

2011-03-12

Bioglass (registered) 45S5 was co-sintered with hydroxyapatite at 1200 deg. C. When small amounts (< 5 wt.%) of Bioglass (registered) 45S5 was added it behaved as a sintering aid and also enhanced the decomposition of hydroxyapatite to {beta}-tricalcium phosphate. However when 10 wt.% and 25 wt.% Bioglass (registered) 45S5 was used it resulted in the formation of Ca{sub 5}(PO{sub 4}){sub 2}SiO{sub 4} and Na{sub 3}Ca{sub 6}(PO{sub 4}){sub 5} in an amorphous silicate matrix respectively. These chemistries show improved bioactivity compared to hydroxyapatite and are the subject of this study. The structure of several crystalline calcium and sodium phosphates and silicates as well as the co-sintered hydroxyapatite-Bioglass (registered) 45S5 bioceramics were examined using XANES spectroscopy. The nature of the crystalline and amorphous phases were studied using silicon (Si) and phosphorus (P) K- and L{sub 2,3}-edge and calcium (Ca) K-edge XANES. Si L{sub 2,3}-edge spectra of sintered bioceramic compositions indicates that the primary silicates present in these compositions are sodium silicates in the amorphous state. From Si K-edge spectra, it is shown that the silicates are in a similar structural environment in all the sintered bioceramic compositions with 4-fold coordination. Using P L{sub 2,3}-edge it is clearly shown that there is no evidence of sodium phosphate present in the sintered bioceramic compositions. In the P K-edge spectra, the post-edge shoulder peak at around 2155 eV indicates that this shoulder to be more defined for calcium phosphate compounds with decreasing solubility and increasing thermodynamic stability. This shoulder peak is more noticeable in hydroxyapatite and {beta}-TCP indicating greater stability of the phosphate phase. The only spectra that does not show a noticeable peak is the composition with Na{sub 3}Ca{sub 6}(PO{sub 4}){sub 5} in a silicate matrix indicating that it is more soluble compared to the other compositions.

Synthesis of β-tricalcium phosphate.

Science.gov (United States)

Chaair, H; Labjar, H; Britel, O

2017-09-01

Ceramics play a key role in several biomedical applications. One of them is bone grafting, which is used for treating bone defects caused by injuries or osteoporosis. Calcium-phosphate based ceramic are preferred as bone graft biomaterials in hard tissue surgery because their chemical composition is close to the composition of human bone. They also have a marked bioresorbability and bioactivity. In this work, we have developed methods for synthesis of β-tricalcium phosphate apatite (β-TCP). These products were characterized by different techniques such as X-ray diffraction, infrared spectroscopy, scanning electron microscopy and chemical analysis. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Tricalcium phosphate powder: Preparation, characterization and compaction abilities

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Abida Fatima

2017-02-01

Full Text Available In this work, we characterize tricalcium phosphate powders Ca9(HPO4(PO45(OH resulting from a reaction between calcium hydroxide and orthophosphoric acid at room temperature, without pH adjustment and in absence of ionic impurities. The prepared powder has an atomic ratio Ca/P of 1.512 ± 0.005. The real density is 2.68 ± 0.02 g/cm3 and the specific surface area is 80 ± 02 m2/g. During compression, the microstructure of Ca-deficient apatite powder with the presence of HPO4 groups seems to support the cohesion between particles. The transmission ratio is 90%, the transfer ratio is 41.8 and the ratio of the die-wall friction is 0.22. These results show that apatitic tricalcium powder gives a good aptitude to the compaction which leads to a good tensile strength (0.79 MPa. The heat treatment of the prepared powder shows the precise temperature for the formation of pyrophosphate, β-TCP and α-TCPa phases.  The purity and aptitude to compaction of the prepared powders are very promising for pharmaceutical and medical applications.

Internal friction of hydrated soda-lime-silicate glasses.

Science.gov (United States)

Reinsch, S; Müller, R; Deubener, J; Behrens, H

2013-11-07

The internal friction of hydrated soda-lime-silica glasses with total water content (C(W)) up to 1.9 wt. % was studied by dynamic mechanical analysis (DMA) using temperature-frequency sweeps from 723 K to 273 K and from 1 s(-1) to 50 s(-1). Total water content and concentrations of H2O molecules (C(H2O)) and OH groups (C(OH)) in the DMA specimens were determined by infrared spectroscopy. For low water contents (C(W) ≈ C(OH) friction peaks below the glass transition (α relaxation) were assigned to the low-temperature motion of alkali ions (γ relaxation) and cooperative movements of dissimilar mobile species under participation of OH at higher temperature (β(OH) relaxation). For large water contents (C(W) > 1 wt. %), where significant amounts of molecular water are evident (C(H2O) > 0.15 wt. %), however, internal friction spectra change unexpectedly: the β(OH) peak heights saturate and a low temperature shoulder appears on the β-relaxation peak. This emerging relaxation mode (β(H2O) relaxation) was assigned to the motions of H2O molecules. β(H2O) relaxation was found to be faster than β(OH) but slower than γ relaxation. Activation energy of the different relaxation modes increased in the order γ < β(H2O) < β(OH) < α.

Microbeam recoil detection for hydration of minerals studies

Energy Technology Data Exchange (ETDEWEB)

Sie, S.H.; Suter, G.F. [CSIRO, North Ryde, NSW (Australia). Exploration and Mining Div.; Chekhmir, A.; Green, T.H. [Macquarie Univ., North Ryde, NSW (Australia)

1993-12-31

The glancing angle geometry is chosen to enable application of the elastic recoil detection microanalysis on thick geological samples, for hydrogen content determination. Simultaneous PIXE measurements can be used to eliminate the problem of uncertainties in beam charge collection. The method is applied to determine the hydration characteristics of silicates, produced experimentally at high pressure and temperature simulating the lower crust and upper mantle conditions. Preliminary results show that the technique can be applied readily on a microscopic (<100 {mu}m) scale for determination of H at fraction of atomic percent level. 9 refs., 3 figs.

Microbeam recoil detection for hydration of minerals studies

Energy Technology Data Exchange (ETDEWEB)

Sie, S H; Suter, G F [CSIRO, North Ryde, NSW (Australia). Exploration and Mining Div.; Chekhmir, A; Green, T H [Macquarie Univ., North Ryde, NSW (Australia)

1994-12-31

The glancing angle geometry is chosen to enable application of the elastic recoil detection microanalysis on thick geological samples, for hydrogen content determination. Simultaneous PIXE measurements can be used to eliminate the problem of uncertainties in beam charge collection. The method is applied to determine the hydration characteristics of silicates, produced experimentally at high pressure and temperature simulating the lower crust and upper mantle conditions. Preliminary results show that the technique can be applied readily on a microscopic (<100 {mu}m) scale for determination of H at fraction of atomic percent level. 9 refs., 3 figs.

In vitro and in vivo evaluation of polylactic acid-based composite with tricalcium phosphate microsphere for enhanced biodegradability and osseointegration.

Science.gov (United States)

Shin, Da Yong; Kang, Min-Ho; Kang, In-Gu; Kim, Hyoun-Ee; Jeong, Seol-Ha

2018-05-01

A biodegradable polylactic acid composite containing tricalcium phosphate microsphere was fabricated. The composite exhibited enhanced biocompatibility and a well-interconnected porous structure that enabled tissue ingrowth after degradation. The tricalcium phosphate microspheres had an average size of 106 ± 43 μm and were incorporated into the polylactic acid matrix using a high-shear mixer. The resulting bioactivity and hydrophilicity were enhanced to levels comparable to those of a polylactic acid composite containing tricalcium phosphate powder, which is a well-known material used in the medical field. An accelerated 30-day degradation test in HCl revealed successful generation of an open porous structure with ∼98% interconnectivity in the polylactic acid-tricalcium phosphate microsphere composite, demonstrating the potential of this material to induce enhanced osseointegration in the later stage of bone regeneration. The early stage osseointegration was also evaluated by implanting the composite in vivo using a rabbit femoral defect model. After 16 weeks of implantation, the bone-to-implant contact ratio of the polylactic acid-tricalcium phosphate microsphere composite was enhanced owing to tissue ingrowth through the generated pores near the surface.

Chemistry and Bioactivity of NeoMTA Plus™ versus MTA Angelus® Root Repair Materials

Directory of Open Access Journals (Sweden)

Sawsan T. Abu Zeid

2017-01-01

Full Text Available Objectives. To analyse the chemistry and bioactivity of NeoMTA Plus in comparison with the conventional root repair materials. Method and Materials. Unhydrated and hydrated (initial and final sets materials were analysed by Fourier transform infrared (FTIR spectroscopy and X-ray diffraction (XRD. For bioactivity study, small holes of dentin discs were filled with either materials, immersed in PBS for 15 days, and analysed with FTIR and scanning electron microscope with energy dispersive X-ray (SEM/EDX. The calculation of crystallinity and carbonate/phosphate (CO3/PO4 ratio of surface precipitates (from FTIR and calcium/phosphate (Ca/P ratio (from EDX was statistically analysed using t-test or ANOVA, respectively, at 0.05 significance. Results. Both materials are tricalcium silicate-based that finally react to be calcium silicate hydrate. NeoMTA Plus has relatively high aluminium and sulfur content, with tantalum oxide as an opacifier instead of zirconium oxide in MTA Angelus. NeoMTA Plus showed better apatite formation, higher crystallinity and Ca/P but lower CO3/PO4 ratio than MTA Angelus. SEM showed globular structure with a small particle size in NeoMTA Plus while spherical structure with large particle size in MTA Angelus. Conclusion. Due to fast setting, higher crystallinity, and better bioactivity of NeoMTA Plus, it can be used as a pulp and root repair material.

New insight into atmospheric alteration of alkali-lime silicate glasses

International Nuclear Information System (INIS)

Alloteau, Fanny; Lehuédé, Patrice; Majérus, Odile; Biron, Isabelle; Dervanian, Anaïs; Charpentier, Thibault; Caurant, Daniel

2017-01-01

Highlights: •Glass silicate network hydrolysis is by far the predominant reaction at 80 °C. •Atmospheric conditions yield different altered layer structure than in immersion. •The altered layer bears about 10 wt% of water mainly as H-bonded SiOH groups. •Alkali ions stay embedded into the altered layer closed to SiOH and H 2 O species. -- Abstract: A mixed alkali lime silicate glass altered in atmospheric conditions (80 °C/85%RH, Relative Humidity) for various lengths of time was characterized at all scales. The altered glass forms a hydrated solid phase bearing about 10 wt% of H 2 O in the form of Si-OH groups and molecular water. No alkali depletion was observed after ageing tests. Structural results from 1 H, 23 Na and 29 Si MAS NMR point out the close proximity of Si-OH, H 2 O and Na + species. This study gives new insight into the mechanisms of the atmospheric alteration, essential to conservation strategies in industry and cultural heritage.

Local Structures around Si, Al and Na in Hydrated Silicate Glasses

International Nuclear Information System (INIS)

Farges, Francois; Wispelaere, Sidoine de; Rossano, Stephanie; Munos, Manuel; Wilke, Max; Flank, Anne-Marie; Lagarde, Pierre

2007-01-01

XANES spectra were collected at the Si-, Al-, and Na K-edge in hydrous silicate glasses to understand the effect of water on the local structure around these cations. Around network forming Si and Al, no drastic changes are observed. Around Na, the dissolution of water creates more ordered environments in Al-bearing glasses and less ordered environment in Al-free glasses. Ab-initio XANES calculations were undertaken to understand the structural origins for these features. Based on these results, a bond valence model was refined that considers not only the present XANES experiments and models but also NMR information. The double percolation model refined explains, among others, the explosive properties of water-bearing hydrous melts, at the origin of a number of cataclysmic eruptions in subduction zones

TSDC and impedance spectroscopy measurements on hydroxyapatite, β-tricalcium phosphate and hydroxyapatite/β-tricalcium phosphate biphasic bioceramics

Science.gov (United States)

Prezas, P. R.; Melo, B. M. G.; Costa, L. C.; Valente, M. A.; Lança, M. C.; Ventura, J. M. G.; Pinto, L. F. V.; Graça, M. P. F.

2017-12-01

Bone grafting and surgical interventions related with orthopaedic disorders consist in a big business, generating large revenues worldwide every year. There is a need to replace the biomaterials that currently still dominate this market, i.e., autografts and allografts, due to their disadvantages, such as limited availability, need for additional surgeries and diseases transmission possibilities. The most promising replacement materials are biomaterials with bioactive properties, such as the calcium phosphate-based bioceramics group. The bioactivity of these materials, i.e., the rate at which they promote the growth and directly bond with the new host biological bone, can be enhanced through their electrical polarization. In the present work, the electrical polarization features of pure hydroxyapatite (Hap), pure β-tricalcium phosphate (β-TCP) and biphasic hydroxyapatite/β-tricalcium phosphate composites (HTCP) were analyzed by measuring thermally stimulated depolarization currents (TSDC). The samples were thermoelectrically polarized at 500 °C under a DC electric field with a magnitude of 5 kV/cm. The biphasic samples were also polarized under electric fields with different magnitudes: 2, 3, 4 and 5 kV/cm. Additionally, the depolarization processes detected in the TSDC measurements were correlated with dielectric relaxation processes observed in impedance spectroscopy (IS) measurements. The results indicate that the β-TCP crystalline phase has a considerable higher ability to store electrical charge compared with the Hap phase. This indicates that it has a suitable composition and structure for ionic conduction and establishment of a large electric charge density, providing great potential for orthopaedic applications.

Developing a novel magnesium glycerophosphate/silicate-based organic-inorganic composite cement for bone repair.

Science.gov (United States)

Ding, Zhengwen; Li, Hong; Wei, Jie; Li, Ruijiang; Yan, Yonggang

2018-06-01

Considering that the phospholipids and glycerophosphoric acid are the basic materials throughout the metabolism of the whole life period and the bone is composed of organic polymer collagen and inorganic mineral apatite, a novel self-setting composite of magnesium glycerophosphate (MG) and di-calcium silicate(C2S)/tri-calcium silicate(C3S) was developed as bio-cement for bone repair, reconstruction and regeneration. The composite was prepared by mixing the MG, C2S and C3S with the certain ratios, and using the deionized water and phosphoric acid solution as mixed liquid. The combination and formation of the composites was characterized by FTIR, XPS and XRD. The physicochemical properties were studied by setting time, compressive strength, pH value, weight loss in the PBS and surface change by SEM-EDX. The biocompatibility was evaluated by cell culture in the leaching solution of the composites. The preliminary results showed that when di- and tri-calcium silicate contact with water, there are lots of Ca(OH) 2 generated making the pH value of solution is higher than 9 which is helpful for the formation of hydroxyapatite(HA) that is the main bone material. The new organic-inorganic self-setting bio-cements showed initial setting time is ranged from 20 min to 85 min and the compressive strength reached 30 MPa on the 7th days, suitable as the bone fillers. The weight loss was 20% in the first week, and 25% in the 4th week. Meanwhile, the new HA precipitated on the composite surface during the incubation in the SBF showed bioactivity. The cell cultured in the leaching liquid of the composite showed high proliferation inferring the new bio-cement has good biocompatibility to the cells. Copyright © 2018 Elsevier B.V. All rights reserved.

Histomorphometric evaluation of bone regeneration using autogenous bone and beta-tricalcium phosphate in diabetic rabbits

Directory of Open Access Journals (Sweden)

Živadinović Milka

2016-01-01

Full Text Available Background/Aim. The mechanism of impaired bone healing in diabetes mellitus includes different tissue and cellular level activities due to micro- and macrovascular changes. As a chronic metabolic disease with vascular complications, diabetes affects a process of bone regeneration as well. The therapeutic approach in bone regeneration is based on the use of osteoinductive autogenous grafts as well as osteoconductive synthetic material, like a β-tricalcium phosphate. The aim of the study was to determine the quality and quantity of new bone formation after the use of autogenous bone and β-tricalcium phosphate in the model of calvarial critical-sized defect in rabbits with induced diabetes mellitus type I. Methods. The study included eight 4-month-old Chincilla rabbits with alloxan-induced diabetes mellitus type I. In all animals, there were surgically created two calvarial bilateral defects (diameter 12 mm, which were grafted with autogenous bone and β-tricalcium phosphate (n = 4 or served as unfilled controls (n = 4. After 4 weeks of healing, animals were sacrificed and calvarial bone blocks were taken for histologic and histomorphometric analysis. Beside descriptive histologic evaluation, the percentage of new bone formation, connective tissue and residual graft were calculated. All parameters were statistically evaluated by Friedman Test and post hock Wilcoxon Singed Ranks Test with a significance of p < 0.05. Results. Histology revealed active new bone formation peripherally with centrally located connective tissue, newly formed woven bone and well incorporated residual grafts in all treated defects. Control samples showed no bone bridging of defects. There was a significantly more new bone in autogeonous graft (53% compared with β-tricalcium phosphate (30%, (p < 0.030 and control (7%, (p < 0.000 groups. A significant difference was also recorded between β-tricalcium phosphate and control groups (p < 0.008. Conclusion. In the present

The crucial effect of early-stage gelation on the mechanical properties of cement hydrates

Science.gov (United States)

Ioannidou, Katerina; Kanduč, Matej; Li, Lunna; Frenkel, Daan; Dobnikar, Jure; Del Gado, Emanuela

2016-07-01

Gelation and densification of calcium-silicate-hydrate take place during cement hydration. Both processes are crucial for the development of cement strength, and for the long-term evolution of concrete structures. However, the physicochemical environment evolves during cement formation, making it difficult to disentangle what factors are crucial for the mechanical properties. Here we use Monte Carlo and Molecular Dynamics simulations to study a coarse-grained model of cement formation, and investigate the equilibrium and arrested states. We can correlate the various structures with the time evolution of the interactions between the nano-hydrates during the preparation of cement. The novel emerging picture is that the changes of the physicochemical environment, which dictate the evolution of the effective interactions, specifically favour the early gel formation and its continuous densification. Our observations help us understand how cement attains its unique strength and may help in the rational design of the properties of cement and related materials.

Calcium aluminates hydration in presence of amorphous SiO2 at temperatures below 90 deg. C

International Nuclear Information System (INIS)

Rivas Mercury, J.M.; Turrillas, X.; Aza, A.H. de; Pena, P.

2006-01-01

The hydration behaviour of Ca 3 Al 2 O 6 , Ca 12 Al 14 O 33 and CaAl 2 O 4 with added amorphous silica at 40, 65 and 90 deg. C has been studied for periods ranging from 1 to 31 days. In hydrated samples crystalline phases like katoite (Ca 3 Al 2 (SiO 4 ) 3- x (OH) 4 x ) and gibbsite, Al(OH) 3 , were identified, likewise amorphous phases like Al(OH) x , calcium silicate hydrates, C-S-H, and calcium aluminosilicate hydrates, C-S-A-H, were identified. The stoichiometry of Ca 3 Al 2 (SiO 4 ) 3- x (OH) 4 x (0≤3-x≤0.334), which was the main crystalline product, was established by Rietveld refinement of X-ray and neutron diffraction data and by transmission electron microscopy. - Graphical abstract: Katoite, Ca 3 Al 2 (SiO 4 ) 3- x (OH) 4 x (0≤3-x≤0.334), was identified besides gibbsite, Al(OH) 3 , as a crystalline stable hydration products in Ca 3 Al 2 O 6 , Ca 12 Al 14 O 33 and CaAl 2 O 4 hydrated with added amorphous silica between 40 and 90 deg. C

Characterization of a calcium phosphate cement based on alpha-tricalcium phosphate obtained by wet precipitation process

International Nuclear Information System (INIS)

Thurmer, M.B.; Diehl, C.E.; Vieira, R.S.; Coelho, W.T.G.; Santos, L.A.

2012-01-01

There are several systems of calcium phosphate cements being studied. Those based on alpha-tricalcium phosphate are of particular interest. After setting they produce calcium deficient hydroxyapatite similar to bone like hydroxyapatite. This work aims to obtain alpha-tricalcium phosphate powders by the wet precipitation process, using calcium nitrate and phosphoric acid as reagents. This powder was characterized by infrared spectroscopy, X-ray diffraction and particle size distribution. In order to prepare the calcium phosphate cement, the powder was mixed with an accelerator in an aqueous solution. The mechanical properties of the cement were assessed and it was evaluated by means of apparent density, X-ray diffraction and scanning electron microscopy. The described method produced crystalline alpha-tricalcium phosphate as the major phase. The calcium phosphate cement showed high values of compression strength (50 MPa). The soaking of the cement in a simulated body fluid (SBF) formed a layer of hydroxyapatite like crystals in the surface of the samples. (author)

Modeling of Cation Binding in Hydrated 2:1 Clay Minerals - Final Report

International Nuclear Information System (INIS)

Smith, David E.

2000-01-01

Hydrated 2:1 clay minerals are high surface area, layered silicates that play a unique role in determining the fate of radionuclides in the environment. This project consisted of developing and implementing computer simulation methods for molecular characterization of the swelling and ion exchange properties of Hydrated 2:1 clay minerals, and the subsequent analysis and theoretical modeling with a view toward improving contaminant transport modeling as well as soil remediation and radionuclide containment strategies. Project results included the (a) development of simulation methods to treat clays under environmentally relevant conditions of variable water vapor pressure; (b) calculation of clay swelling thermodynamics as a function of interlayer ion size and charge (calculated quantities include immersion energies, free energies, and entropies of swelling); and (c) calculation of ion exchange free energies, including contributions from changing interlayer water contents and layer spacing

Liposomal clodronate inhibition of osteoclastogenesis and osteoinduction by submicrostructured beta-tricalcium phosphate

NARCIS (Netherlands)

Davison, N.L.; Gambin, A.-L.; Layrolle, P.; Yuan, Huipin; de Bruijn, Joost Dick; Barrère-de Groot, F.

2014-01-01

Bone graft substitutes such as calcium phosphates are subject to the innate inflammatory reaction, which may bear important consequences for bone regeneration. We speculate that the surface architecture of osteoinductive β-tricalcium phosphate (TCP) stimulates the differentiation of invading

Wear and chemistry of zirconium-silicate, aluminium-silicate and zirconium-aluminium-silicate glasses in alkaline medium

International Nuclear Information System (INIS)

Rouse, C.G.; Lemos Guenaga, C.M. de

1984-01-01

A study of the chemical durability, in alkaline solutions, of zirconium silicate, aluminium silicate, zirconium/aluminium silicate glasses as a function of glass composition is carried out. The glasses were tested using standard DIN-52322 method, where the glass samples are prepared in small polished pieces and attacked for 3 hours in a 800 ml solution of 1N (NaOH + NA 2 CO 3 ) at 97 0 C. The results show that the presence of ZrO 2 in the glass composition increases its chemical durability to alkaline attack. Glasses of the aluminium/zirconium silicate series were melted with and without TiO 2 . It was shown experimentally that for this series of glasses, the presence of both TiO 2 and ZrO 2 gave better chemical durability results. However, the best overall results were obtained from the simpler zirconium silicate glasses, where it was possible to make glasses with higher values of ZrO 2 . (Author) [pt

Transformation of meta-stable calcium silicate hydrates to tobermorite: reaction kinetics and molecular structure from XRD and NMR spectroscopy

Science.gov (United States)

2009-01-01

Understanding the integrity of well-bore systems that are lined with Portland-based cements is critical to the successful storage of sequestered CO2 in gas and oil reservoirs. As a first step, we investigate reaction rates and mechanistic pathways for cement mineral growth in the absence of CO2 by coupling water chemistry with XRD and NMR spectroscopic data. We find that semi-crystalline calcium (alumino-)silicate hydrate (Al-CSH) forms as a precursor solid to the cement mineral tobermorite. Rate constants for tobermorite growth were found to be k = 0.6 (± 0.1) × 10-5 s-1 for a solution:solid of 10:1 and 1.6 (± 0.8) × 10-4 s-1 for a solution:solid of 5:1 (batch mode; T = 150°C). This data indicates that reaction rates for tobermorite growth are faster when the solution volume is reduced by half, suggesting that rates are dependent on solution saturation and that the Gibbs free energy is the reaction driver. However, calculated solution saturation indexes for Al-CSH and tobermorite differ by less than one log unit, which is within the measured uncertainty. Based on this data, we consider both heterogeneous nucleation as the thermodynamic driver and internal restructuring as possible mechanistic pathways for growth. We also use NMR spectroscopy to characterize the site symmetry and bonding environment of Al and Si in a reacted tobermorite sample. We find two [4]Al coordination structures at δiso = 59.9 ppm and 66.3 ppm with quadrupolar product parameters (PQ) of 0.21 MHz and 0.10 MHz (± 0.08) from 27Al 3Q-MAS NMR and speculate on the Al occupancy of framework sites by probing the protonation environment of Al metal centers using 27Al{1H}CP-MAS NMR. PMID:19144195

Thermodynamic and structural characteristics of cement minerals at elevated temperature

International Nuclear Information System (INIS)

Bruton, C.J.; Meike, A.; Viani, B.E.; Martin, S.; Phillips, B.L.

1994-05-01

We have instituted an experimental and including program designed to elucidate the structural and thermodynamic response of cement minerals to elevated temperature. Components of the program involve: (a) synthesis of hydrated Ca-silicates; (b) structural analysis of cement phases induced by heating and dehydration/rehydration; (c) mechanistic and thermodynamic descriptions of the hydration/dehydration behavior of hydrated Ca-silicates as a function of temperature, pressure and relative humidity; (d) study of naturally occurring hydrated Ca-silicates; and (e) measurements of thermodynamic data for hydrated Ca-silicates

Retrogressive hydration of calc-silicate xenoliths in the eastern Bushveld complex: evidence for late magmatic fluid movement

Science.gov (United States)

Wallmach, T.; Hatton, C. J.; De Waal, S. A.; Gibson, R. L.

1995-11-01

Two calc-silicate xenoliths in the Upper Zone of the Bushveld complex contain mineral assemblages which permit delineation of the metamorphic path followed after incorporation of the xenoliths into the magma. Peak metamorphism in these xenoliths occurred at T=1100-1200°C and P <1.5 kbar. Retrograde metamorphism, probably coinciding with the late magmatic stage, is characterized by the breakdown of akermanite to monticellite and wollastonite at 700°C and the growth of vesuvianite from melilite. The latter implies that water-rich fluids (X CO 2 <0.2) were present and probably circulating through the cooling magmatic pile. In contrast, calc-silicate xenoliths within the lower zones of the Bushveld complex, namely in the Marginal and Critical Zones, also contain melilite, monticellite and additional periclase with only rare development of vesuvianite. This suggests that the Upper Zone cumulate pile was much 'wetter' in the late-magmatic stage than the earlier-formed Critical and Marginal Zone cumulate piles.

Reconsideration on Hydration of Sodium Ion: From Micro-Hydration to Bulk Hydration

Science.gov (United States)

Yongquan, Zhou; Chunhui, Fang; Yan, Fang; Fayan, Zhu; Haiwen, Ge; Hongyan, Liu

2017-12-01

Micro hydration structures of the sodium ion, [Na(H2O) n ]+, n = 1-12, were probed by density functional theory (DFT) at B3LYP/aug-cc-pVDZ level in both gaseous and aqueous phase. The predicted equilibrium sodium-oxygen distance of 0.240 nm at the present level of theory. The four-, five- and six-coordinated cluster can transform from each other at the ambient condition. The analysis of the successive water binding energy and natural charge population (NBO) on Na+ clearly shows that the influence of Na+ on the surrounding water molecules goes beyond the first hydration shell with the hydration number of 6. The Car-Parrinello molecular dynamic simulation shows that only the first hydration sphere can be found, and the hydration number of Na+ is 5.2 and the hydration distance ( r Na-O) is 0.235 nm. All our simulations mentioned in the present paper show an excellent agreement with the diffraction result from X-ray scattering study.

Advanced Nanoscale Characterization of Cement Based Materials Using X-Ray Synchrotron Radiation: A Review

KAUST Repository

Chae, Sejung R.

2013-05-22

We report various synchrotron radiation laboratory based techniques used to characterize cement based materials in nanometer scale. High resolution X-ray transmission imaging combined with a rotational axis allows for rendering of samples in three dimensions revealing volumetric details. Scanning transmission X-ray microscope combines high spatial resolution imaging with high spectral resolution of the incident beam to reveal X-ray absorption near edge structure variations in the material nanostructure. Microdiffraction scans the surface of a sample to map its high order reflection or crystallographic variations with a micron-sized incident beam. High pressure X-ray diffraction measures compressibility of pure phase materials. Unique results of studies using the above tools are discussed-a study of pores, connectivity, and morphology of a 2,000 year old concrete using nanotomography; detection of localized and varying silicate chain depolymerization in Al-substituted tobermorite, and quantification of monosulfate distribution in tricalcium aluminate hydration using scanning transmission X-ray microscopy; detection and mapping of hydration products in high volume fly ash paste using microdiffraction; and determination of mechanical properties of various AFm phases using high pressure X-ray diffraction. © 2013 The Author(s).

New french uranium mineral species; Nouvelles especes uraniferes francaises

Energy Technology Data Exchange (ETDEWEB)

Branche, G; Chervet, J; Guillemin, C [Commissariat a l' Energie Atomique, Lab. du Fort de Chatillon, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1952-07-01

In this work, the authors study the french new uranium minerals: parsonsite and renardite, hydrated phosphates of lead and uranium; kasolite: silicate hydrated of uranium and lead uranopilite: sulphate of uranium hydrated; bayleyite: carbonate of uranium and of hydrated magnesium; {beta} uranolite: silicate of uranium and of calcium hydrated. For all these minerals, the authors give the crystallographic, optic characters, and the quantitative chemical analyses. On the other hand, the following species, very rare in the french lodgings, didn't permit to do quantitative analyses. These are: the lanthinite: hydrated uranate oxide; the {alpha} uranotile: silicate of uranium and of calcium hydrated; the bassetite: uranium phosphate and of hydrated iron; the hosphuranylite: hydrated uranium phosphate; the becquerelite: hydrated uranium oxide; the curite: oxide of uranium and lead hydrated. Finally, the authors present at the end of this survey a primary mineral: the brannerite, complex of uranium titanate. (author) [French] Dans ce travail, les auteurs etudient les nouveaux mineraux uraniferes francais: parsonsite et renardite, phosphates hydrates de plomb et d'uranium; kasolite: silicate hydrate d'uranium et de plomb uranopilite: sulfate d'uranium hydrate; bayleyite: carbonate d'uranium et de magnesium hydrate; {beta} uranolite: silicate d'uranium et de calcium hydrate. Pour tous ces mineraux, les auteurs donnent les caracteres cristallographiques, optiques, et les analyses chimiques quantitatives. Par contre, les especes suivantes, tres rares dans les gites francais, n'ont pas permis d'effectuer d'analyses quantitatives. Ce sont: l'ianthinite: oxyde uraneux hydrate; l'{alpha} uranotile: silicate d'uranium et de calcium hydrate; le bassetite: phosphate d'uranium et de fer hydrate; la hosphuranylite: phosphate duranium hydrate; la becquerelite: oxyde d'uranium hydrate; la curite: oxyde d'uranium et de plomb hydrate. Enfin, les auteurs presentent a la fin de cette etude

Impregnation of β-​tricalcium phosphate robocast scaffolds by in situ polymerization

NARCIS (Netherlands)

Martinez-Vazquez, F.J.; Perera, F.H.; Meulen, van der I.; Heise, A.; Pajares, A.; Miranda, P.

2013-01-01

Ring-¿opening polymn. of e-¿caprolactone (e-¿CL) and L-¿lactide (LLA) was performed to impregnate ß-¿tricalcium phosphate (ß-¿TCP) scaffolds fabricated by robocasting. Concd. colloidal inks prepd. from ß-¿TCP com. powders were used to fabricate porous structures consisting of a 3D mesh of

Hydrate-CASM for modeling Methane Hydrate-Bearing Sediments

Science.gov (United States)

De La Fuente Ruiz, M.; Vaunat, J.; Marin Moreno, H.

2017-12-01

A clear understanding of the geomechanical behavior of methane hydrate-bearing sediments (MHBS) is crucial to assess the stability of the seafloor and submarine infrastructures to human and natural loading changes. Here we present the Hydrate-CASM, a new elastoplastic constitutive model to predict the geomechanical behavior of MHBS. Our model employs the critical state model CASM (Clay and Sand Model) because of its flexibility in describing the shape of the yield surface and its proven ability to predict the mechanical behavior of sands, the most commercially viable hydrate reservoirs. The model considers MHBS as a deformable elastoplastic continuum, and hydrate-related changes in the stress-strain behavior are predicted by a densification mechanism. The densification attributes the mechanical contribution of hydrate to; a reduction of the available void ratio; a decrease of the swelling line slope; and an increase of the volumetric yield stress. It is described by experimentally derived physical parameters except from the swelling slope coefficient that requires empirical calibration. The Hydrate-CASM is validated against published triaxial laboratory tests performed at different confinement stresses, hydrate saturations, and hydrate morphologies. During the validation, we focused on capturing the mechanical behavior of the host sediment and consider perturbations of the sediment's mechanical properties that could result from the sample preparation. Our model successfully captures the experimentally observed influence of hydrate saturation in the magnitude and trend of the stiffness, shear strength, and dilatancy of MHBS. Hence, we propose that hydrate-related densification changes might be a major factor controlling the geomechanical response of MHBS.

Biocompatibility behavior of β–tricalcium phosphate-chitosan coatings obtained on 316L stainless steel

International Nuclear Information System (INIS)

Mina, A.; Caicedo, H.H.; Uquillas, J.A.; Aperador, W.; Gutiérrez, O.; Caicedo, J.C.

2016-01-01

Biological interfaces involve the interaction of complex macromolecular systems and other biomolecules or biomaterials. Researchers have used a combination of cell, material sciences and engineering approaches to create functional biointerfaces to help improve biological functions. Materials such as hydroxyapatite (HA), β-tricalcium phosphate (β-TCP) and chitosan are important biomaterials to be used in biomedical applications such as bone-prosthesis interfaces. In this work, it was evaluated the effect of different concentrations of chitosan on the structural, electrochemical and biocompatible properties of β-tricalcium phosphate-chitosan ((β-Ca 3 (PO 4 ) 2 )-(C 6 H 11 NO 4 )n) hybrid coatings. β–tricalcium phosphate-chitosan coatings were deposited on 316L stainless steel substrates applying 260 mA AC, an agitation velocity of 250 rpm, and temperature deposition of 60 °C. It was possible to obtain coatings of 600 μm of thickness. Structure and surface properties were analyzed by X-ray diffraction (XRD) and dispersive X-ray analysis (EDX). It was found that the arrangement of the β-TCP crystal lattice changed with increasing chitosan weight concentration, showing that the orthorhombic structure of β-TCP is under tensile stress. The electrochemical properties of β–tricalcium phosphate/chitosan (β-TCP–Ch) coatings were analyzed by electrochemical impedance spectroscopy (EIS). Cellular biocompatibility was determined by lactate dehydrogenase (LDH) cytotoxicity assay using primary chinese hamster ovary (CHO) cells. β-TCP–Ch coatings with chitosan concentrations up to 25% caused cytotoxic effects to only 5–10% of CHO cells. Obtained results showed the influence of chitosan in the structural, electrochemical, and biocompatible properties of AISI 316L Stainless Steel. Consequently, the electrochemical and cytotoxic behavior of β-TCP–Ch on 316L Stainless Steel indicated that the coatings might be a promising material in biomedical applications

Cement hydration from hours to centuries controlled by diffusion through barrier shells of C-S-H

Science.gov (United States)

Rahimi-Aghdam, Saeed; Bažant, Zdeněk P.; Abdolhosseini Qomi, M. J.

2017-02-01

Although a few good models for cement hydration exist, they have some limitations. Some do not take into account the complete range of variation of pore relative humidity and temperature, and apply over durations limited from up a few months to up to about a year. The ones that are applicable for long durations are either computationally too intensive for use in finite element programs or predict the hydration to terminate after few months. However, recent tests of autogenous shrinkage and swelling in water imply that the hydration may continue, at decaying rate, for decades, provided that a not too low relative pore humidity (above 0.7) persists for a long time, as expected for the cores of thick concrete structural members. Therefore, and because design lifetimes of over hundred years are required for large concrete structures, a new hydration model for a hundred year lifespan and beyond is developed. The new model considers that, after the first day of hydration, the remnants of anhydrous cement grains, gradually consumed by hydration, are enveloped by contiguous, gradually thickening, spherical barrier shells of calcium-silicate hydrate (C-S-H). The hydration progress is controlled by transport of water from capillary pores through the barrier shells toward the interface with anhydrous cement. The transport is driven by a difference of humidity, defined by equivalence with the difference in chemical potential of water. Although, during the period of 4-24 h, the C-S-H forms discontinuous nano-globules around the cement grain, an equivalent barrier shell control was formulated for this period, too, for ease and effectiveness of calculation. The entire model is calibrated and validated by published test data on the evolution of hydration degree for various cement types, particle size distributions, water-cement ratios and temperatures. Computationally, this model is sufficiently effective for calculating the evolution of hydration degree (or aging) at every

Final report on the safety assessment of potassium silicate, sodium metasilicate, and sodium silicate.

Science.gov (United States)

Elmore, Amy R

2005-01-01

Potassium Silicate, Sodium Metasilicate, and Sodium Silicate combine metal cations with silica to form inorganic salts used as corrosion inhibitors in cosmetics. Sodium Metasilicate also functions as a chelating agent and Sodium Silicate as a buffering and pH adjuster. Sodium Metasilicate is currently used in 168 formulations at concentrations ranging from 13% to 18%. Sodium Silicate is currently used in 24 formulations at concentrations ranging from 0.3% to 55%. Potassium Silicate and Sodium Silicate have been reported as being used in industrial cleaners and detergents. Sodium Metasilicate is a GRAS (generally regarded as safe) food ingredient. Aqueous solutions of Sodium Silicate species are a part of a chemical continuum of silicates based on an equilibrium of alkali, water, and silica. pH determines the solubility of silica and, together with concentration, determines the degree of polymerization. Sodium Silicate administered orally is readily absorbed from the alimentary canal and excreted in the urine. The toxicity of these silicates has been related to the molar ratio of SiO2/Na2O and the concentration being used. The Sodium Metasilicate acute oral LD50 ranged from 847 mg/kg in male rats to 1349.3 mg/kg in female rats and from 770 mg/kg in female mice to 820 mg/kg in male mice. Gross lesions of variable severity were found in the oral cavity, pharynx, esophagus, stomach, larynx, lungs, and kidneys of dogs receiving 0.25 g/kg or more of a commercial detergent containing Sodium Metasilicate; similar lesions were also seen in pigs administered the same detergent and dose. Male rats orally administered 464 mg/kg of a 20% solution containing either 2.0 or 2.4 to 1.0 ratio of sodium oxide showed no signs of toxicity, whereas doses of 1000 and 2150 mg/kg produced gasping, dypsnea, and acute depression. Dogs fed 2.4 g/kg/day of Sodium Silicate for 4 weeks had gross renal lesions but no impairment of renal function. Dermal irritation of Potassium Silicate, Sodium

Nanostructured silicate polymer concrete

Directory of Open Access Journals (Sweden)

Figovskiy Oleg L'vovich

2014-03-01

Full Text Available It has been known that acid-resistant concretes on the liquid glass basis have high porosity (up to 18~20 %, low strength and insufficient water resistance. Significant increasing of silicate matrix strength and density was carried out by incorporation of special liquid organic alkali-soluble silicate additives, which block superficial pores and reduce concrete shrinkage deformation. It was demonstrated that introduction of tetrafurfuryloxisilane additive sharply increases strength, durability and shock resistance of silicate polymer concrete in aggressive media. The experiments showed, that the strength and density of silicate polymer concrete increase in case of decreasing liquid glass content. The authors obtained optimal content of silicate polymer concrete, which possesses increased strength, durability, density and crack-resistance. Diffusive permeability of concrete and its chemical resistance has been investigated in various corroding media.

Density and water content of nanoscale solid C–S–H formed in alkali-activated slag (AAS) paste and implications for chemical shrinkage

International Nuclear Information System (INIS)

Thomas, Jeffrey J.; Allen, Andrew J.; Jennings, Hamlin M.

2012-01-01

Alkali-activated slag (AAS) paste was analyzed using small-angle neutron scattering (SANS). The scattering response indicates that the microstructure consists of a uniform matrix of hydration product with a high surface area studded with unhydrated cores of slag particles. In contrast with portland cement paste, no surface fractal scattering regime was detected, and elevated temperature curing (at 60 °C) had no detectable effect on the microstructure at any length scale studied. The specific surface area of the AAS pastes is about 25% higher than that of a portland cement paste cured under the same conditions. The composition and mass density of the nanoscale solid C–S–H phase formed in the AAS paste was determined using a previously developed neutron scattering method, in conjunction with a hydration model. The result ((CaO) 0.99 –SiO 2 –(Al 2 O 3 ) 0.06 –(H 2 O) 0.97 , d = (2.73 ± 0.02) g/cm 3 ) is significantly lower in calcium and in water as compared to portland cement or pure tricalcium silicate paste. These values were used to calculate the chemical shrinkage that would result from complete hydration of the AAS paste. The result, (12.2 ± 1.5) cm 3 of volumetric shrinkage per 100 g of unhydrated cement, is about twice the amount of chemical shrinkage exhibited by normal cement pastes.

Impact of the use of alternative fuels on clinker reactivity

International Nuclear Information System (INIS)

Serrano-González, K.; Reyes-Valdez, A.; Chowaniec, O.

2017-01-01

The use of alternative fuels in the cement industry has increased its relevance in the past decades due to their ecological and economic benefits. In concert with the efforts to increase its use, several studies have focused on their potential impact with respect to clinker reactivity and how they could affect the expected physical and mechanical properties. This work studied the effects of five alternative fuels on the reactivity of eight industrial clinker samples, considering several analytical techniques. Differences were identified among the clinker samples after replacing the alternative fuels, mainly with simultaneous eliminations, as in samples S4, S5 and S8. The modifications were related to the polymorph, size and reactivity of tricalcium silicate and to the clinker profile during the hydration process, due to the SO3 consumption rate. These changes were expressed in the higher compressive strengths in comparison with the original reference clinker. [es

21 CFR 573.260 - Calcium silicate.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium silicate. 573.260 Section 573.260 Food and... Listing § 573.260 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely used as an anticaking agent in animal feed, provided that the amount of calcium silicate does not...

The role of pH in the vapor hydration at 175 °C of the French SON68 glass

International Nuclear Information System (INIS)

Ait Chaou, Abdelouahed; Abdelouas, Abdesselam; El Mendili, Yassine; Martin, Christelle

2017-01-01

The French simulated nuclear waste SON68 glass was altered in the presence of water vapor at 175 °C and 98% of relative humidity under several atmospheres (NH_3, H_2S, CO_2 and argon). The objectives were to study the role of pH on hydration kinetics and secondary phases formation. The hydration was followed by infrared spectroscopy and the nature and extent of alteration products were determined by characterizing the reacted glass surface with scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), μ-Raman spectroscopy and X-ray diffraction (XRD). The glass hydration/alteration rate clearly increased with increasing pH, that is controlled by the gas atmosphere, as the following: NH_3 > Ar > CO_2 > H_2S. This can directly be linked to the secondary phases precipitated on the glass surface. Hence, the major alteration products observed at high pH (under NH_3 and Ar) are analcime and Ca-silicates hydrates (CSH) while at low pH (under CO_2 and H_2S) only a hydrated gel layer was identified. - Highlights: • The vapor hydration study of the SON68 glass under geological conditions. • The secondary phases formation in the alteration of SON68 glass. • The pH effect on the alteration kinetics of glass.

Incorporation of phosphorus guest ions in the calcium silicate phases of Portland cement from 31P MAS NMR spectroscopy.

Science.gov (United States)

Poulsen, Søren L; Jakobsen, Hans J; Skibsted, Jørgen

2010-06-21

Portland cements may contain small quantities of phosphorus (typically below 0.5 wt % P(2)O(5)), originating from either the raw materials or alternative sources of fuel used to heat the cement kilns. This work reports the first (31)P MAS NMR study of anhydrous and hydrated Portland cements that focuses on the phase and site preferences of the (PO(4))(3-) guest ions in the main clinker phases and hydration products. The observed (31)P chemical shifts (10 to -2 ppm), the (31)P chemical shift anisotropy, and the resemblance of the lineshapes in the (31)P and (29)Si MAS NMR spectra strongly suggest that (PO(4))(3-) units are incorporated in the calcium silicate phases, alite (Ca(3)SiO(5)) and belite (Ca(2)SiO(4)), by substitution for (SiO(4))(4-) tetrahedra. This assignment is further supported by a determination of the spin-lattice relaxation times for (31)P in alite and belite, which exhibit the same ratio as observed for the corresponding (29)Si relaxation times. From simulations of the intensities, observed in inversion-recovery spectra for a white Portland cement, it is deduced that 1.3% and 2.1% of the Si sites in alite and belite, respectively, are replaced by phosphorus. Charge balance may potentially be achieved to some extent by a coupled substitution mechanism where Ca(2+) is replaced by Fe(3+) ions, which may account for the interaction of the (31)P spins with paramagnetic Fe(3+) ions as observed for the ordinary Portland cements. A minor fraction of phosphorus may also be present in the separate phase Ca(3)(PO(4))(2), as indicated by the observation of a narrow resonance at delta((31)P) = 3.0 ppm for two of the studied cements. (31)P{(1)H} CP/MAS NMR spectra following the hydration of a white Portland cement show that the resonances from the hydrous phosphate species fall in the same spectral range as observed for (PO(4))(3-) incorporated in alite. This similarity and the absence of a large (31)P chemical shift ansitropy indicate that the hydrous (PO(4

Revealing the Effect of Irradiation on Cement Hydrates: Evidence of a Topological Self-Organization.

Science.gov (United States)

Krishnan, N M Anoop; Wang, Bu; Sant, Gaurav; Phillips, James C; Bauchy, Mathieu

2017-09-20

Despite the crucial role of concrete in the construction of nuclear power plants, the effects of radiation exposure (i.e., in the form of neutrons) on the calcium-silicate-hydrate (C-S-H, i.e., the glue of concrete) remain largely unknown. Using molecular dynamics simulations, we systematically investigate the effects of irradiation on the structure of C-S-H across a range of compositions. Expectedly, although C-S-H is more resistant to irradiation than typical crystalline silicates, such as quartz, we observe that radiation exposure affects C-S-H's structural order, silicate mean chain length, and the amount of molecular water that is present in the atomic network. By topological analysis, we show that these "structural effects" arise from a self-organization of the atomic network of C-S-H upon irradiation. This topological self-organization is driven by the (initial) presence of atomic eigenstress in the C-S-H network and is facilitated by the presence of water in the network. Overall, we show that C-S-H exhibits an optimal resistance to radiation damage when its atomic network is isostatic (at Ca/Si = 1.5). Such an improved understanding of the response of C-S-H to irradiation can pave the way to the design of durable concrete for radiation applications.

Design and production of sintered β-tricalcium phosphate 3D scaffolds for bone tissue regeneration

International Nuclear Information System (INIS)

Santos, Carlos F.L.; Silva, Abílio P.; Lopes, Luís; Pires, Inês; Correia, Ilidio J.

2012-01-01

The characteristics of sintered β-tricalcium phosphate (β-TCP) scaffolds produced by 3D printing were studied by means of X-ray diffraction, Scanning Electron Microscopy, Fourier transform infrared spectroscopy, uniaxial compression tests and cytotoxicity tests, using human osteoblast cells. The results reported include details of the β-TCP scaffolds' porosity, density, phase stability, mechanical behavior and cytotoxic profile. Collectively, these properties are fundamental for the future application of these scaffolds as bone substitutes for individualized therapy. Highlights: ► β-Tricalcium phosphate (β-TCP) 3D scaffolds were produced by rapid prototyping. ► Scaffold properties were assessed by SEM, FTIR, XRD and by mechanical tests. ► The cytotoxic profile of the scaffolds was characterized by in vitro assays. ► Scaffolds have good properties for its application as bone substitutes for individualized therapy.

Experimental Evaluation of Sodium Silicate-Based Nanosilica against Chloride Effects in Offshore Concrete

Science.gov (United States)

Kim, Kyoung-Min; Kim, Hak-Young; Heo, Young-Sun; Jung, Sang-Jin

2014-01-01

This study investigates the effect of a new pore filling material, named sodium silicate-based nanosilica (SS), on resisting the diffusion of the chloride ions. The proposed SS is chosen, mainly due to its smaller particle size, compared to the conventional ethyl silicate-based nanosilica. Each particle of SS is chemically treated to have the negative (−) charge on its surface. Four types of mixes with different amounts of partial replacement with fly ash and slag are prepared. Effect of water to binder ratios (0.35, 0.40, and 0.45) is also examined. Test results showed that the inclusion of SS was significantly beneficial for protecting the concrete from chloride attack. At a given strength, the SS inclusion in concrete was up to three times more effective than the control concrete without SS. It is believed that these excellent results are attributed to the small particle size and the chemical surface treatment of SS. In this study, experiments of compressive strength, hydration heat, accelerated neutralization, and sulfate erosion tests were also conducted to find the general effect of SS inclusion on the fundamental properties and durability of concrete. PMID:25574486

Experimental Evaluation of Sodium Silicate-Based Nanosilica against Chloride Effects in Offshore Concrete

Directory of Open Access Journals (Sweden)

Kyoung-Min Kim

2014-01-01

Full Text Available This study investigates the effect of a new pore filling material, named sodium silicate-based nanosilica (SS, on resisting the diffusion of the chloride ions. The proposed SS is chosen, mainly due to its smaller particle size, compared to the conventional ethyl silicate-based nanosilica. Each particle of SS is chemically treated to have the negative (− charge on its surface. Four types of mixes with different amounts of partial replacement with fly ash and slag are prepared. Effect of water to binder ratios (0.35, 0.40, and 0.45 is also examined. Test results showed that the inclusion of SS was significantly beneficial for protecting the concrete from chloride attack. At a given strength, the SS inclusion in concrete was up to three times more effective than the control concrete without SS. It is believed that these excellent results are attributed to the small particle size and the chemical surface treatment of SS. In this study, experiments of compressive strength, hydration heat, accelerated neutralization, and sulfate erosion tests were also conducted to find the general effect of SS inclusion on the fundamental properties and durability of concrete.

Study of belite calcium sulfo-aluminate cement potential for zinc conditioning: From hydration to durability

International Nuclear Information System (INIS)

Berger, St.

2009-12-01

Calcium silicate cements are widely used for low- and intermediate-level radioactive waste conditioning. However, wastes produced by nuclear activities are very diverse and some of their components may chemically react with cement phases. For instance, ashes resulting from the incineration of technological wastes including neoprene and polyvinylchloride may contain substantial amounts of soluble zinc chloride. This compound is known to strongly delay or inhibit Portland cement setting. One approach to limit adverse cement-waste interactions is to select a binder showing a better compatibility with the waste while keeping cement matrix advantages (low cost, simple process, hydration with water provided by the waste...). This work thus investigates the potential of calcium sulfo-aluminate cement for zinc Zn(II) immobilization. Four aspects were considered: hydration (kinetics and products formed), properties of hydrated binders, mechanisms of zinc retention and durability of the cement pastes (based on leaching experiments and modelling). The influence of three main parameters was assessed: the gypsum content of the cement, the concentration of ZnCl 2 and the thermal evolution at early age. It follows that materials based on a calcium sulfo-aluminate cement containing 20% gypsum are interesting candidates for zinc Zn(II) stabilization/solidification: there is no delay in hydration, mineralogy of the hydrated phases is slightly dependent on thermal history, mechanical strength is high, dimensional changes are limited and zinc Zn(II) is well immobilized, even if the cement paste is leached by pure water during a long period (90 d). (author)

Platelet rich fibrin (Prf) and β-tricalcium phosphate with coronally advanced flap for the management of grade-II furcation defect.

Science.gov (United States)

Sambhav, Jain; Rohit, Rai; Ranjana, Mohan; Shalabh, Mehrotra

2014-07-01

Multirooted teeth offer unique and challenging problems due to the furcation area, creates situations in which routine periodontal procedures are somewhat limited and special procedures are generally required. The present case was showing the management of grade II furcation defect by platelet rich fibrin (PRF) and β-Tricalcium phosphate with coronally advanced flap. Platelet rich fibrin and β-Tricalcium phosphate with coronally advanced flap have been shown to be a promising and successful approach for the treatment of furcation defect. Its gaining clinical attachment significantly manages both the gingival recession and furcation involvement simultaneously.

Biocompatibility behavior of β–tricalcium phosphate-chitosan coatings obtained on 316L stainless steel

Energy Technology Data Exchange (ETDEWEB)

Mina, A. [Tribology, Powder Metallurgy and Processing of Solid Recycled Research Group, Universidad del Valle, Cali (Colombia); Caicedo, H.H. [Department of Anatomy and Cell Biology, University of Illinois at Chicago, IL, 60612 (United States); National Biotechnology & Pharmaceutical Association, Chicago, IL, 60606 (United States); Uquillas, J.A. [Universidad San Francisco de Quito USFQ, Colegio de Ciencias de la Salud COCSA, Escuela de Medicina, Hospital de los Valles, Edificio de Especialidades Médicas, Av. Interoceánica km 12 1/2 Cumbayá, Quito (Ecuador); Biomaterials Innovation Research Center, Department of Medicine, Brigham and Women' s Hospital, Harvard Medical School, Boston, MA, 02139 (United States); Aperador, W. [Departament of Engineering, Universidad Militar Nueva Granada, Bogotá (Colombia); Gutiérrez, O. [Departament of Pharmacology Universidad del Valle, Cali (Colombia); Caicedo, J.C., E-mail: julio.cesar.caicedo@correounivalle.edu.co [Tribology, Powder Metallurgy and Processing of Solid Recycled Research Group, Universidad del Valle, Cali (Colombia)

2016-06-01

Biological interfaces involve the interaction of complex macromolecular systems and other biomolecules or biomaterials. Researchers have used a combination of cell, material sciences and engineering approaches to create functional biointerfaces to help improve biological functions. Materials such as hydroxyapatite (HA), β-tricalcium phosphate (β-TCP) and chitosan are important biomaterials to be used in biomedical applications such as bone-prosthesis interfaces. In this work, it was evaluated the effect of different concentrations of chitosan on the structural, electrochemical and biocompatible properties of β-tricalcium phosphate-chitosan ((β-Ca{sub 3}(PO{sub 4}){sub 2})-(C{sub 6}H{sub 11}NO{sub 4})n) hybrid coatings. β–tricalcium phosphate-chitosan coatings were deposited on 316L stainless steel substrates applying 260 mA AC, an agitation velocity of 250 rpm, and temperature deposition of 60 °C. It was possible to obtain coatings of 600 μm of thickness. Structure and surface properties were analyzed by X-ray diffraction (XRD) and dispersive X-ray analysis (EDX). It was found that the arrangement of the β-TCP crystal lattice changed with increasing chitosan weight concentration, showing that the orthorhombic structure of β-TCP is under tensile stress. The electrochemical properties of β–tricalcium phosphate/chitosan (β-TCP–Ch) coatings were analyzed by electrochemical impedance spectroscopy (EIS). Cellular biocompatibility was determined by lactate dehydrogenase (LDH) cytotoxicity assay using primary chinese hamster ovary (CHO) cells. β-TCP–Ch coatings with chitosan concentrations up to 25% caused cytotoxic effects to only 5–10% of CHO cells. Obtained results showed the influence of chitosan in the structural, electrochemical, and biocompatible properties of AISI 316L Stainless Steel. Consequently, the electrochemical and cytotoxic behavior of β-TCP–Ch on 316L Stainless Steel indicated that the coatings might be a promising material in

Hydration of Concrete: The First Steps.

Science.gov (United States)

Thissen, Peter; Natzeck, Carsten; Giraudo, Nicolas; Weidler, Peter; Wöll, Christof

2018-04-12

Concrete is the most important construction material used by mankind and, at the same time, one of the most complex substances known in materials science. Since this mineral compound is highly porous, a better understanding of its surface chemistry, and in particular the reaction with water, is urgently required to understand and avoid corrosion of infrastructure like buildings and bridges. We have gained insight into proton transfer from concrete upon contact with water by applying the so-called Surface Science approach to a well-defined mineral, Wollastonite. Data from IR (infrared) spectroscopy reveal that exposure of this calcium-silicate (CS) substrate to H 2 O leads to dissociation and the formation of OH-species. This proton transfer is a chemical reaction of key importance, since on the one hand it triggers the conversion of cement into concrete (a calcium-silicate-hydrate phase), but on the other hand also governs the corrosion of concrete. Interestingly, we find that no proton transfer takes place when the same surface is exposed to methanol. In order to understand this unexpected difference, the analysis of the spectroscopic data obtained was aided by a detailed, first-principles computational study employing density functional theory (DFT). The combined experimental and theoretical effort allows derivation of a consistent picture of proton transfer reactions occurring in CS and CSH phases. Implications for strategies to protect this backbone of urban infrastructure from corrosion in harsh, aqueous environments will be discussed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

21 CFR 172.410 - Calcium silicate.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium silicate. 172.410 Section 172.410 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely...

Design and production of sintered {beta}-tricalcium phosphate 3D scaffolds for bone tissue regeneration

Energy Technology Data Exchange (ETDEWEB)

Santos, Carlos F.L. [CICS-UBI - Centro de Investigacao em Ciencias da Saude, Universidade da Beira Interior, Covilha (Portugal); Silva, Abilio P. [Centro de Ciencia e Tecnologia Aeroespaciais, Universidade da Beira Interior, Covilha (Portugal); Lopes, Luis [CICS-UBI - Centro de Investigacao em Ciencias da Saude, Universidade da Beira Interior, Covilha (Portugal); Pires, Ines [Instituto de Engenharia Mecanica - Lisboa (IDMEC Lisboa/IST/UTL), Avenida Rovisco Pais, 1049-001 Lisboa (Portugal); Correia, Ilidio J., E-mail: icorreia@ubi.pt [CICS-UBI - Centro de Investigacao em Ciencias da Saude, Universidade da Beira Interior, Covilha (Portugal)

2012-07-01

The characteristics of sintered {beta}-tricalcium phosphate ({beta}-TCP) scaffolds produced by 3D printing were studied by means of X-ray diffraction, Scanning Electron Microscopy, Fourier transform infrared spectroscopy, uniaxial compression tests and cytotoxicity tests, using human osteoblast cells. The results reported include details of the {beta}-TCP scaffolds' porosity, density, phase stability, mechanical behavior and cytotoxic profile. Collectively, these properties are fundamental for the future application of these scaffolds as bone substitutes for individualized therapy. Highlights: Black-Right-Pointing-Pointer {beta}-Tricalcium phosphate ({beta}-TCP) 3D scaffolds were produced by rapid prototyping. Black-Right-Pointing-Pointer Scaffold properties were assessed by SEM, FTIR, XRD and by mechanical tests. Black-Right-Pointing-Pointer The cytotoxic profile of the scaffolds was characterized by in vitro assays. Black-Right-Pointing-Pointer Scaffolds have good properties for its application as bone substitutes for individualized therapy.

Can hydrate dissolution experiments predict the fate of a natural hydrate system?

Energy Technology Data Exchange (ETDEWEB)

Hester, K.C.; Peltzer, E.T.; Dunk, R.M.; Walz, P.M.; Brewer, P.G. [Monterey Bay Aquarium Research Inst., Moss Landing, CA (United States); Dendy Sloan, E. [Colorado School of Mines, Golden, CO (United States). Center for Hydrate Research

2008-07-01

Gas hydrates are naturally occurring compounds found in permafrost regions and in oceans. In the natural environment, sufficient temperature and pressure conditions for hydrate formation exist over a significant portion of the ocean. However, in addition to pressure and temperature, the chemical potential of the gas in the hydrate must be equal to the surrounding waters. If the concentration of the gas in surrounding water is under-saturated with respect to the gas in the hydrate, the hydrate will dissolve to drive the system towards chemical equilibrium. This paper presented a dissolution study of exposed hydrate from outcrops at Barkley Canyon, located off Vancouver Island, British Columbia. A previous field experiment on synthetic methane hydrate samples had demonstrated that mass transfer controlled dissolution in under-saturated seawater. However, seafloor hydrate outcrops have been shown to have significant longevity compared to expected dissolution rates based upon convective boundary layer diffusion calculations. An in-situ dissolution experiment was performed on two distinct natural hydrate fabrics in order to help resolve this apparent disconnect between the dissolution rates of synthetic and natural hydrate. The paper presented a map of Barkley Canyon and discussed the field measurements and methods for the study. Exposed outcrops of gas hydrates were cored using a specially constructed stainless steel coring device and a hydraulic ram was located inside the corer. Hydrate samples were cored directly using the a manipulator arm and then injected into a sampling cell. The hydrate was then added to an open mesh exposure container, which allowed for exposure to ambient benthic currents with minimal disturbance. As well, in order to observe the slow dissolution of the hydrate in seawater at Barkley Canyon, time-lapse photography was employed. Last, the paper presented the results of the hydrate fabric porosities and hydrate dissolution rates. It was

Environ: E00192 [KEGG MEDICUS

Lifescience Database Archive (English)

Full Text Available E00192 Aluminum silicate hydrate with silicon dioxide (JP17) Hydrated halloysite T...me as: D06895 Clay mineral comprised of natural hydrated aluminium silicate and silicon dioxide; Standards for non-pharmacopoeial crude drugs ...

Tolerance Induction of Temperature and Starvation with Tricalcium Phosphate on Preservation and Sporulation in Bacillus amyloliquefaciens Detected by Flow Cytometry.

Science.gov (United States)

Shahrokh Esfahani, Samaneh; Emtiazi, Giti; Shafiei, Rasoul; Ghorbani, Najmeh; Zarkesh Esfahani, Seyed Hamid

2016-09-01

The Bacillus species have many applications in the preparation of various enzymes, probiotic, biofertilizer, and biomarkers for which the survival of resting cells and spore formation under different conditions are important. In this study, water and saline along with different mineral substances such as calcium carbonate, calcium phosphate, and silica were used for the detection of survival and preservation of Bacillus amyloliquefaciens. The results showed intensive death of resting cells at 8 °C, but significant survival at 28 °C after one month. However, preservation by minerals significantly decreased the rate of death and induced sporulation at both the temperatures. The resting cells were maintained at room temperature (about 60 % of the initial population survived after a month) in the presence of tricalcium phosphate. The results showed that temperature has more effect on sporulation compare with starvation. The sporulation in normal saline at 28 °C was 70 times more than that at 8 °C; meanwhile, addition of tricalcium phosphate increases sporulation by 90 times. Also, the FTIR data showed the interaction of tricalcium phosphate with spores and resting cells. The discrimination of sporulation from non-sporulation state was performed by nucleic acid staining with thiazole orange and detected by flow cytometry. The flow cytometric studies confirmed that the rates of sporulation in pure water were significantly more at 28 °C. This is the first report on the detection of bacterial spore with thiazole orange by flow cytometry and also on the interaction of tricalcium phosphate with spores by FTIR analyses.

Gas hydrate nucleation

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-12-31

The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

Gas hydrate nucleation

Energy Technology Data Exchange (ETDEWEB)

NONE

1998-12-31

The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

Gas hydrates

Digital Repository Service at National Institute of Oceanography (India)

Ramprasad, T.

, not all of them are white like snow. Some hydrates from the deep Gulf of Mexico are richly colored in shades of yellow, orange, or even red. The ice-like masses are beautiful, and contrast with the dull gray of deep sea muds. Hydrates from the Blake... volcanoes and associated gas hydrates: Marine Geology, v. 167, p. 29-42. Milkov, A.V. and R. Sassen, 2001a, Estimate of gas hydrate resource, northwestern Gulf of Mexico continental slope: Marine Geology, v. 179, pp. 71-83. Milkov, A.V., Sassen, R...

Shifting Focus: From Hydration for Performance to Hydration for Health.

Science.gov (United States)

Perrier, Erica T

2017-01-01

Over the past 10 years, literature on hydration biomarkers has evolved considerably - from (de)hydration assessment towards a more global definition of biomarkers of hydration in daily life. This shift in thinking about hydration markers was largely driven by investigating the differences that existed between otherwise healthy individuals whose habitual, ad-libitum drinking habits differ, and by identifying physiological changes in low-volume drinkers who subsequently increase their water intake. Aside from obvious differences in urinary volume and concentration, a growing body of evidence is emerging that links differences in fluid intake with small, but biologically significant, differences in vasopressin (copeptin), glomerular filtration rate, and markers of metabolic dysfunction or disease. Taken together, these pieces of the puzzle begin to form a picture of how much water intake should be considered adequate for health, and represent a shifting focus from hydration for performance, toward hydration for health outcomes. This narrative review outlines the key areas of research in which the global hydration process - including water intake, urinary hydration markers, and vasopressin - has been associated with health outcomes, focusing on kidney and metabolic endpoints. It will also provide a commentary on how various hydration biomarkers may be used in hydration for health assessment. Finally, if adequate water intake can play a role in maintaining health, how might we tell if we are drinking enough? Urine output is easily measured, and can take into account differences in daily physical activity, climate, dietary solute load, and other factors that influence daily water needs. Today, targets have been proposed for urine osmolality, specific gravity, and color that may be used by researchers, clinicians, and individuals as simple indicators of optimal hydration. However, there remain a large number of incomplete or unanswered research questions regarding the

Environmental silicate nano-biocomposites

CERN Document Server

Pollet, Eric

2012-01-01

Environmental Silicate Nano-Biocomposites focuses on nano-biocomposites, which are obtained by the association of silicates such as bioclays with biopolymers. By highlighting recent developments and findings, green and biodegradable nano-composites from both renewable and biodegradable polymers are explored. This includes coverage of potential markets such as packaging, agricultures, leisure and the fast food industry. The knowledge and experience of more than twenty international experts in diverse fields, from chemical and biochemical engineering to applications, is brought together in four different sections covering: Biodegradable polymers and Silicates, Clay/Polyesters Nano-biocomposites, Clay/Agropolymers Nano-biocomposites, and Applications and biodegradation of Nano-biocomposites. By exploring the relationships between the biopolymer structures, the processes, and the final properties Environmental Silicate Nano-Biocomposites explains how to design nano-materials to develop new, valuable, environmenta...

Impacts of Hydrate Distribution on the Hydro-Thermo-Mechanical Properties of Hydrate-Bearing Sediments

Science.gov (United States)

Dai, S.; Seol, Y.

2015-12-01

In general, hydrate makes the sediments hydraulically less conductive, thermally more conductive, and mechanically stronger; yet the dependency of these physical properties on hydrate saturation varies with hydrate distribution and morphology. Hydrate distribution in sediments may cause the bulk physical properties of their host sediments varying several orders of magnitude even with the same amount of hydrate. In natural sediments, hydrate morphology is inherently governed by the burial depth and the grain size of the host sediments. Compare with patchy hydrate, uniformly distributed hydrate is more destructive to fluid flow, yet leads to higher gas and water permeability during hydrate dissociation due to the easiness of forming percolation paths. Water and hydrate have similar thermal conductivity values; the bulk thermal conductivity of hydrate-bearing sediments depends critically on gas-phase saturation. 60% of gas saturation may result in evident thermal conductivity drop and hinder further gas production. Sediments with patchy hydrate yield lower stiffness than that with cementing hydrate but higher stiffness than that with pore filling and loading bearing hydrate. Besides hydrate distribution, the stress state and loading history also play an important role in the mechanical behavior of hydrate-bearing sediments.

SILICATE COMPOSITION OF THE INTERSTELLAR MEDIUM

International Nuclear Information System (INIS)

Fogerty, S.; Forrest, W.; Watson, D. M.; Koch, I.; Sargent, B. A.

2016-01-01

The composition of silicate dust in the diffuse interstellar medium and in protoplanetary disks around young stars informs our understanding of the processing and evolution of the dust grains leading up to planet formation. An analysis of the well-known 9.7 μ m feature indicates that small amorphous silicate grains represent a significant fraction of interstellar dust and are also major components of protoplanetary disks. However, this feature is typically modeled assuming amorphous silicate dust of olivine and pyroxene stoichiometries. Here, we analyze interstellar dust with models of silicate dust that include non-stoichiometric amorphous silicate grains. Modeling the optical depth along lines of sight toward the extinguished objects Cyg OB2 No. 12 and ζ Ophiuchi, we find evidence for interstellar amorphous silicate dust with stoichiometry intermediate between olivine and pyroxene, which we simply refer to as “polivene.” Finally, we compare these results to models of silicate emission from the Trapezium and protoplanetary disks in Taurus.

SILICATE COMPOSITION OF THE INTERSTELLAR MEDIUM

Energy Technology Data Exchange (ETDEWEB)

Fogerty, S.; Forrest, W.; Watson, D. M.; Koch, I. [Department of Physics and Astronomy, University of Rochester, Rochester, NY 14627 (United States); Sargent, B. A., E-mail: sfogerty@pas.rochester.edu [Center for Imaging Science and Laboratory for Multiwavelength Astrophysics, Rochester Institute of Technology, 54 Lomb Memorial Drive, Rochester, NY 14623 (United States)

2016-10-20

The composition of silicate dust in the diffuse interstellar medium and in protoplanetary disks around young stars informs our understanding of the processing and evolution of the dust grains leading up to planet formation. An analysis of the well-known 9.7 μ m feature indicates that small amorphous silicate grains represent a significant fraction of interstellar dust and are also major components of protoplanetary disks. However, this feature is typically modeled assuming amorphous silicate dust of olivine and pyroxene stoichiometries. Here, we analyze interstellar dust with models of silicate dust that include non-stoichiometric amorphous silicate grains. Modeling the optical depth along lines of sight toward the extinguished objects Cyg OB2 No. 12 and ζ Ophiuchi, we find evidence for interstellar amorphous silicate dust with stoichiometry intermediate between olivine and pyroxene, which we simply refer to as “polivene.” Finally, we compare these results to models of silicate emission from the Trapezium and protoplanetary disks in Taurus.

Osteogenic potential of bone marrow stromal cells on smooth, roughened, and tricalcium phosphate-modified titanium alloy surfaces.

LENUS (Irish Health Repository)

Colombo, John S

2012-09-01

This study investigated the influence of smooth, roughened, and tricalcium phosphate (TCP)-coated roughened titanium-aluminum-vanadium (Ti-6Al-4V) surfaces on the osteogenic potential of rat bone marrow stromal cells (BMSCs).

New french uranium mineral species

International Nuclear Information System (INIS)

Branche, G.; Chervet, J.; Guillemin, C.

1952-01-01

In this work, the authors study the french new uranium minerals: parsonsite and renardite, hydrated phosphates of lead and uranium; kasolite: silicate hydrated of uranium and lead uranopilite: sulphate of uranium hydrated; bayleyite: carbonate of uranium and of hydrated magnesium; β uranolite: silicate of uranium and of calcium hydrated. For all these minerals, the authors give the crystallographic, optic characters, and the quantitative chemical analyses. On the other hand, the following species, very rare in the french lodgings, didn't permit to do quantitative analyses. These are: the lanthinite: hydrated uranate oxide; the α uranotile: silicate of uranium and of calcium hydrated; the bassetite: uranium phosphate and of hydrated iron; the hosphuranylite: hydrated uranium phosphate; the becquerelite: hydrated uranium oxide; the curite: oxide of uranium and lead hydrated. Finally, the authors present at the end of this survey a primary mineral: the brannerite, complex of uranium titanate. (author) [fr

A simple, rapid and eco friendly method for determination of uranium in geological samples of low silicate matrix by ICP-OES

International Nuclear Information System (INIS)

Hanuman, V.V.; Chakrapani, G.; Singh, A.K.

2013-01-01

A simple, rapid, cost effective and eco friendly decomposition and dissolution method is developed for the determination of uranium (U 3 O 8 ) by Inductively Coupled Plasma - Optical Emission Spectrometer (ICP-OES) in low silicate geological samples. The salts of Sodium di-hydrogen phosphate monohydrate and Sodium pyrophosphate deca hydrate are used in the ratio of 1:1 (phosphate flux) for the decomposition of low silicate matrix geological samples. Samples are decomposed by fusion with the phosphate flux after ignition and the dissolution is carried out using distilled water. If the samples contain >10% silica, they have been treated with little amount of (HF+HNO 3 ) prior to fusion with phosphate flux. These samples, are analysed by ICP-OES directly without any separation from the matrix. The spectral interferences of major matrix elements (Al, Ti, Fe, Mn, etc present in the sample) on uranium are studied and it is observed that their interferences are negligible, as dilution is required to bring uranium concentration into calibration range of instrument. This is the first time, the phosphate flux is used for decomposition of low silicate geological samples for uranium determination by ICP-OES

Effect of Zn and Mg in tricalcium phosphate and in culture medium on apoptosis and actin ring formation of mature osteoclasts

International Nuclear Information System (INIS)

Li Xia; Ito, Atsuo; Sogo, Yu; Senda, Koji; Yamazaki, Atsushi

2008-01-01

This study investigated the resorptive activity of osteoclasts on tricalcium phosphate (TCP), zinc-containing tricalcium phosphate (ZnTCP) and magnesium-containing tricalcium phosphate (MgTCP) ceramics in different Zn- or Mg-containing culture media. On the TCP ceramic, an increase in Zn ions in the culture medium within the range between 0.3 and 6.8 ppm significantly induced an increase in osteoclast apoptosis and a decrease in actin ring formation. However, even a high level of Mg ions up to 100 ppm in the culture medium was unlikely to induce an increase in osteoclast apoptosis. Mg ions in the MgTCP ceramics have no effect on osteoclast apoptosis and actin ring formation. There was almost no significant difference in osteoclast apoptosis and actin ring formation between ZnTCP and MgTCP ceramics which have the same solubility and dissolution rates. It is indicated that only an increase in Zn level outside resorption lacuna has an inhibitory effect on osteoclast resorption and that an increase in Zn level inside resorption lacuna could not influence the osteoclast activity.

Fluorescence emission behavior of Eu(III) sorbed on calcium silicate hydrates as a secondary mineral formed without drying process

International Nuclear Information System (INIS)

Niibori, Yuichi; Narita, Masayuki; Chida, Taiji; Mimura, Hitoshi; Kirishima, Akira

2014-01-01

Calcium silicate hydrate (CSH) is a main component of cement-based material required for constructing the geological repository. As in many countries, since the repository in Japan is constructed below water table, we must consider the interaction of radionuclide with cement materials altered around the repository after the backfill. Using fluorescence emission spectra, so far, the authors have investigated the interaction of Eu(III) (as a chemical analog of Am(III)) with CSH gels as a secondary mineral formed without drying process, considering a condition saturated with groundwater. However, in such fluorescence emission behaviors, a deexcitation process of OH vibrators of light water and a quenching effect caused by Eu-Eu energy transfer between Eu atoms incorporated in the CSH gel must be considered. This study examined the fluorescence emission behavior of Eu(III) sorbed on CSH gels, by using La(III) (non-fluorescent ions) as a diluent of Eu(III). Furthermore, CSH samples were synthesized with CaO, SiO 2 , and heavy water (D 2 O) as a solvent in order to avoid the obvious deexcitation process of OH vibrators of light water. In the results, the peak around 618 nm was split into two peaks of 613 nm and 622 nm in the cases of Ca/Si=1.0 and 1.6. Then, the peak of 613 nm decreased with increment of Eu(III)/La(III) ratio. This means that the relative intensity of 613 nm is useful to quantify the amount of Eu(III) incorporated in CSH gel. Besides, the decay behavior of the fluorescence emission did not depend on the Eu/La concentration ratio. That is, such a quenching effect is neglectable. Additionally, the fluorescence emission spectra of Eu(III) showed that the state of Eu(III) depended on Ca/Si ratio of CSH. This suggested that there was several sites in CSH to incorporate Eu(III). When CSH is altered, whole cementitious material in repository must be altered forming cracks and leaching some calcium compositions. Therefore, the adsorptive capacity of CSH might

Modifying Silicates for Better Dispersion in Nanocomposites

Science.gov (United States)

Campbell, Sandi

2005-01-01

An improved chemical modification has been developed to enhance the dispersion of layered silicate particles in the formulation of a polymer/silicate nanocomposite material. The modification involves, among other things, the co-exchange of an alkyl ammonium ion and a monoprotonated diamine with interlayer cations of the silicate. The net overall effects of the improved chemical modification are to improve processability of the nanocomposite and maximize the benefits of dispersing the silicate particles into the polymer. Some background discussion is necessary to give meaning to a description of this development. Polymer/silicate nanocomposites are also denoted polymer/clay composites because the silicate particles in them are typically derived from clay particles. Particles of clay comprise layers of silicate platelets separated by gaps called "galleries." The platelet thickness is 1 nm. The length varies from 30 nm to 1 m, depending on the silicate. In order to fully realize the benefits of polymer/silicate nanocomposites, it is necessary to ensure that the platelets become dispersed in the polymer matrices. Proper dispersion can impart physical and chemical properties that make nanocomposites attractive for a variety of applications. In order to achieve nanometer-level dispersion of a layered silicate into a polymer matrix, it is typically necessary to modify the interlayer silicate surfaces by attaching organic functional groups. This modification can be achieved easily by ion exchange between the interlayer metal cations found naturally in the silicate and protonated organic cations - typically protonated amines. Long-chain alkyl ammonium ions are commonly chosen as the ion-exchange materials because they effectively lower the surface energies of the silicates and ease the incorporation of organic monomers or polymers into the silicate galleries. This completes the background discussion. In the present improved modification of the interlayer silicate surfaces

Biocompatibility and bioactivity of porous polymer-derived Ca-Mg silicate ceramics.

Science.gov (United States)

Fiocco, L; Li, S; Stevens, M M; Bernardo, E; Jones, J R

2017-03-01

Magnesium is a trace element in the human body, known to have important effects on cell differentiation and the mineralisation of calcified tissues. This study aimed to synthesise highly porous Ca-Mg silicate foamed scaffolds from preceramic polymers, with analysis of their biological response. Akermanite (Ak) and wollastonite-diopside (WD) ceramic foams were obtained from the pyrolysis of a liquid silicone mixed with reactive fillers. The porous structure was obtained by controlled water release from selected fillers (magnesium hydroxide and borax) at 350°C. The homogeneous distribution of open pores, with interconnects of modal diameters of 160-180μm was obtained and maintained after firing at 1100°C. Foams, with porosity exceeding 80%, exhibited compressive strength values of 1-2MPa. In vitro studies were conducted by immersion in SBF for 21days, showing suitable dissolution rates, pH and ionic concentrations. Cytotoxicity analysis performed in accordance with ISO10993-5 and ISO10993-12 standards confirmed excellent biocompatibility of both Ak and WD foams. In addition, MC3T3-E1 cells cultured on the Mg-containing scaffolds demonstrated enhanced osteogenic differentiation and the expression of osteogenic markers including Collagen Type I, Osteopontin and Osteocalcin, in comparison to Mg-free counterparts. The results suggest that the addition of magnesium can further enhance the bioactivity and the potential for bone regeneration applications of Ca-silicate materials. Here, we show that the incorporation of Mg in Ca-silicates plays a significant role in the enhancement of the osteogenic differentiation and matrix formation of MC3T3-E1 cells, cultured on polymer-derived highly porous scaffolds. Reduced degradation rates and improved mechanical properties are also observed, compared to Mg-free counterparts, suggesting the great potential of Ca-Mg silicates as bone tissue engineering materials. Excellent biocompatibility of the new materials, in accordance to

A new quantification method based on SEM-EDS to assess fly ash composition and study the reaction of its individual components in hydrating cement paste

Energy Technology Data Exchange (ETDEWEB)

Durdziński, Paweł T., E-mail: pawel.durdzinski@gmail.com [Laboratory of Construction Materials, École Polytechnique Fédérale de Lausanne (EPFL), Station 12, CH-1015 Lausanne (Switzerland); Dunant, Cyrille F. [Laboratory of Construction Materials, École Polytechnique Fédérale de Lausanne (EPFL), Station 12, CH-1015 Lausanne (Switzerland); Haha, Mohsen Ben [HeidelbergCement Technology Center GmbH (HeidelbergCement AG), Rohrbacher Str. 95, 69181 Leimen (Germany); Scrivener, Karen L. [Laboratory of Construction Materials, École Polytechnique Fédérale de Lausanne (EPFL), Station 12, CH-1015 Lausanne (Switzerland)

2015-07-15

Calcareous fly ashes are high-potential reactive residues for blended cements, but their qualification and use in concrete are hindered by heterogeneity and variability. Current characterization often fails to identify the dominant, most reactive, amorphous fraction of the ashes. We developed an approach to characterize ashes using electron microscopy. EDS element composition of millions of points is plotted in a ternary frequency plot. A visual analysis reveals number and ranges of chemical composition of populations: silicate, calcium-silicate, aluminosilicate, and calcium-rich aluminosilicate. We quantified these populations in four ashes and followed their hydration in two Portland-ash systems. One ash reacted at a moderate rate: it was composed of 70 vol.% of aluminosilicates and calcium-silicates and reached 60% reaction at 90 days. The other reacted faster, reaching 60% at 28 days due to 55 vol.% of calcium-rich aluminosilicates, but further reaction was slower and 15 vol.% of phases, the silica-rich ones, did not react.

A new quantification method based on SEM-EDS to assess fly ash composition and study the reaction of its individual components in hydrating cement paste

International Nuclear Information System (INIS)

Durdziński, Paweł T.; Dunant, Cyrille F.; Haha, Mohsen Ben; Scrivener, Karen L.

2015-01-01

Calcareous fly ashes are high-potential reactive residues for blended cements, but their qualification and use in concrete are hindered by heterogeneity and variability. Current characterization often fails to identify the dominant, most reactive, amorphous fraction of the ashes. We developed an approach to characterize ashes using electron microscopy. EDS element composition of millions of points is plotted in a ternary frequency plot. A visual analysis reveals number and ranges of chemical composition of populations: silicate, calcium-silicate, aluminosilicate, and calcium-rich aluminosilicate. We quantified these populations in four ashes and followed their hydration in two Portland-ash systems. One ash reacted at a moderate rate: it was composed of 70 vol.% of aluminosilicates and calcium-silicates and reached 60% reaction at 90 days. The other reacted faster, reaching 60% at 28 days due to 55 vol.% of calcium-rich aluminosilicates, but further reaction was slower and 15 vol.% of phases, the silica-rich ones, did not react

Sodium Silicate Gel Effect on Cemented Tailing Backfill That Contains Lead-Zinc Smelting Slag at Early Ages

Directory of Open Access Journals (Sweden)

Lijie Guo

2018-01-01

Full Text Available This paper presents the results of an experimental study on the priming effect of sodium silicate gel (SS on cemented tailing backfill (CTB that contains lead-zinc smelting slag. CTB and cemented paste (CP containing lead-zinc smelting slag samples with SS of 0 and 0.4% of the mass of the slag were prepared and cured at 20°C for 1, 3, 7, and 28 days. Mechanical test and pore structure analyses were performed on the studied CTB samples, microstructural analyses (X-ray diffraction analysis and thermal gravity analysis were performed on the studied CP samples, whereas the electrical conductivity of CTB was monitored. The results reveal that SS has a significant positive effect on cementitious activity of binder mixed by cement and lead-zinc smelting slag. This activation leads to the acceleration of binder hydration process, the formation of more cement hydration products in the CTBs, and the refinement of their pore structure, which is favorable for the strength development of CTB.

The role of integrin αv in proliferation and differentiation of human dental pulp cell response to calcium silicate cement.

Science.gov (United States)

Hung, Chi-Jr; Hsu, Hsin-I; Lin, Chi-Chang; Huang, Tsui-Hsien; Wu, Buor-Chang; Kao, Chia-Tze; Shie, Ming-You

2014-11-01

It has been proved that integrin αv activity is related to cell proliferation, differentiation, migration, and organ development. However, the biological functions of integrin αv in human dental pulp cells (hDPCs) cultured on silicate-based materials have not been explored. The aim of this study was to investigate the role of integrin αv in the proliferation and odontogenic differentiation of hDPCs cultured with the effect of calcium silicate (CS) cement and β-tricalcium phosphate (TCP) cement. In this study, hDPCs were cultured on CS and TCP materials, and we evaluated fibronectin (FN) secretion and integrin αv expression during the cell attachment stage. After small interfering RNA transfection targeting integrin αv, the proliferation and odontogenesis differentiation behavior of hDPCs were analyzed. The results indicate that CS releases Si ion-increased FN secretion and adsorption, which promote cell attachment more effectively than TCP. The CS cement facilitates FN and αv subintegrin expression. However, the FN adsorption and integrin expression of TCP are similar to that observed in the control dish. Integrin αv small interfering RNA inhibited odontogenic differentiation of hDPCs with the decreased formation of mineralized nodules on CS. It also down-regulated the protein expression of multiple markers of odontogenesis and the expression of dentin sialophosphoprotein protein. These results establish composition-dependent differences in integrin binding and its effectiveness as a mechanism regulating cellular responses to biomaterial surface. Copyright © 2014 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Bone Regeneration of Rat Tibial Defect by Zinc-Tricalcium Phosphate (Zn-TCP Synthesized from Porous Foraminifera Carbonate Macrospheres

Directory of Open Access Journals (Sweden)

Joshua Chou

2013-12-01

Full Text Available Foraminifera carbonate exoskeleton was hydrothermally converted to biocompatible and biodegradable zinc-tricalcium phosphate (Zn-TCP as an alternative biomimetic material for bone fracture repair. Zn-TCP samples implanted in a rat tibial defect model for eight weeks were compared with unfilled defect and beta-tricalcium phosphate showing accelerated bone regeneration compared with the control groups, with statistically significant bone mineral density and bone mineral content growth. CT images of the defect showed restoration of cancellous bone in Zn-TCP and only minimal growth in control group. Histological slices reveal bone in-growth within the pores and porous chamber of the material detailing good bone-material integration with the presence of blood vessels. These results exhibit the future potential of biomimetic Zn-TCP as bone grafts for bone fracture repair.

21 CFR 582.2227 - Calcium silicate.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium silicate. 582.2227 Section 582.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

Hydrothermal synthesis of porous triphasic hydroxyapatite/(alpha and beta) tricalcium phosphate.

Science.gov (United States)

Vani, R; Girija, E K; Elayaraja, K; Prakash Parthiban, S; Kesavamoorthy, R; Narayana Kalkura, S

2009-12-01

A novel, porous triphasic calcium phosphate composed of nonresorbable hydroxyapatite (HAp) and resorbable tricalcium phosphate (alpha- and beta-TCP) has been synthesized hydrothermally at a relatively low temperature. The calcium phosphate precursor for hydrothermal treatment was prepared by gel method in the presence of ascorbic acid. XRD, FT-IR, Raman analyses confirmed the presence of HAp/TCP. The surface area and average pore size of the samples were found to be 28 m2/g and 20 nm, respectively. The samples were found to be bioactive in simulated body fluid (SBF).

Long-term Effects of Relative Humidity on Properties of Microwave Hardened Moulding Sand with Sodium Silicate

Directory of Open Access Journals (Sweden)

Stachowicz M.

2017-09-01

Full Text Available Moulding sands containing sodium silicate (water-glass belong to the group of porous mixture with low resistance to increased humidity. Thanks to hydrophilic properties of hardened or even overheated binder, possible is application of effective methods of hydrous reclamation consisting in its secondary hydration. For the same reason (hydrophilia of the binder, moulds and foundry cores made of high-silica moulding sands with sodium silicate are susceptible to the action of components of atmospheric air, including the contained steam. This paper presents results of a research on the effect of (relative humidity on mechanical and technological properties of microwave-hardened moulding mixtures. Specimens of the moulding sand containing 1.5 wt% of sodium water-glass with module 2.5 were subjected, in a laboratory climatic chamber, to long-term action of steam contained in the chamber atmosphere. Concentration of water in atmospheric air was stabilized for 28 days (672 h according to the relative humidity parameter that was ca. 40%, 60% and 80% at constant temperature 20 °C. In three cycles of the examinations, the specimens were taken out from the chamber every 7 days (168 h and their mechanical and technological parameters were determined. It was found on the grounds of laboratory measurements that moulds and cores hardened with microwaves are susceptible to action of atmospheric air and presence of water (as steam intensifies action of the air components on glassy film of sodium silicate. Microwave-hardened moulding sands containing sodium silicate may be stored on a long-term basis in strictly determined atmospheric conditions only, at reduced humidity. In spite of a negative effect of steam contained in the air, the examined moulding mixtures maintain a part of their mechanical and technological properties, so the moulds and foundry cores stored in specified, controlled conditions could be still used in manufacture.

21 CFR 182.2227 - Calcium silicate.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium silicate. 182.2227 Section 182.2227 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Calcium silicate. (a) Product. Calcium silicate. (b) Tolerance. 2 percent and 5 percent. (c) Limitations...

The effect of adding magnesium oxide on the mechanical properties of the tricalcium phosphate-zirconia composites

Energy Technology Data Exchange (ETDEWEB)

Sallemi, Imen, E-mail: imen.sallemi@hotmail.com; Bouaziz, Jamel; Ben Ayed, Foued

2015-02-01

The effect of magnesium oxide on the mechanical properties of the tricalcium phosphate – 50 wt.% zirconia composites was investigated during a sintering process between 1300 °C and 1400 °C. The characteristics of the samples before and after the sintering process were realized by using the differential thermal analysis, dilatometry, X-ray diffraction, the {sup 31}P magic angle scanning nuclear magnetic resonance, the scanning electron microscope and by considering such mechanical properties as the rupture strength and Vickers hardness. The mechanical performances of the tricalcium phosphate-50 wt.% zirconia composites increased with both the percentage of magnesium oxide and the sintering temperature. At 1400 °C, the mechanical properties of the composites sintered with 10 wt.% magnesium oxide reached their maximum value. Thus, Vickers hardness increased from 554 to 6350 MPa and the rupture strength of the corresponding composites varied from 5.2 to 25 MPa. The increase of the mechanical properties of the samples is due to the formation of both the tetragonal zirconia phase and the liquid phase which helps to fill the pores. The microstructure of needle form is most probably phosphate precipitates which are formed from this liquid phase. Furthermore, the presence of magnesium oxide in the composites prevented the inverse allotropic transformation of zirconia. - Highlights: • We measure the rupture strength and Vickers hardness of bioceramics. • We characterize the effect of MgO on the mechanical properties of the tricalcium phosphate – 50 wt% zirconia composites. • MgO increase the mechanical properties of the composites.

Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

Science.gov (United States)

Circone, S.; Kirby, S.H.; Stern, L.A.

2005-01-01

The composition of methane hydrate, namely nW for CH 4??nWH2O, was directly measured along the hydrate equilibrium boundary under conditions of excess methane gas. Pressure and temperature conditions ranged from 1.9 to 9.7 MPa and 263 to 285 K. Within experimental error, there is no change in hydrate composition with increasing pressure along the equilibrium boundary, but nW may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n W = 5.81-6.10 H2O describes the entire range of measured values, with an average composition of CH4??5.99(??0.07) H2O along the equilibrium boundary. These results, consistent with previously measured values, are discussed with respect to the widely ranging values obtained by thermodynamic analysis. The relatively constant composition of methane hydrate over the geologically relevant pressure and temperature range investigated suggests that in situ methane hydrate compositions may be estimated with some confidence. ?? 2005 American Chemical Society.

The increase of apatite layer formation by the poly(3-hydroxybutyrate) surface modification of hydroxyapatite and β-tricalcium phosphate.

Science.gov (United States)

Szubert, M; Adamska, K; Szybowicz, M; Jesionowski, T; Buchwald, T; Voelkel, A

2014-01-01

The aim of this study was the surface modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) grafting and characterization of modificates. The bioactivity examination was carried out by the determination to grow an apatite layer on modified materials during incubation in simulated body fluid at 37°C. The additional issue taken up in this paper was to investigate the influence of fluid replacement. The process of the surface modification of biomaterials was evaluated by means of infrared and Raman spectroscopy. Formation of the apatite layer was assessed by means of scanning electron microscopy and confirmed by energy dispersive, Raman and Fourier transformed infrared spectroscopy. During exposure in simulated body fluid, the variation of the zeta potential, pH measurement and relative weight was monitored. Examination of scanning electron microscopy micrographs suggests that modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) significantly increases apatite layer formation. Raman spectroscopy evaluation revealed that the formation of the apatite layer was more significant in the case of hydroxyapatite modificate, when compared to the β-tricalcium phosphate modificate. Both modificates were characterized by stable pH, close to the natural pH of human body fluids. Furthermore, we have shown that a weekly changed, simulated body fluid solution increases apatite layer formation. © 2013.

Effects of 3D-Printed Polycaprolactone/?-Tricalcium Phosphate Membranes on Guided Bone Regeneration

OpenAIRE

Shim, Jin-Hyung; Won, Joo-Yun; Park, Jung-Hyung; Bae, Ji-Hyeon; Ahn, Geunseon; Kim, Chang-Hwan; Lim, Dong-Hyuk; Cho, Dong-Woo; Yun, Won-Soo; Bae, Eun-Bin; Jeong, Chang-Mo; Huh, Jung-Bo

2017-01-01

This study was conducted to compare 3D-printed polycaprolactone (PCL) and polycaprolactone/β-tricalcium phosphate (PCL/β-TCP) membranes with a conventional commercial collagen membrane in terms of their abilities to facilitate guided bone regeneration (GBR). Fabricated membranes were tested for dry and wet mechanical properties. Fibroblasts and preosteoblasts were seeded into the membranes and rates and patterns of proliferation were analyzed using a kit-8 assay and by scanning electron micro...

Regularities in Low-Temperature Phosphatization of Silicates

Science.gov (United States)

Savenko, A. V.

2018-01-01

The regularities in low-temperature phosphatization of silicates are defined from long-term experiments on the interaction between different silicate minerals and phosphate-bearing solutions in a wide range of medium acidity. It is shown that the parameters of the reaction of phosphatization of hornblende, orthoclase, and labradorite have the same values as for clayey minerals (kaolinite and montmorillonite). This effect may appear, if phosphotization proceeds, not after silicate minerals with a different structure and composition, but after a secondary silicate phase formed upon interaction between silicates and water and stable in a certain pH range. Variation in the parameters of the reaction of phosphatization at pH ≈ 1.8 is due to the stability of the silicate phase different from that at higher pH values.

Gas hydrate in nature

Science.gov (United States)

Ruppel, Carolyn D.

2018-01-17

Gas hydrate is a naturally occurring, ice-like substance that forms when water and gas combine under high pressure and at moderate temperatures. Methane is the most common gas present in gas hydrate, although other gases may also be included in hydrate structures, particularly in areas close to conventional oil and gas reservoirs. Gas hydrate is widespread in ocean-bottom sediments at water depths greater than 300–500 meters (m; 984–1,640 feet [ft]) and is also present in areas with permanently frozen ground (permafrost). Several countries are evaluating gas hydrate as a possible energy resource in deepwater or permafrost settings. Gas hydrate is also under investigation to determine how environmental change may affect these deposits.

[Skin hydration and hydrating products].

Science.gov (United States)

Duplan, H; Nocera, T

2018-05-01

One of the skin's principal functions is to protect the body against its environment by maintaining an effective epidermal barrier, not only against external factors, but also to prevent water loss from the body. Indeed, water homeostasis is vital for the normal physiological functioning of skin. Hydration levels affect not only visible microscopic parameters such as the suppleness and softness of skin, but also molecular parameters, enzyme activities and cellular signalling within the epidermis. The body is continually losing some of its water, but this phenomenon is limited and the optimal hydration gradient in skin is ensured via a set of sophisticated regulatory processes that rely on the functional and dynamic properties of the uppermost level of the skin consisting of the stratum corneum. The present article brings together data recently acquired in the fields of skin hydration and the characterisation of dehydrated or dry skin, whether through study of the regulatory processes involved or as a result of changes in the techniques used for in situ measurement, and thus in optimisation of management. Copyright © 2018. Published by Elsevier Masson SAS.

Drug: D06895 [KEGG MEDICUS

Lifescience Database Archive (English)

Full Text Available D06895 Crude ... Drug Aluminum silicate hydrate with silicon dioxide (JP17); Hydra...21] ... Same as: E00192 Therapeutic category: 5100 ... Clay mineral comprised of natural hydrated aluminium silicate and silico

Thermodynamics and Kinetics of Silicate Vaporization

Science.gov (United States)

Jacobson, Nathan S.; Costa, Gustavo C. C.

2015-01-01

Silicates are a common class of materials that are often exposed to high temperatures. The behavior of these materials needs to be understood for applications as high temperature coatings in material science as well as the constituents of lava for geological considerations. The vaporization behavior of these materials is an important aspect of their high temperature behavior and it also provides fundamental thermodynamic data. The application of Knudsen effusion mass spectrometry (KEMS) to silicates is discussed. There are several special considerations for silicates. The first is selection of an appropriate cell material, which is either nearly inert or has well-understood interactions with the silicate. The second consideration is proper measurement of the low vapor pressures. This can be circumvented by using a reducing agent to boost the vapor pressure without changing the solid composition or by working at very high temperatures. The third consideration deals with kinetic barriers to vaporization. The measurement of these barriers, as encompassed in a vaporization coefficient, is discussed. Current measured data of rare earth silicates for high temperature coating applications are discussed. In addition, data on magnesium-iron-silicates (olivine) are presented and discussed.

Reactions between rocks and the hydroxides of calcium, sodium and potassium: progress report no. 1

International Nuclear Information System (INIS)

Van Aardt, J.H.P.; Visser, S.

1982-01-01

The reaction between the hydroxides of calcium, sodium and potassium, and clay minerals, feldspars, and some rocks (aggregates for use in concrete) was investigated. The reaction products were examined by means of x-ray diffraction and chemical analysis. The solid reaction products identified were hydrated calcium silicates,hydrated calcium aluminates, and hydrated calcium alumina silicates. It was found that, in the presence of water, calcium hydroxide liberated alkali into solution if the rocks and minerals contained alkali metals in their structure. Two crystalline hydrated sodium calcium silicates (12A and 16A) were prepared in the system Na 2 O-CaO-SiO 2 -H 2 O at 80 degrees Celsius. The one compound (12A) was also observed when sodium hydroxide plus calcium hydroxide and water reacted with silica- or silicate-containing rocks

Historical methane hydrate project review

Science.gov (United States)

Collett, Timothy; Bahk, Jang-Jun; Frye, Matt; Goldberg, Dave; Husebo, Jarle; Koh, Carolyn; Malone, Mitch; Shipp, Craig; Torres, Marta

2013-01-01

In 1995, U.S. Geological Survey made the first systematic assessment of the volume of natural gas stored in the hydrate accumulations of the United States. That study, along with numerous other studies, has shown that the amount of gas stored as methane hydrates in the world greatly exceeds the volume of known conventional gas resources. However, gas hydrates represent both a scientific and technical challenge and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of gas hydrates in nature, (2) assessing the volume of natural gas stored within various gas hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural gas hydrates, and (5) analyzing the effects of methane hydrate on drilling safety.Methane hydrates are naturally occurring crystalline substances composed of water and gas, in which a solid water-­‐lattice holds gas molecules in a cage-­‐like structure. The gas and water becomes a solid under specific temperature and pressure conditions within the Earth, called the hydrate stability zone. Other factors that control the presence of methane hydrate in nature include the source of the gas included within the hydrates, the physical and chemical controls on the migration of gas with a sedimentary basin containing methane hydrates, the availability of the water also included in the hydrate structure, and the presence of a suitable host sediment or “reservoir”. The geologic controls on the occurrence of gas hydrates have become collectively known as the “methane hydrate petroleum system”, which has become the focus of numerous hydrate research programs.Recognizing the importance of methane hydrate research and the need for a coordinated

Crustal thermal state and origin of silicic magma in Iceland: the case of Torfajökull, Ljósufjöll and Snæfellsjökull volcanoes

Science.gov (United States)

Martin, E.; Sigmarsson, O.

2007-05-01

Pleistocene and Holocene peralkaline rhyolites from Torfajökull (South Iceland Volcanic Zone) and Ljósufjöll central volcanoes and trachytes from Snæfellsjökull (Snæfellsnes Volcanic Zone) allow the assessment of the mechanism for silicic magma genesis as a function of geographical location and crustal geothermal gradient. The low δ18O (2.4‰) and low Sr concentration (12.2 ppm) measured in Torfajökull rhyolites are best explained by partial melting of hydrated metabasaltic crust followed by major fractionation of feldspar. In contrast, very high 87Sr/86Sr (0.70473) and low Ba (8.7 ppm) and Sr (1.2 ppm) concentrations measured in Ljósufjöll silicic lavas are best explained by fractional crystallisation and subsequent 87Rb decay. Snæfellsjökull trachytes are also generated by fractional crystallisation, with less than 10% crustal assimilation, as inferred from their δ18O. The fact that silicic magmas within, or close to, the rift zone are principally generated by crustal melting whereas those from off-rift zones are better explained by fractional crystallisation clearly illustrates the controlling influence of the thermal state of the crust on silicic magma genesis in Iceland.

Hydraulic and Mechanical Effects from Gas Hydrate Conversion and Secondary Gas Hydrate Formation during Injection of CO2 into CH4-Hydrate-Bearing Sediments

Science.gov (United States)

Bigalke, N.; Deusner, C.; Kossel, E.; Schicks, J. M.; Spangenberg, E.; Priegnitz, M.; Heeschen, K. U.; Abendroth, S.; Thaler, J.; Haeckel, M.

2014-12-01

The injection of CO2 into CH4-hydrate-bearing sediments has the potential to drive natural gas production and simultaneously sequester CO2 by hydrate conversion. The process aims at maintaining the in situ hydrate saturation and structure and causing limited impact on soil hydraulic properties and geomechanical stability. However, to increase hydrate conversion yields and rates it must potentially be assisted by thermal stimulation or depressurization. Further, secondary formation of CO2-rich hydrates from pore water and injected CO2 enhances hydrate conversion and CH4 production yields [1]. Technical stimulation and secondary hydrate formation add significant complexity to the bulk conversion process resulting in spatial and temporal effects on hydraulic and geomechanical properties that cannot be predicted by current reservoir simulation codes. In a combined experimental and numerical approach, it is our objective to elucidate both hydraulic and mechanical effects of CO2 injection and CH4-CO2-hydrate conversion in CH4-hydrate bearing soils. For the experimental approach we used various high-pressure flow-through systems equipped with different online and in situ monitoring tools (e.g. Raman microscopy, MRI and ERT). One particular focus was the design of triaxial cell experimental systems, which enable us to study sample behavior even during large deformations and particle flow. We present results from various flow-through high-pressure experimental studies on different scales, which indicate that hydraulic and geomechanical properties of hydrate-bearing sediments are drastically altered during and after injection of CO2. We discuss the results in light of the competing processes of hydrate dissociation, hydrate conversion and secondary hydrate formation. Our results will also contribute to the understanding of effects of temperature and pressure changes leading to dissociation of gas hydrates in ocean and permafrost systems. [1] Deusner C, Bigalke N, Kossel E

Strength Estimation for Hydrate-Bearing Sediments From Direct Shear Tests of Hydrate-Bearing Sand and Silt

Science.gov (United States)

Liu, Zhichao; Dai, Sheng; Ning, Fulong; Peng, Li; Wei, Houzhen; Wei, Changfu

2018-01-01

Safe and economic methane gas production, as well as the replacement of methane while sequestering carbon in natural hydrate deposits, requires enhanced geomechanical understanding of the strength and volume responses of hydrate-bearing sediments during shear. This study employs a custom-made apparatus to investigate the mechanical and volumetric behaviors of carbon dioxide hydrate-bearing sediments subjected to direct shear. The results show that both peak and residual strengths increase with increased hydrate saturation and vertical stress. Hydrate contributes mainly the cohesion and dilatancy constraint to the peak strength of hydrate-bearing sediments. The postpeak strength reduction is more evident and brittle in specimens with higher hydrate saturation and under lower stress. Significant strength reduction after shear failure is expected in silty sediments with high hydrate saturation Sh ≥ 0.65. Hydrate contribution to the residual strength is mainly by increasing cohesion at low hydrate saturation and friction at high hydrate saturation. Stress state and hydrate saturation are dominating both the stiffness and the strength of hydrate-bearing sediments; thus, a wave velocity-based peak strength prediction model is proposed and validated, which allows for precise estimation of the shear strength of hydrate-bearing sediments through acoustic logging data. This method is advantageous to geomechanical simulators, particularly when the experimental strength data of natural samples are not available.

Gas hydrate concentration and characteristics within Hydrate Ridge inferred from multicomponent seismic reflection data

Science.gov (United States)

Kumar, Dhananjay; Sen, Mrinal K.; Bangs, Nathan L.

2007-12-01

A seismic experiment composed of streamer and ocean bottom seismometer (OBS) surveys was conducted in the summer of 2002 at southern Hydrate Ridge, offshore Oregon, to map the gas hydrate distribution within the hydrate stability zone. Gas hydrate concentrations within the reservoir can be estimated with P wave velocity (Vp); however, we can further constrain gas hydrate concentrations using S wave velocity (Vs), and use Vs through its relationship to Vp (Vp/Vs) to reveal additional details such as gas hydrate form within the matrix (i.e., hydrate cements the grains, becomes part of the matrix frame or floats in pore space). Both Vp and Vs can be derived simultaneously by inverting multicomponent seismic data. In this study, we use OBS data to estimate seismic velocities where both gas hydrate and free gas are present in the shallow sediments. Once Vp and Vs are estimated, they are simultaneously matched with modeled velocities to estimate the gas hydrate concentration. We model Vp using an equation based on a modification of Wood's equation that incorporates an appropriate rock physics model and Vs using an empirical relation. The gas hydrate concentration is estimated to be up to 7% of the rock volume, or 12% of the pore space. However, Vp and Vs do not always fit the model simultaneously. Vp can vary substantially more than Vs. Thus we conclude that a model, in which higher concentrations of hydrate do not affect shear stiffness, is more appropriate. Results suggest gas hydrates form within the pore space of the sediments and become part of the rock framework in our survey area.

Compositional Evolution of Calcium Silicate Hydrate (C-S-H) Structures by Total X-Ray Scattering

KAUST Repository

Soyer-Uzun, Sezen; Chae, Sejung Rosie; Benmore, Chris J.; Wenk, Hans-Rudolf; Monteiro, Paulo J. M.

2011-01-01

High-energy X-ray diffraction was employed to study the structural characteristics of a set of C-S-H samples with 0.6 ≤ C/S a;circ 1.75. It has been observed that Si is tetrahedrally coordinated to O for all samples irrespective of chemical composition and the Ca-O coordination number gradually decreases from ∼7 to ∼6 with increasing C/S ratio. This suggests that the C-S-H structure evolves from a tobermorite-like structure into a jennite-like structure as a function of increasing C/S ratio as the interlayer space decreases from ∼1.3 to ∼1 nm. Evolution of these short- and medium-range order structural characteristics in the C-S-H system is associated with the alteration of the Ca-O layers and silicate depolymerization with increasing C/S. © 2011 The American Ceramic Society.

Compositional Evolution of Calcium Silicate Hydrate (C-S-H) Structures by Total X-Ray Scattering

KAUST Repository

Soyer-Uzun, Sezen

2011-12-09

High-energy X-ray diffraction was employed to study the structural characteristics of a set of C-S-H samples with 0.6 ≤ C/S a;circ 1.75. It has been observed that Si is tetrahedrally coordinated to O for all samples irrespective of chemical composition and the Ca-O coordination number gradually decreases from ∼7 to ∼6 with increasing C/S ratio. This suggests that the C-S-H structure evolves from a tobermorite-like structure into a jennite-like structure as a function of increasing C/S ratio as the interlayer space decreases from ∼1.3 to ∼1 nm. Evolution of these short- and medium-range order structural characteristics in the C-S-H system is associated with the alteration of the Ca-O layers and silicate depolymerization with increasing C/S. © 2011 The American Ceramic Society.

Polymer-Layer Silicate Nanocomposites

DEFF Research Database (Denmark)

Potarniche, Catalina-Gabriela

Nowadays, some of the material challenges arise from a performance point of view as well as from recycling and biodegradability. Concerning these aspects, the development of polymer layered silicate nanocomposites can provide possible solutions. This study investigates how to obtain polymer layered...... with a spectacular improvement up to 300 % in impact strength were obtained. In the second part of this study, layered silicate bio-nanomaterials were obtained starting from natural compounds and taking into consideration their biocompatibility properties. These new materials may be used for drug delivery systems...... and as biomaterials due to their high biocompatible properties, and because they have the advantage of being biodegradable. The intercalation process of natural compounds within silicate platelets was investigated. By uniform dispersing of binary nanohybrids in a collagen matrix, nanocomposites with intercalated...

LABORATORY INVESTIGATIONS OF SILICATE MUD CONTAMINATION WITH CALCIUM

Directory of Open Access Journals (Sweden)

Nediljka Gaurina-Međimurec

2004-12-01

Full Text Available The silicate-based drilling fluid is a low solids KCl/polymer system with the addition of soluble sodium or potassium silicate to enhance inhibition and wellbore stability. Silicate-based drilling fluids exhibit remarkable shale and chalk stabilizing properties, resulting in gauge hole and the formation of firm cuttings when drilling reactive shales and soft chalks. Silicates protect shales by in-situ gellation when exposed to the neutral pore fluid and precipitation, which occurs on contact with divalent ions present at the surface of the shale. Also, silicates prevent the dispersion and washouts when drilling soft chalk by reacting with the Ca2+ ions present on chalk surfaces of cutting and wellbore to form a protective film. The silicate-based drilling fluid can be used during drilling hole section through shale interbeded anhydrite formations because of its superior shale stabilizing characteristics. However, drilling through the anhydrite can decrease the silicate concentration and change rheological and filtration fluid properties. So, the critical concentration of calcium ions should be investigated by lab tests. This paper details the mechanism of shale inhibition using silicate-based drilling fluid, and presents results of lab tests conducted to ascertain the effect of Ca2+ ions on silicate level in the fluid and the fluid properties.

Sintering and robocasting of beta-tricalcium phosphate scaffoldsfor orthopaedic applications

Energy Technology Data Exchange (ETDEWEB)

Miranda, Pedro; Saiz, Eduardo; Gryn Karol; Tomsia, Antoni P.

2005-11-01

{beta}-tricalcium phosphate ({beta}-TCP) scaffolds with designed, three-dimensional (3-D) geometry and mesoscale porosity have been fabricated by direct-write assembly (robocasting) techniques. Concentrated {beta}-TCP inks with suitable viscoelastic properties were developed to enable the fabrication of the complex 3-D structures. A comprehensive study of the sintering behavior of TCP as a function of the calcium content in the starting powder was also carried out, and the optimal heat treatment for fabricating scaffolds with dense {beta}-TCP rods has been determined. Such analysis provides clues to controlling the microstructure of the fabricated structures and, therefore, enabling the fabrication by robocasting of TCP scaffolds with tailored performance for bone tissue engineering applications.

21 CFR 582.2122 - Aluminum calcium silicate.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Aluminum calcium silicate. 582.2122 Section 582.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

21 CFR 182.2122 - Aluminum calcium silicate.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Aluminum calcium silicate. 182.2122 Section 182.2122 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED....2122 Aluminum calcium silicate. (a) Product. Aluminum calcium silicate. (b) Tolerance. 2 percent. (c...

Antibacterial Activity of Silicate Bioceramics

Institute of Scientific and Technical Information of China (English)

HU Sheng; NING Congqin; ZHOU Yue; CHEN Lei; LIN Kaili; CHANG Jiang

2011-01-01

Four kinds of pure silicate ceramic particles, CaSiO3, Ca3SiO5, bredigite and akermanite were prepared and their bactericidal effects were systematically investigated. The phase compositions of these silicate ceramics were characterized by XRD. The ionic concentration meas urement revealed that the Calcium (Ca) ion concentration were relatively higher in Ca3SiO5 and bredigite, and much lower in CaSiO3 and akermanite. Accordingly, the pH values of the four silicate ceramics extracts showed a positive correlation with the particle concentrations. Meanwhile, by decreasing the particle size, higher Ca ion concentrations can be achieved, leading to the increase of aqueous pH value as well. In summary, all of the four silicate ceramics tested in our study showed antibacterial effect in a dose-dependent manner. Generally, the order of their antibacterial activity against E.coli from strong to weak is Ca3SiO5, bredigite, CaSiO3 and akermanite.

Application of empirical hydration distribution functions around polar atoms for assessing hydration structures of proteins

International Nuclear Information System (INIS)

Matsuoka, Daisuke; Nakasako, Masayoshi

2013-01-01

Highlights: ► Empirical distribution functions of water molecules in protein hydration are made. ► The functions measure how hydrogen-bond geometry in hydration deviate from ideal. ► The functions assess experimentally identified hydration structures of protein. - Abstract: To quantitatively characterize hydrogen-bond geometry in local hydration structures of proteins, we constructed a set of empirical hydration distribution functions (EHDFs) around polar protein atoms in the main and side chains of 11 types of hydrophilic amino acids (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 113 (2009) 11274). The functions are the ensemble average of possible hydration patterns around the polar atoms, and describe the anisotropic deviations from ideal hydrogen bond geometry. In addition, we defined probability distribution function of hydration water molecules (PDFH) over the hydrophilic surface of a protein as the sum of EHDFs of solvent accessible polar protein atoms. The functions envelop most of hydration sites identified in crystal structures of proteins (D. Matsuoka, M. Nakasako, Journal of Physical Chemistry B 114 (2010) 4652). Here we propose the application of EHDFs and PDFHs for assessing crystallographically identified hydration structures of proteins. First, hydration water molecules are classified with respect to the geometry in hydrogen bonds in referring EHDFs. Difference Fourier electron density map weighted by PDFH of protein is proposed to identify easily density peaks as candidates of hydration water molecules. A computer program implementing those ideas was developed and used for assessing hydration structures of proteins

Amended Silicated for Mercury Control

Energy Technology Data Exchange (ETDEWEB)

James Butz; Thomas Broderick; Craig Turchi

2006-12-31

Amended Silicates{trademark}, a powdered, noncarbon mercury-control sorbent, was tested at Duke Energy's Miami Fort Station, Unit 6 during the first quarter of 2006. Unit 6 is a 175-MW boiler with a cold-side electrostatic precipitator (ESP). The plant burns run-of-the-river eastern bituminous coal with typical ash contents ranging from 8-15% and sulfur contents from 1.6-2.6% on an as-received basis. The performance of the Amended Silicates sorbent was compared with that for powdered activated carbon (PAC). The trial began with a period of baseline monitoring during which no sorbent was injected. Sampling during this and subsequent periods indicated mercury capture by the native fly ash was less than 10%. After the baseline period, Amended Silicates sorbent was injected at several different ratios, followed by a 30-day trial at a fixed injection ratio of 5-6 lb/MMACF. After this period, PAC was injected to provide a comparison. Approximately 40% mercury control was achieved for both the Amended Silicates sorbent and PAC at injection ratios of 5-6 lbs/MMACF. Higher injection ratios did not achieve significantly increased removal. Similar removal efficiencies have been reported for PAC injection trials at other plants with cold-side ESPs, most notably for plants using medium to high sulfur coal. Sorbent injection did not detrimentally impact plant operations and testing confirmed that the use of Amended Silicates sorbent does not degrade fly ash quality (unlike PAC). The cost for mercury control using either PAC or Amended Silicates sorbent was estimated to be equivalent if fly ash sales are not a consideration. However, if the plant did sell fly ash, the effective cost for mercury control could more than double if those sales were no longer possible, due to lost by-product sales and additional cost for waste disposal. Accordingly, the use of Amended Silicates sorbent could reduce the overall cost of mercury control by 50% or more versus PAC for locations where

Interstellar silicate analogs for grain-surface reaction experiments: Gas-phase condensation and characterization of the silicate dust grains

Energy Technology Data Exchange (ETDEWEB)

Sabri, T.; Jäger, C. [Laboratory Astrophysics Group of the Max Planck Institute for Astronomy at the Friedrich Schiller University Jena Institute of Solid State Physics, Helmholtzweg 3, D-07743 Jena (Germany); Gavilan, L.; Lemaire, J. L.; Vidali, G. [Observatoire de Paris/Université de Cergy-Pontoise, 5 mail Gay Lussac, F-95000 Cergy-Pontoise (France); Mutschke, H. [Laboratory Astrophysics Group of the Astrophysical Institute and University Observatory, Friedrich Schiller University Jena Schillergässchen 3, D-07743 Jena (Germany); Henning, T., E-mail: tolou.sabri@uni-jena.de [Max Planck Institute for Astronomy Königstuhl 17, D-69117 Heidelberg (Germany)

2014-01-10

Amorphous, astrophysically relevant silicates were prepared by laser ablation of siliceous targets and subsequent quenching of the evaporated atoms and clusters in a helium/oxygen gas atmosphere. The described gas-phase condensation method can be used to synthesize homogeneous and astrophysically relevant silicates with different compositions ranging from nonstoichiometric magnesium iron silicates to pyroxene- and olivine-type stoichiometry. Analytical tools have been used to characterize the morphology, composition, and spectral properties of the condensates. The nanometer-sized silicate condensates represent a new family of cosmic dust analogs that can generally be used for laboratory studies of cosmic processes related to condensation, processing, and destruction of cosmic dust in different astrophysical environments. The well-characterized silicates comprising amorphous Mg{sub 2}SiO{sub 4} and Fe{sub 2}SiO{sub 4}, as well as the corresponding crystalline silicates forsterite and fayalite, produced by thermal annealing of the amorphous condensates, have been used as real grain surfaces for H{sub 2} formation experiments. A specifically developed ultra-high vacuum apparatus has been used for the investigation of molecule formation experiments. The results of these molecular formation experiments on differently structured Mg{sub 2}SiO{sub 4} and Fe{sub 2}SiO{sub 4} described in this paper will be the topic of the next paper of this series.

Synthesis and in vitro Experiment of Biomaterial Tricalcium Phosphate

Directory of Open Access Journals (Sweden)

X.V Bui

2016-12-01

as an ideal candidate for bone graft in hard tissue engineering due to its high biocompatibility, bioactivity and bone bonding. The preparation, as well as the application of this powder material, has been the important topic of research in material science. In this paper, β-tricalcium phosphate (β-TCP, a component that has chemical formulation similar to bone structure, was synthesized by the precipitate method and then calcinated at 1000oC for 5 h. The physico-chemical properties of synthetic material were examined by XRD, FT-IR and SEM methods. In vitro experience was also carried by soaking β-TCP simulated body fluid powder in a different period of time. Obtained results confirmed the quality of β-TCP synthetic material and its bioactivity.

In Situ Raman Analyses of Natural Gas and Gas Hydrates at Hydrate Ridge, Oregon

Science.gov (United States)

Peltzer, E. T.; White, S. N.; Dunk, R. M.; Brewer, P. G.; Sherman, A. D.; Schmidt, K.; Hester, K. C.; Sloan, E. D.

2004-12-01

During a July 2004 cruise to Hydrate Ridge, Oregon, MBARI's sea-going laser Raman spectrometer was used to obtain in situ Raman spectra of natural gas hydrates and natural gas venting from the seafloor. This was the first in situ analysis of gas hydrates on the seafloor. The hydrate spectra were compared to laboratory analyses performed at the Center for Hydrate Research, Colorado School of Mines. The natural gas spectra were compared to MBARI gas chromatography (GC) analyses of gas samples collected at the same site. DORISS (Deep Ocean Raman In Situ Spectrometer) is a laboratory model laser Raman spectrometer from Kaiser Optical Systems, Inc modified at MBARI for deployment in the deep ocean. It has been successfully deployed to depths as great as 3600 m. Different sampling optics provide flexibility in adapting the instrument to a particular target of interest. An immersion optic was used to analyze natural gas venting from the seafloor at South Hydrate Ridge ( ˜780 m depth). An open-bottomed cube was placed over the vent to collect the gas. The immersion optic penetrated the side of the cube as did a small heater used to dissociate any hydrate formed during sample collection. To analyze solid hydrates at both South and North Hydrate Ridge ( ˜590 m depth), chunks of hydrate were excavated from the seafloor and collected in a glass cylinder with a mesh top. A stand-off optic was used to analyze the hydrate inside the cylinder. Due to the partial opacity of the hydrate and the small focal volume of the sampling optic, a precision underwater positioner (PUP) was used to focus the laser spot onto the hydrate. PUP is a stand-alone system with three degrees-of-freedom, capable of moving the DORISS probe head with a precision of 0.1 mm. In situ Raman analyses of the gas indicate that it is primarily methane. This is verified by GC analyses of samples collected from the same site. Other minor constituents (such as CO2 and higher hydrocarbons) are present but may be in

Hydration characteristics of zirconium oxide replaced Portland cement for use as a root-end filling material.

Science.gov (United States)

Camilleri, J; Cutajar, A; Mallia, B

2011-08-01

Zirconium oxide can be added to dental materials rendering them sufficiently radiopaque. It can thus be used to replace the bismuth oxide in mineral trioxide aggregate (MTA). Replacement of Portland cement with 30% zirconium oxide mixed at a water/cement ratio of 0.3 resulted in a material with adequate physical properties. This study aimed at investigating the microstructure, pH and leaching in physiological solution of Portland cement replaced zirconium oxide at either water-powder or water-cement ratios of 0.3 for use as a root-end filling material. The hydration characteristics of the materials which exhibited optimal behavior were evaluated. Portland cement replaced by zirconium oxide in varying amounts ranging from 0 to 50% in increments of 10 was prepared and divided into two sets. One set was prepared at a constant water/cement ratio while the other set at a constant water/powder ratio of 0.3. Portland cement and MTA were used as controls. The materials were analyzed under the scanning electron microscope (SEM) and the hydration products were determined. X-ray energy dispersive analysis (EDX) was used to analyze the elemental composition of the hydration products. The pH and the amount of leachate in Hank's balanced salt solution (HBSS) were evaluated. A material that had optimal properties that satisfied set criteria and could replace MTA was selected. The microstructure of the prototype material and Portland cement used as a control was assessed after 30 days using SEM and atomic ratio diagrams of Al/Ca versus Si/Ca and S/Ca versus Al/Ca were plotted. The hydration products of Portland cement replaced with 30% zirconium oxide mixed at water/cement ratio of 0.3 were calcium silicate hydrate, calcium hydroxide and minimal amounts of ettringite and monosulphate. The calcium hydroxide leached in HBSS solution resulted in an increase in the pH value. The zirconium oxide acted as inert filler and exhibited no reaction with the hydration by-products of Portland

Ductile flow of methane hydrate

Science.gov (United States)

Durham, W.B.; Stern, L.A.; Kirby, S.H.

2003-01-01

Compressional creep tests (i.e., constant applied stress) conducted on pure, polycrystalline methane hydrate over the temperature range 260-287 K and confining pressures of 50-100 MPa show this material to be extraordinarily strong compared to other icy compounds. The contrast with hexagonal water ice, sometimes used as a proxy for gas hydrate properties, is impressive: over the thermal range where both are solid, methane hydrate is as much as 40 times stronger than ice at a given strain rate. The specific mechanical response of naturally occurring methane hydrate in sediments to environmental changes is expected to be dependent on the distribution of the hydrate phase within the formation - whether arranged structurally between and (or) cementing sediments grains versus passively in pore space within a sediment framework. If hydrate is in the former mode, the very high strength of methane hydrate implies a significantly greater strain-energy release upon decomposition and subsequent failure of hydrate-cemented formations than previously expected.

Hydration rate of obsidian.

Science.gov (United States)

Friedman, I; Long, W

1976-01-30

The hydration rates of 12 obsidian samples of different chemical compositions were measured at temperatures from 95 degrees to 245 degrees C. An expression relating hydration rate to temperature was derived for each sample. The SiO(2) content and refractive index are related to the hydration rate, as are the CaO, MgO, and original water contents. With this information it is possible to calculate the hydration rate of a sample from its silica content, refractive index, or chemical index and a knowledge of the effective temperature at which the hydration occurred. The effective hydration temperature can be either measured or approximated from weather records. Rates have been calculated by both methods, and the results show that weather records can give a good approximation to the true EHT, particularly in tropical and subtropical climates. If one determines the EHT by any of the methods suggested, and also measures or knows the rate of hydration of the particular obsidian used, it should be possible to carry out absolute dating to +/- 10 percent of the true age over periods as short as several years and as long as millions of years.

Effect of moisture and chitosan layered silicate on morphology and properties of chitosan/layered silicates films

International Nuclear Information System (INIS)

Silva, J.R.M.B. da; Santos, B.F.F. dos; Leite, I.F.

2014-01-01

Thin chitosan films have been for some time an object of practical assessments. However, to obtain biopolymers capable of competing with common polymers a significant improvement in their properties is required. Currently, the technology of obtaining polymer/layered silicates nanocomposites has proven to be a good alternative. This work aims to evaluate the effect of chitosan content (CS) and layered silicates (AN) on the morphology and properties of chitosan/ layered silicate films. CS/AN bionanocomposites were prepared by the intercalation by solution in the proportion 1:1 and 5:1. Then were characterized by infrared spectroscopy (FTIR), diffraction (XRD) and X-ray thermogravimetry (TG). It is expected from the acquisition of films, based on different levels of chitosan and layered silicates, choose the best composition to serve as a matrix for packaging drugs and thus be used for future research. (author)

Chemical alteration of calcium silicate hydrates in saline groundwater. Mechanism of sorption of Na on C-S-H and effect of NaCl on leaching of Ca from C-S-H

International Nuclear Information System (INIS)

Sugiyama, Daisuke; Fujita, Tomonari

2004-01-01

In the concept for TRU waste disposal in Japan, cement is a potential waste packaging and backfilling material and is expected to provide chemical containment. In the presence of some reactive ions in a saline groundwater, the chemical properties of cement materials should be affected. In this study, the mechanism of sorption of sodium (Na) on C-S-H and the effect of sodium chloride (NaCl) concentration on dissolution of Calcium Silicate Hydrate (C-S-H) are discussed by measuring the sorption isotherm of sodium onto C-S-H gel (Ca/Si = 0.65-1.2). Based on the experimental results, it is showed that sodium sorbs by substitution for Ca in C-S-H phases and leaching of Ca from C-S-H is enhanced in NaCl solution ( -1 mol dm -3 ). The results of sorption experiments are reasonably well modelled by the ion-exchange model assuming some calcium sites with different ion-exchange log K values. It is also suggested that the dissolution of C-S-H can be modelled reasonably well by considering the effect of ionic strength on activity coefficients of aqueous species for high Ca/Si ratio of C-S-H, and the effect of exchange of sodium with calcium of C-S-H on leaching of Ca becomes obvious for lower Ca/Si ratio of C-S-H. (author)

Overview: Nucleation of clathrate hydrates.

Science.gov (United States)

Warrier, Pramod; Khan, M Naveed; Srivastava, Vishal; Maupin, C Mark; Koh, Carolyn A

2016-12-07

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

Overview: Nucleation of clathrate hydrates

Science.gov (United States)

Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

2016-12-01

Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

Exogenous origin of hydration on asteroid (16) Psyche: the role of hydrated asteroid families

Science.gov (United States)

Avdellidou, C.; Delbo', M.; Fienga, A.

2018-04-01

Asteroid (16) Psyche, which for a long time was the largest M-type with no detection of hydration features in its spectrum, was recently discovered to have a weak 3-μm band and thus it was eventually added to the group of hydrated asteroids. Its relatively high density, in combination with the high radar albedo, led researchers to classify the asteroid as a metallic object. It is believed that it is possibly a core of a differentiated body, a remnant of `hit-and-run' collisions. The detection of hydration is, in principle, inconsistent with a pure metallic origin for this body. Here, we consider the scenario in which the hydration on its surface is exogenous and was delivered by hydrated impactors. We show that impacting asteroids that belong to families whose members have the 3-μm band can deliver hydrated material to Psyche. We developed a collisional model with which we test all dark carbonaceous asteroid families, which contain hydrated members. We find that the major source of hydrated impactors is the family of Themis, with a total implanted mass on Psyche of the order of ˜1014 kg. However, the hydrated fraction could be only a few per cent of the implanted mass, as the water content in carbonaceous chondrite meteorites, the best analogue for the Themis asteroid family, is typically a few per cent of their mass.

Induction of bone formation by smart biphasic hydroxyapatite tricalcium phosphate biomimetic matrices in the non-human primate Papio ursinus

CSIR Research Space (South Africa)

Ripamonti, U

2008-01-01

Full Text Available Long-term studies in the non-human primate Chacma baboon Papio ursinus were set to investigate the induction of bone formation by biphasic hydroxyapatite/β-tricalcium phosphate (HA/β-TCP) biomimetic matrices. HA/β-TCP biomimetic matrices in a pre...

Methane Hydrates: Chapter 8

Science.gov (United States)

Boswell, Ray; Yamamoto, Koji; Lee, Sung-Rock; Collett, Timothy S.; Kumar, Pushpendra; Dallimore, Scott

2008-01-01

Gas hydrate is a solid, naturally occurring substance consisting predominantly of methane gas and water. Recent scientific drilling programs in Japan, Canada, the United States, Korea and India have demonstrated that gas hydrate occurs broadly and in a variety of forms in shallow sediments of the outer continental shelves and in Arctic regions. Field, laboratory and numerical modelling studies conducted to date indicate that gas can be extracted from gas hydrates with existing production technologies, particularly for those deposits in which the gas hydrate exists as pore-filling grains at high saturation in sand-rich reservoirs. A series of regional resource assessments indicate that substantial volumes of gas hydrate likely exist in sand-rich deposits. Recent field programs in Japan, Canada and in the United States have demonstrated the technical viability of methane extraction from gas-hydrate-bearing sand reservoirs and have investigated a range of potential production scenarios. At present, basic reservoir depressurisation shows the greatest promise and can be conducted using primarily standard industry equipment and procedures. Depressurisation is expected to be the foundation of future production systems; additional processes, such as thermal stimulation, mechanical stimulation and chemical injection, will likely also be integrated as dictated by local geological and other conditions. An innovative carbon dioxide and methane swapping technology is also being studied as a method to produce gas from select gas hydrate deposits. In addition, substantial additional volumes of gas hydrate have been found in dense arrays of grain-displacing veins and nodules in fine-grained, clay-dominated sediments; however, to date, no field tests, and very limited numerical modelling, have been conducted with regard to the production potential of such accumulations. Work remains to further refine: (1) the marine resource volumes within potential accumulations that can be

In-situ gas hydrate hydrate saturation estimated from various well logs at the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

Science.gov (United States)

Lee, M.W.; Collett, T.S.

2011-01-01

In 2006, the U.S. Geological Survey (USGS) completed detailed analysis and interpretation of available 2-D and 3-D seismic data and proposed a viable method for identifying sub-permafrost gas hydrate prospects within the gas hydrate stability zone in the Milne Point area of northern Alaska. To validate the predictions of the USGS and to acquire critical reservoir data needed to develop a long-term production testing program, a well was drilled at the Mount Elbert prospect in February, 2007. Numerous well log data and cores were acquired to estimate in-situ gas hydrate saturations and reservoir properties.Gas hydrate saturations were estimated from various well logs such as nuclear magnetic resonance (NMR), P- and S-wave velocity, and electrical resistivity logs along with pore-water salinity. Gas hydrate saturations from the NMR log agree well with those estimated from P- and S-wave velocity data. Because of the low salinity of the connate water and the low formation temperature, the resistivity of connate water is comparable to that of shale. Therefore, the effect of clay should be accounted for to accurately estimate gas hydrate saturations from the resistivity data. Two highly gas hydrate-saturated intervals are identified - an upper ???43 ft zone with an average gas hydrate saturation of 54% and a lower ???53 ft zone with an average gas hydrate saturation of 50%; both zones reach a maximum of about 75% saturation. ?? 2009.

Formation of submarine gas hydrates

Energy Technology Data Exchange (ETDEWEB)

Soloviev, V.; Ginsburg, G.D. (Reserch Institute of Geology and Mineral Resources of the Ocean ' ' VNII Okeangeologia' ' , St. Petersburg (Russian Federation))

1994-03-01

Submarine gas hydrates have been discoverd in the course of deep-sea drilling (DSDP and ODP) and bottom sampling in many offshore regions. This paper reports on expeditions carried out in the Black, Caspian and Okhotsk Seas. Gas hydrate accumulations were discovered and investigated in all these areas. The data and an analysis of the results of the deep-sea drilling programme suggest that the infiltration of gas-bearing fluids is a necessary condition for gas hydrate accumulation. This is confirmed by geological observations at three scale levels. Firstly, hydrates in cores are usually associated with comparatively coarse-grained, permeable sediments as well as voids and fractures. Secondly, hydrate accumulations are controlled by permeable geological structures, i.e. faults, diapirs, mud volcanos as well as layered sequences. Thirdly, in the worldwide scale, hydrate accumulations are characteristic of continental slopes and rises and intra-continental seas where submarine seepages also are widespread. Both biogenic and catagenic gas may occur, and the gas sources may be located at various distances from the accumulation. Gas hydrates presumably originate from water-dissolved gas. The possibility of a transition from dissolved gas into hydrate is confirmed by experimental data. Shallow gas hydrate accumulations associated with gas-bearing fluid plumes are the most convenient features for the study of submarine hydrate formation in general. These accumulations are known from the Black, Caspian and Okhotsk Seas, the Gulf of Mexico and off northern California. (au) (24 refs.)

New nanostructural biomaterials based on active silicate systems and hydroxyapatite: characterization and genotoxicity in human peripheral blood lymphocytes.

Science.gov (United States)

Opačić-Galić, V; Petrović, V; Zivković, S; Jokanović, V; Nikolić, B; Knežević-Vukčević, J; Mitić-Ćulafić, D

2013-06-01

To characterize and investigate the genotoxic effect of a new endodontic cement based on dicalcium- and tricalcium-silicate (CS) with hydroxyapatite (HA) on human lymphocytes. Hydrothermal treatment was applied for synthesis of CS and HA. The final mixture HA-CS, with potential to be used in endodontic practice, is composed of CS (34%) and HA (66%). Human lymphocytes were incubated with HA, HA-CS and CS for 1 h, at 37 °C and 5% CO2. Cell viability was determined using the trypan blue exclusion assay. To evaluate the level of DNA damage comet assay (single cell gel electrophoresis) was performed. For the statistical analysis anova and Duncan's Post Hoc Test were used. The SEM analysis indicated that CS consisted mostly of agglomerates of several micrometers in size, built up from smaller particles, with dimensions between 117 and 477 nm. This is promising because dimensions of agglomerates are not comparable with channels inside the cell membranes, whereas their nano-elements provide evident activity, important for faster setting of these mixtures compared to MTA. Values of DNA damage obtained in the comet assay indicated low genotoxic risk of the new endodontic materials. The significantly improved setting characteristics and low genotoxic risk of the new material support further research. © 2012 International Endodontic Journal.

Adsorption of aqueous silicate on hematite

International Nuclear Information System (INIS)

Taylor, P.; Ticknor, K.V.

1997-08-01

During radioisotope sorption studies, adsorption of silicate from synthetic groundwaters by synthetic hematite was observed. To further investigate this observation, the adsorption of silicate onto hematite (α-Fe 2 O 3 ) powder from a neutral, aqueous NaC1 solution (0.1 mol/dm 3 ), containing 2.56 x 10 -4 mol/dm 3 of Si added as Na 2 SiO 3 ·9H 2 O, was measured at ∼21 deg C. Equilibrium adsorption of silicate amounted to ∼1.93 μmol/m 2 (one Si(O,OH) 4 moiety per 86 A 2 ). It is important to take this adsorption into account when evaluating the ability of iron oxides to adsorb other species, especially anions, from groundwaters. Silicate adsorption is known to diminish the ability of iron oxides to adsorb other anions. (author)

Silicates materials of high vacuum technology

CERN Document Server

Espe, Werner

2013-01-01

Materials of High Vacuum Technology, Volume 2: Silicates covers silicate insulators of special importance to vacuum technology. The book discusses the manufacture, composition, and physical and chemical properties of technical glasses, quartz glass, quartzware, vycor glass, ceramic materials, mica, and asbestos.

Methods to determine hydration states of minerals and cement hydrates

Energy Technology Data Exchange (ETDEWEB)

Baquerizo, Luis G., E-mail: luis.baquerizoibarra@holcim.com [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Matschei, Thomas [Innovation, Holcim Technology Ltd., CH-5113 Holderbank (Switzerland); Scrivener, Karen L. [Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Saeidpour, Mahsa; Thorell, Alva; Wadsö, Lars [Building Materials, Lund University, Box 124, 221 000 Lund (Sweden)

2014-11-15

This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate are presented. Some of the methods used were validated with the system Na{sub 2}SO{sub 4}–H{sub 2}O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions.

Methods to determine hydration states of minerals and cement hydrates

International Nuclear Information System (INIS)

Baquerizo, Luis G.; Matschei, Thomas; Scrivener, Karen L.; Saeidpour, Mahsa; Thorell, Alva; Wadsö, Lars

2014-01-01

This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate are presented. Some of the methods used were validated with the system Na 2 SO 4 –H 2 O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions

Enthalpy of dissociation and hydration number of methane hydrate from the Clapeyron equation

International Nuclear Information System (INIS)

Anderson, Graydon K.

2004-01-01

The enthalpies of the reactions in which methane hydrate is dissociated to methane vapor and either (1) water, or (2) ice are determined by a new analysis using the Clapeyron equation. The difference in enthalpies of the two reactions is used to infer the hydration number at the quadruple point where hydrate, ice, liquid water, and methane vapor coexist. By appropriate corrections, the hydration number at points removed from the quadruple point is also determined. The most important feature of the new analysis is the direct use of the Clapeyron equation. The method avoids the use of certain simplifying assumptions that have compromised the accuracy of previous analyses in which the Clausius-Clapeyron equation was used. The analysis takes into account the finite volumes of all phases, the non-ideality of the vapor phase, and the solubility of methane in water. The results show that the enthalpy of dissociation and hydration number are constant within experimental error over the entire (hydrate, liquid, vapor) coexistence region. The results are more accurate than but entirely consistent with almost all previous studies

Fire extinction utilizing carbon dioxide hydrate

Energy Technology Data Exchange (ETDEWEB)

Hatakeyama, T.; Aida, E.; Yokomori, T.; Ohmura, R.; Ueda, T. [Keio Univ., Hiyoshi, Kohoku-ku, Yokohama (Japan)

2008-07-01

Clathrate hydrates formed with nonflammable gases may be suitable for use as fire extinguishing agents because dissociation of the hydrates results in the temperature decrease in the combustion field and the nonflammable gases released from the dissociated hydrates prevent the supply of the oxygen to the combustion field. This paper discussed experiments in which ordinary ice and dry ice were used to evaluate the performance of CO{sub 2} hydrate as a fire extinguishing agent. The paper described the apparatus and procedure for the preparation of CO{sub 2} hydrate crystals. A schematic of the reactor to form CO{sub 2} hydrate and a photograph of CO{sub 2} hydrate crystal formed in the study were also presented. Other illustrations, photographs, and tables that were presented included a schematic diagram of the experimental apparatus used for the flame extinction experiments; a photograph of CO{sub 2} hydrate powder; sequential video graphs of the flame extinction by the supply of CO{sub 2} hydrate crystals to the methanol pool flame and the relevant illustration; and heat of CO{sub 2} hydrate dissociation, water vaporization and sublimation of dry ice. It was concluded that the critical mass of the CO{sub 2} hydrate required to extinguish a flame was much less than that of ordinary ice, indicating the superiority of CO{sub 2} hydrate to the ice. In addition, the experiments also revealed that the size of the CO{sub 2} hydrate particles had a significant effect on the performance of flame extinction. 5 refs., 2 tabs., 7 figs.

Hydrates on tap: scientists say natural gas hydrates may be tough nut to crack

Energy Technology Data Exchange (ETDEWEB)

Mahoney, J.

2001-12-01

Gas hydrates are methane molecules trapped in cages of water molecules, yielding a substance with a slushy, sherbet-like consistency. Drilling for hydrates is similar to conventional oil and gas drilling, however, the secret to economic production still remains hidden. Hydrates exist in abundance in such places as deep ocean floor and below ground in some polar regions. The real challenge lies in producing gas from this resource, inasmuch as there is no existing technology for production of gas specifically from methane hydrates. This paper describes an international research program, involving a five-country partnership to spud the first of three wells into the permafrost of the Mackenzie River Delta in the Northwest Territories. The project, worth about $15 million, has brought together public funding and expertise from Japan, Germany, India as well as the Canadian and US Geological Surveys and the US Dept. of Energy in an effort to gain information on the production response of gas hydrates. The operator of the project is Japan Petroleum Exploration Company of Canada, a subsidiary of Japan National Oil Corporation. Since Japan is poor in domestic hydrocarbon resources, but is surrounded by deep water that contains potential for gas hydrates, Japan has a great deal riding on the success of this project. Germany and the United States are also very much interested. Current thinking is that gas is in contact with the hydrates and that it should be possible to develop a free gas reservoir as if it were a conventional deposit. As the free gas is drawn off, the pressure is reduced on the hydrates in contact with it , the hydrates dissociate from the gas and replenish the conventional reservoir. So far this is still only a theory, but it appears to be a sensible approach to hydrate production. 1 photo.

Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

Science.gov (United States)

Barlag, Rebecca; Nyasulu, Frazier

2011-01-01

The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

Methane hydrate dissociation using inverted five-spot water flooding method in cubic hydrate simulator

International Nuclear Information System (INIS)

Li, Gang; Li, Xiao-Sen; Li, Bo; Wang, Yi

2014-01-01

The combination forms of the hydrate dissociation methods in different well systems are divided into 6 main patterns. Dissociation processes of methane hydrate in porous media using the inverted five-spot water flooding method (Pattern 4) are investigated by the experimental observation and numerical simulation. In situ methane hydrate is synthesized in the Cubic Hydrate Simulator (CHS), a 5.832-L cubic reactor. A center vertical well is used as the hot water injection well, while the four vertical wells at the corner are the gas and water production wells. The gas production begins simultaneously with the hot water injection, while after approximately 20 min of compression, the water begins to be produced. One of the common characteristics of the inverted five-spot water flooding method is that both the gas and water production rates decrease with the reduction of the hydrate dissociation rate. The evaluation of the energy efficiency ratio might indicate the inverted five-spot water flooding as a promising gas producing method from the hydrate reservoir. - Highlights: • A three-dimensional 5.8-L cubic pressure vessel is developed. • Gas production of hydrate using inverted five-spot flooding method is studied. • Water/gas production rate and energy efficiency ratio are evaluated. • Temperature distributions of numerical simulation and experiment agree well. • Hydrate dissociation process is a moving boundary problem in this study

Location of silicic caldera formation in arc settings

Energy Technology Data Exchange (ETDEWEB)

Hughes, Gwyneth R; Mahood, Gail A [Department of Geological and Environmental Sciences, Stanford University, 450 Serra, Mall, Building 320, Stanford, CA 94305-2115 (United States)

2008-10-01

Silicic calderas are the surface expressions of silicic magma chambers, and thus their study may yield information about what tectonic and crustal features favor the generation of evolved magma. The goal of this study is to determine whether silicic calderas in arc settings are preferentially located behind the volcanic front. After a global analysis of young, arc-related calderas, we find that silicic calderas at continental margins do form over a wide area behind the front, as compared to other types of arc volcanoes.

Influence of the redox state on the neptunium sorption under alkaline conditions. Batch sorption studies on titanium dioxide and calcium silicate hydrates

International Nuclear Information System (INIS)

Tits, Jan; Laube, Andreas; Wieland, Erich; Gaona, Xavier

2014-01-01

Wet chemistry experiments were carried out to investigate the effect of the redox state and aqueous speciation on the uptake of neptunium by titanium dioxide (TiO 2 ) and by calcium silicate hydrates (C-S-H) under alkaline conditions. TiO 2 was chosen as a reference sorbent to determine the surface complexation behaviour of neptunium under alkaline conditions. C-S-H phases are important constituents of cement and concrete. They may contribute significantly to radionuclide retention due to their high recrystallization rates making incorporation the dominating sorption mechanism for many radionuclides (e.g. the actinides) on these materials. The sorption of neptunium on both solids was found to depend strongly on the degree of hydrolysis. On TiO 2 R d values for Np(IV), Np(V) and Np(VI) are identical at pH = 10 and decrease with progressing hydrolysis in case of Np(V) and Np(VI). On C-S-H phases, R d values for the three redox states are also identical at pH = 10. While the R d values for Np(VI) sorption on C-S-H phases decrease with progressing hydrolysis, the R d values for Np(IV) and Np(V) sorption are not affected by the pH. In addition to the effect of hydrolysis, the presence of Ca is found to promote Np(V) and Np(VI) sorption on TiO 2 whereas on C-S-H phases, the present wet chemistry data do not give unambiguous evidence. Thus, the aqueous speciation appears to have a similar influence on the sorption of the actinides on both types of solids despite the different sorption mechanism. The similar R d values for Np(IV,V,VI) sorption at pH = 10 can be explained qualitatively by invoking inter-ligand electrostatic repulsion between OH groups in the coordination sphere of Np(V) and Np(VI). This mechanism was proposed earlier in the literature for the prediction of actinide complexation constants with inorganic ligands. A limiting coordination number for each Np redox state, resulting from the inter-ligand electrostatic repulsion, allows the weaker sorption of the

Characterization and in vitro evaluation of biphasic α-tricalcium phosphate/β-tricalcium phosphate cement

Energy Technology Data Exchange (ETDEWEB)

Arahira, Takaaki; Maruta, Michito, E-mail: maruta@college.fdcnet.ac.jp; Matsuya, Shigeki

2017-05-01

Biphasic calcium phosphate consisting of hydroxyapatite (HA) and β-tricalcium phosphate(β-TCP) is an excellent bone substitute with controllable bioresorbability. Fabrication of biphasic calcium phosphate with self-setting ability is expected to enhance its potential application as bone substitute. In this study, mixtures of α-TCP and β-TCP with various compositions were prepared through α-β phase transition of α-TCP powder at 1000 °C for various periods. These powders were mixed with 0.25 M Na{sub 2}HPO{sub 4} at a P/L ratio of 2, and then hardened at 37 °C at 100% RH for up to 24 h. Material properties of biphasic HA/β-TCP cement with different α-TCP/β-TCP composition were characterized. These cements were also evaluated with respect to cell response in vitro using MC3T3-E1 cell lines. In conclusion, mechanical and biological properties of HA/β-TCP cement could be controlled by changing the heat treatment time of α-TCP powder at 1000 °C. In vitro results indicated that cell proliferation and ALP activity increased with increase β-TCP content. - Highlights: • We could fabricate biphasic HA/β-TCP cements using heat treated α-TCP powder. • It is easy to control the ratio of α-TCP to β-TCP changing the heat treatment time up to 48 h. • Both cell number and ALP activity increased with increase in β-TCP content. • In vitro results showed that β-TCP has superior cell affinity to HA.

Characterization of early-age hydration processes in lime-ceramic binders using isothermal calorimetry, X-ray diffraction and scanning electron microscopy

Energy Technology Data Exchange (ETDEWEB)

Jerman, Miloš; Tydlitát, Vratislav; Keppert, Martin; Čáchová, Monika; Černý, Robert, E-mail: cernyr@fsv.cvut.cz

2016-06-10

Highlights: • Early age hydration processes in lime-ceramic binders are analyzed within a wide range of component ratios. • The applied waste ceramic dust exhibits partial hydraulic properties, ettringite and calcite are formed. • Transition from tobermorite- to jennite-like structures is identified by SEM within the first 48 h. • The highest specific hydration heat after 300 h, 63 J/g, is measured for the binder containing 70% ceramic. • Substantial effect of the heat of wetting is observed, ranging from 10 J/g for lime to 3.9 J/g for ceramic. - Abstract: Early-age hydration processes in a lime-ceramic-water system are analyzed within the whole range of possible lime/ceramic ratios. The isothermal calorimetry shows a substantial effect of the heat of wetting on the total heat evolved, ranging from 10 J/g for lime to 3.9 J/g for ceramic. The highest specific hydration heat of 63 J/g during the analyzed 300-h hydration period exhibits the blended binder containing 70% ceramic and 30% lime which correlates well with the highest compressive and bending strengths of the paste prepared using this blend. Portlandite, ettringite and calcite are the main phases identified by the X-ray diffraction analysis after the hydration of ceramic-rich blends. According to the results of scanning electron microscopy, the initial course of pozzolanic reaction is for this type of binders characterized by the transition from tobermorite-like calcium-silicate-hydrate structures into jennite-like structures within the first 48 h. Blends with the ceramic content lower than 70% show a high portion of portlandite, calcite is present in low amount, and the jennite-like structures are observed after 48 h, following the initial formation of components with a very high Ca content. The favorable properties of the ceramic-rich blended binders can be explained by the partial hydraulic character of the ceramic. With the specific hydration heat of 29 J/g after 300 h and compressive strength

Characterization of early-age hydration processes in lime-ceramic binders using isothermal calorimetry, X-ray diffraction and scanning electron microscopy

International Nuclear Information System (INIS)

Jerman, Miloš; Tydlitát, Vratislav; Keppert, Martin; Čáchová, Monika; Černý, Robert

2016-01-01

Highlights: • Early age hydration processes in lime-ceramic binders are analyzed within a wide range of component ratios. • The applied waste ceramic dust exhibits partial hydraulic properties, ettringite and calcite are formed. • Transition from tobermorite- to jennite-like structures is identified by SEM within the first 48 h. • The highest specific hydration heat after 300 h, 63 J/g, is measured for the binder containing 70% ceramic. • Substantial effect of the heat of wetting is observed, ranging from 10 J/g for lime to 3.9 J/g for ceramic. - Abstract: Early-age hydration processes in a lime-ceramic-water system are analyzed within the whole range of possible lime/ceramic ratios. The isothermal calorimetry shows a substantial effect of the heat of wetting on the total heat evolved, ranging from 10 J/g for lime to 3.9 J/g for ceramic. The highest specific hydration heat of 63 J/g during the analyzed 300-h hydration period exhibits the blended binder containing 70% ceramic and 30% lime which correlates well with the highest compressive and bending strengths of the paste prepared using this blend. Portlandite, ettringite and calcite are the main phases identified by the X-ray diffraction analysis after the hydration of ceramic-rich blends. According to the results of scanning electron microscopy, the initial course of pozzolanic reaction is for this type of binders characterized by the transition from tobermorite-like calcium-silicate-hydrate structures into jennite-like structures within the first 48 h. Blends with the ceramic content lower than 70% show a high portion of portlandite, calcite is present in low amount, and the jennite-like structures are observed after 48 h, following the initial formation of components with a very high Ca content. The favorable properties of the ceramic-rich blended binders can be explained by the partial hydraulic character of the ceramic. With the specific hydration heat of 29 J/g after 300 h and compressive strength

Formation rate of natural gas hydrate

Energy Technology Data Exchange (ETDEWEB)

Mork, Marit

2002-07-01

The rate of methane hydrate and natural gas hydrate formation was measured in a 9.5 litre stirred tank reactor of standard design. The experiments were performed to better understand the performance and scale-up of a reactor for continuous production of natural gas hydrates. The hydrate formation rate was measured at steady-state conditions at pressures between 70 and 90 bar and temperatures between 7 and 15 deg C. Between 44 and 56 % of the gas continuously supplied to the reactor was converted to hydrate. The experimental results show that the rate of hydrate formation is strongly influenced by gas injection rate and pressure. The effect of stirring rate is less significant and subcooling has no observable effect on the formation rate. Hydrate crystal concentration and gas composition do not influence the hydrate formation rate. Observations of produced hydrate crystals indicate that the crystals are elongated, about 5 micron in diameter and 10 micron long. Analysis of the results shows that the rate of hydrate formation is dominated by gas-liquid mass transfer. A mass transfer model, the bubble-to-crystal model, was developed for the hydrate formation rate in a continuous stirred tank reactor, given in terms of concentration driving force and an overall mass transfer coefficient. The driving force is the difference between the gas concentration at the gas-liquid interface and at the hydrate crystal surface. These concentrations correspond to the solubility of gas in water at experimental temperature and pressure and the solubility of gas at hydrate equilibrium temperature and experimental pressure, respectively. The overall mass transfer coefficient is expressed in terms of superficial gas velocity and impeller power consumption, parameters commonly used in study of stirred tank reactors. Experiments and modeling show that the stirred tank reactor has a considerable potential for increased production capacity. However, at higher hydrate production rates the

Flow assurance intervention, hydrates remediation

Energy Technology Data Exchange (ETDEWEB)

Mancini, Christopher S. [Oceaneering International Inc., Houston, TX (United States)

2012-07-01

This paper addresses the issues of removing hydrates in sub sea flow lines and associated equipment with an Remotely Operated Vehicle (ROV) of opportunity and a multi-service-vessel (MSV). The paper is split into three topics: the equipment used with the ROV, assessing the interface points and handling fluids produced from drawing down the pressure. Each section is explained thoroughly and backed up with real world experience. The equipment section details information from actual jobs performed and why the particular components were utilized. The system is generally contained in an ROV mounted skid. Pumps are utilized to draw down the pressure inside the hydrated section of equipment, removing one of the three necessary components for hydrates formation. Once the section is pumped down, several options exist for handling the fluids pumped out of the system: pumping to surface, re-injection into the well, or injection into an operating flow line. This method of hydrates remediation is both economical and timely. Hydrate blockages form in low temperatures and high pressures. Reducing the pressure or increasing the temperature so the conditions lie to the right of the hydrate dissociation curve will slowly decompose the blockage. Depressurization and the use of MEG or methanol will give favorable conditions to remove the hydrate plug. Oceaneering has the capabilities to remove hydrates using the FRS in conjunction with an installation vessel to dispose of the gas and fluid removed from the flow line. Hydrate remediation techniques should be implemented into the initial design to reduce costs later. The cost of stopped production combined with the day rate for equipment needed for hydrate removal outweighs the costs if no technique is utilized. (author)

Obtención de silicatos de calcio utilizando el método de precipitación controlada

OpenAIRE

Rodríguez-Páez, J. E.; Ahumada, L. M.; Bustamante, J. M.; Ruiz de Murgueitio, J.

2005-01-01

Calcium silicate hydrates are compounds of SiO2 – CaO – H2O system. These materials are used to make lime-sand bricks concretes, or “cellular concretes”, lime-flint brices and as fillers in rubber, paint and plastic products industries, among others. Undoubtedly, the tobermoritas is the most interesting group given its important role in concrete hydration: hydrated calcium silicate (C – S- H) is the main concrete hydration product and its primary bounding phase. The hydrothermal method is the...

Dgroup: DG01980 [KEGG MEDICUS

Lifescience Database Archive (English)

Full Text Available DG01980 DGroup Calcium ... D00931 ... Calcium acetate (USP) ... D00932 ... Calcium carbonat...e (USP); Precipitated calcium carbonate (JP17); Calcium carbonate, precipitated (JAN) ... D00933 ... Calcium citrate (USP) D00934 ... Calciu...m gluceptate (USP); Calcium glucoheptonate (INN) ... D00935 ... Calcium gluconate (USP) ... D00936 ... Calcium... lactate (USP) D00937 ... Calcium phosphate, dihydrate, dibasic (...USP); Dibasic calcium phosphate hydrate (JP17) ... D00938 ... Tricalcium phosphate D02254 ... Calcium lactate hydrate (JP17) ... D02256 ... Calc

Indian continental margin gas hydrate prospects : results of the Indian National Gas Hydrate Program (NGHP) expedition 01

Energy Technology Data Exchange (ETDEWEB)

Collett, T [United States Geological Survey, Denver, CO (United States); Riedel, M. [McGill Univ., Montreal, PQ (Canada). Dept. of Earth and Planetary Sciences; Cochran, J.R. [Columbia Univ., Palisades, NY (United States). Lamont Doherty Earth Observatory; Boswell, R. [United States Dept. of Energy, Morgantown, WV (United States). National Energy Technology Lab; Kumar, P. [Pushpendra Kumar Oil and Natural Gas Corp. Ltd., Mumbai (India). Inst. of Engineering and Ocean Technology; Sathe, A.V. [Oil and Natural Gas Corp. Ltd., Uttaranchal (India). KDM Inst. of Petroleum Exploration

2008-07-01

The geologic occurrence of gas hydrate deposits along the continental margins of India were investigated in the first expedition of the Indian National Gas Hydrate Program (NGHP). The objective was to determine the regional context and characteristics of the gas hydrate deposits through scientific ocean drilling, logging, and analytical activities. A research drill ship was the platform for the drilling operation. The geological and geophysical studies revealed 2 geologically distinct areas with inferred gas hydrate occurrences, notably the passive continental margins of the Indian Peninsula and along the Andaman convergent margin. The NGHP Expedition 01 focused on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these 2 diverse settings. The study established the presence of gas hydrates in Krishna-Godavari, Mahanadi and Andaman basins. Site 10 in the Krishna-Godavari Basin was discovered to be the one of the richest gas hydrate accumulations yet documented, while site 17 in the Andaman Sea had the thickest and deepest gas hydrate stability zone yet known. The existence of a fully-developed gas hydrate system in the Mahanadi Basin was also discovered. Most of the gas hydrate occurrences discovered during this expedition appeared to contain mostly methane which was generated by microbial processes. However, there was also evidence of a thermal origin for a portion of the gas within the hydrates of the Mahanadi Basin and the Andaman offshore area. Gas hydrate in the Krishna-Godavari Basin appeared to be closely associated with large scale structural features, in which the flux of gas through local fracture systems, generated by the regional stress regime, controlled the occurrence of gas hydrate. 3 refs., 1 tab., 2 figs.

The increase of apatite layer formation by the poly(3-hydroxybutyrate) surface modification of hydroxyapatite and β-tricalcium phosphate

Energy Technology Data Exchange (ETDEWEB)

Szubert, M., E-mail: mm.szubert@gmail.com [Faculty of Chemical Technology, Poznan University of Technology, Poznan (Poland); Adamska, K. [Faculty of Chemical Technology, Poznan University of Technology, Poznan (Poland); Szybowicz, M. [Faculty of Technical Physics, Poznan University of Technology, Poznan (Poland); Jesionowski, T. [Faculty of Chemical Technology, Poznan University of Technology, Poznan (Poland); Buchwald, T. [Faculty of Technical Physics, Poznan University of Technology, Poznan (Poland); Voelkel, A. [Faculty of Chemical Technology, Poznan University of Technology, Poznan (Poland)

2014-01-01

The aim of this study was the surface modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) grafting and characterization of modificates. The bioactivity examination was carried out by the determination to grow an apatite layer on modified materials during incubation in simulated body fluid at 37 °C. The additional issue taken up in this paper was to investigate the influence of fluid replacement. The process of the surface modification of biomaterials was evaluated by means of infrared and Raman spectroscopy. Formation of the apatite layer was assessed by means of scanning electron microscopy and confirmed by energy dispersive, Raman and Fourier transformed infrared spectroscopy. During exposure in simulated body fluid, the variation of the zeta potential, pH measurement and relative weight was monitored. Examination of scanning electron microscopy micrographs suggests that modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) significantly increases apatite layer formation. Raman spectroscopy evaluation revealed that the formation of the apatite layer was more significant in the case of hydroxyapatite modificate, when compared to the β-tricalcium phosphate modificate. Both modificates were characterized by stable pH, close to the natural pH of human body fluids. Furthermore, we have shown that a weekly changed, simulated body fluid solution increases apatite layer formation. - Highlights: • Surface modification of HA and β-TCP was performed by PHB grafting. • The growth of apatite layer on materials was examined in simulated body fluid (SBF). • The bioactivity of obtained materials was proved. • The replacement of SBF solution plays an important role in the process of apatite formation.

The increase of apatite layer formation by the poly(3-hydroxybutyrate) surface modification of hydroxyapatite and β-tricalcium phosphate

International Nuclear Information System (INIS)

Szubert, M.; Adamska, K.; Szybowicz, M.; Jesionowski, T.; Buchwald, T.; Voelkel, A.

2014-01-01

The aim of this study was the surface modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) grafting and characterization of modificates. The bioactivity examination was carried out by the determination to grow an apatite layer on modified materials during incubation in simulated body fluid at 37 °C. The additional issue taken up in this paper was to investigate the influence of fluid replacement. The process of the surface modification of biomaterials was evaluated by means of infrared and Raman spectroscopy. Formation of the apatite layer was assessed by means of scanning electron microscopy and confirmed by energy dispersive, Raman and Fourier transformed infrared spectroscopy. During exposure in simulated body fluid, the variation of the zeta potential, pH measurement and relative weight was monitored. Examination of scanning electron microscopy micrographs suggests that modification of hydroxyapatite and β-tricalcium phosphate by poly(3-hydroxybutyrate) significantly increases apatite layer formation. Raman spectroscopy evaluation revealed that the formation of the apatite layer was more significant in the case of hydroxyapatite modificate, when compared to the β-tricalcium phosphate modificate. Both modificates were characterized by stable pH, close to the natural pH of human body fluids. Furthermore, we have shown that a weekly changed, simulated body fluid solution increases apatite layer formation. - Highlights: • Surface modification of HA and β-TCP was performed by PHB grafting. • The growth of apatite layer on materials was examined in simulated body fluid (SBF). • The bioactivity of obtained materials was proved. • The replacement of SBF solution plays an important role in the process of apatite formation

Zirconia silicate modified with phytic acid (IP6) and its effect on uranyl sorption

International Nuclear Information System (INIS)

Escalante G, D. C.

2016-01-01

In this work the sorption capacity of uranyl ions on zirconium silicate (ZrSiO_4) extracted from sea sand of Baja California Sur was studied, the effect of phytic acid (IP6) accompanied by a perchlorate salt of sodium (NaClO_4) on the surface of the mineral. In the first stage, ZrSiO_4 was obtained from sea sand by extraction using hydrofluoric acid, the purified and hydrated material was later characterized by instrumental techniques such as X-ray diffraction to determine its purity and crystallinity. The ZrSiO_4-purified, ZrSiO_4/NaClO_4 and ZrSiO_4/IP6 were studied by physicochemical and surface characterization. By scanning electron microscopy was observed that ZrSiO_4 initially is formed by flat structures, however, when it is hydrated with NaClO_4 the formation of particles on the material exists, whereas when the IP6 is added the crystals on the surface are elongated forming structures geometric shapes. This modification on the surface of the ZrSiO_4 was corroborated by atomic force microscopy where significant changes were observed in the topography of the purified and hydrated material. By Fourier transform infrared spectroscopy is identifies the presence of functional groups from hydration with IP6 and NaClO_4 on the surface of SrSiO_4. Characterization of surface properties was performed by determining the surface area of the purified ZrSiO_4, SrSiO_4/NaClO_4 and ZrSiO_4/IP6 systems using the Bet multipoint and fractal dimension technique; the hydration time, zero loading point was evaluated by means of a bulk titration and surface site density (Ds). The fluorescence and phosphorescence techniques allowed determining the optimum hydration point and the uranium species sorbed on the surface of the ZrSiO_4 as in the systems hydrated with IP6 and with NaClO_4. This technique provided relevant information about the speciation and complex formation of IP6 with uranyl ions on the surface of ZrSiO_4. Sorption isotherms and kinetics were prepared by the liquid

Thermodynamic properties of hydrated cement phases: C-S-H, C-A-S-H and M-S-H

International Nuclear Information System (INIS)

Roosz, Cedric

2016-01-01

Concrete is one of the most widely used building materials in the world. Durability, mechanical and chemical properties have made it a material of choice in storage concepts proposed by the French National Agency for Radioactive Waste Management (Andra), including the achievement of retaining structures, cell plugs, massive supports or conditioning waste. The study of the stability of the constituent phases of cementitious materials is needed in view of the planned quantities and the durability of the structures, and must consider (i) temperature ranges suitable for cement matrices containment in contact with exothermic waste (25-80 deg. C), and (ii) a representative time scale of the lifetime of the storage. The Andra ThermoChimie project therefore aims to develop a consistent thermodynamic database, to model the chemical evolution of cement materials in the environment of radioactive waste. However, in the present state, the database offers only thermodynamic data of cementitious crystalline phases, as well as a limited data set of three different chemical compositions for nano-crystalline C-S-H. This does not allow to reproduce the degradation of cementitious materials, or model the degradation of the new formulations, such as 'Low pH' concretes. The objective is therefore to acquire a thermodynamic complementary data set on phases such as C-S-H (Calcium Silicate Hydrates) C-A-S-H (Calcium Aluminate Silicate Hydrates) and M-S-H (Magnesium Silicate Hydrates), to complete the ThermoChimie database. This study is based on experimental, analytical and digital work, in order to obtain a set of thermodynamic data (Δ f G 0 , Δ f H 0 , Cp(T), S 0 ) sufficiently representative of the chemical variability of these phases. Finally, this set of data allows the development of a thermodynamic predictive model in extended spaces of compositions and temperatures. Development of this predictive model requires (i) The acquisition of thermodynamic properties on

The rates measurement of methane hydrate formation and dissociation using micro-drilling system application for gas hydrate exploration

Energy Technology Data Exchange (ETDEWEB)

Bin Dou [Engineering Faculty, China Univ. of Geosciences, Wuhan (China)]|[Inst. of Petroleum Engineering, Technology Univ. of Clausthal (Germany); Reinicke, K.M. [Inst. of Petroleum Engineering, Technology Univ. of Clausthal (Germany); Guosheng Jiang; Xiang Wu; Fulong Ning [Engineering Faculty, China Univ. of Geosciences, Wuhan (China)

2006-07-01

When drilling through gas hydrate bearing formations, the energy supplied by virtue of the drilling process may lead to a destabilization of the hydrates surrounding the wellbore. Therefore, as the number of oil and gas fields being development in deepwater and onshore arctic environments increases, greater emphasis should be placed on quantifying the risks, gas hydrates pose to drilling operations. The qualification of these risks requires a comprehensive understanding of gas hydrate-formation and dissociation as a result of drilling induced processes. To develop the required understanding of gas hydrat formation and dissociation, the authors conducted laboratory experiments by using a micro-drilling system, to study the dissociation rates of methane hydrates contained in a tank reactor. The test facility used is a development of China University of Geosciences. The rates of methane hydrate formation and dissociation in the tank reactor were measured at steady-state conditions at pressures ranging from 0.1 to 25 MPa and temperatures ranging from -5 to 20 C. The experimental results show that the rate of hydrate formation is strongly influenced by the fluid system used to form the hydrates, pressure and temperature, with the influence of the temperature on methane hydrate dissociation being stronger than that of the pressure. Drilling speed, drilling fluids and hydrate dissociation inhibitors were also shown to influence hydrate dissociation rate. The derived results have been used to predict hydrate drilling stability for several drilling fluid systems.

Thermal conductivity of hydrate-bearing sediments

Science.gov (United States)

Cortes, Douglas D.; Martin, Ana I.; Yun, Tae Sup; Francisca, Franco M.; Santamarina, J. Carlos; Ruppel, Carolyn D.

2009-01-01

A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate–saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate–bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces.

Experimental investigation of methane release from hydrate formation in sandstone through both hydrate dissociation and CO{sub 2} sequestration

Energy Technology Data Exchange (ETDEWEB)

Husebo, J.; Graue, A.; Kvamme, B. [Bergen Univ., Bergen (Norway). Dept. of Physics and Technology; Stevens, J.; Howard, J.J. [ConocoPhillips, Ponca City, OK (United States); Baldwin, B.A. [Green Country Petrophysics LLC, Dewey, OK (United States)

2008-07-01

Large amounts of natural gas trapped in hydrate reservoirs are found in Arctic regions and in deep offshore locations around the world. Natural gas production from hydrate deposits offer significant potential for future energy needs. However, research is needed in order to propose potential production schemes for natural gas hydrates. Natural gas molecules can be freed from hydrate structured cages by depressurization, by heating and by exposing the hydrate to a substance that will form a thermodynamically more stable hydrate structure. This paper provided a comparison of two approaches for releasing methane from methane hydrate in porous sandstone. The study scope covered the dissociation rate of methane hydrate in porous media through depressurization, and also referred to previous work done on producing methane from hydrates in sandstone while sequestering carbon dioxide (CO{sub 2}). The study was conducted in a laboratory setting. The paper discussed the experimental design which included the placing of a pressure- and temperature-controlled sample holder inside the bore of a magnetic resonance imager. The experimental procedures were then outlined, with reference to hydrate formation; carbon dioxide sequestration; hydrate dissociation experiments with constant volume; and hydrate dissociation experiments at constant pressure. The constant volume experiments demonstrated that in order to dissociate a large amount of hydrate, the initial depressurization had to be significantly lower than the hydrate stability pressure. 9 refs., 9 figs.

Microstructure of natural hydrate host sediments

International Nuclear Information System (INIS)

Jones, K.W.; Kerkar, P.B.; Mahajan, D.; Lindquist, W.B.; Feng, H.

2007-01-01

There is worldwide interest in the study of natural gas hydrate because of its potential impact on world energy resources, control on seafloor stability, significance as a drilling hazard and probable impact on climate as a reservoir of a major greenhouse gas. Gas hydrates can (a) be free floating in the sediment matrix (b) contact, but do not cement, existing sediment grains, or (c) actually cement and stiffen the bulk sediment. Seismic surveys, often used to prospect for hydrates over a large area, can provide knowledge of the location of large hydrate concentrations because the hydrates within the sediment pores modify seismic properties. The ability to image a sample at the grain scale and to determine the porosity, permeability and seismic profile is of great interest since these parameters can help in determining the location of hydrates with certainty. We report here on an investigation of the structure of methane hydrate sediments at the grain-size scale using the synchrotron radiation-based computed microtomography (CMT) technique. Work has started on the measurements of the changes occurring as tetrahydrofuran hydrate, a surrogate for methane hydrate, is formed in the sediment

Observed gas hydrate morphologies in marine sediment

Energy Technology Data Exchange (ETDEWEB)

Holland, M.; Schultheiss, P.; Roberts, J.; Druce, M. [Geotek Ltd., Daventry, Northamptonshire (United Kingdom)

2008-07-01

The morphology of gas hydrate in marine sediments determines the basic physical properties of the sediment-hydrate matrix and provides information regarding the formation of gas hydrate deposits, and the nature of the disruption that will occur on dissociation. Small-scale morphology is useful in estimating the concentrations of gas hydrate from geophysical data. It is also important for predicting their response to climate change or commercial production. Many remote techniques for gas hydrate detection and quantification depend on hydrate morphology. In this study, morphology of gas hydrate was examined in HYACINTH pressure cores from recent seagoing expeditions. Visual and infrared observations from non-pressurized cores were also used. The expeditions and pressure core analysis were described in detail. This paper described the difference between two types of gas hydrate morphologies, notably pore-filling and grain-displacing. Last, the paper addressed the impact of hydrate morphology. It was concluded that a detailed morphology of gas hydrate is an essential component for a full understanding of the past, present, and future of any gas hydrate environment. 14 refs., 4 figs.

Use of combined ion exchangers on the basis of KU-23 and KM-2p cation exchangers for purification of ammonium molybdate and tungstate solutions from phosphate, arsenate, and silicate impurities

International Nuclear Information System (INIS)

Blokhin, A.A.; Majorov, D.Yu.; Kopyrin, A.A.; Taushkanov, V.P.

2002-01-01

Using the Tracer technique ( 32 P) and elementary analysis, potentiality of using combined ionites on the basis of macroporous cation-exchange resins KU-23 or KM-2p and hydrated zirconium oxide for purification of concentrated solutions of ammonium molybdate and tungstate from phosphate-, arsenate-, and silicate-ions impurities was studied. High selectivity of the combined ionites towards impurity ions was ascertained, which permits reducing the content of impurities by a factor of 50-100 compared with the initial one [ru

Gas hydrates forming and decomposition conditions analysis

Directory of Open Access Journals (Sweden)

А. М. Павленко

2017-07-01

Full Text Available The concept of gas hydrates has been defined; their brief description has been given; factors that affect the formation and decomposition of the hydrates have been reported; their distribution, structure and thermodynamic conditions determining the gas hydrates formation disposition in gas pipelines have been considered. Advantages and disadvantages of the known methods for removing gas hydrate plugs in the pipeline have been analyzed, the necessity of their further studies has been proved. In addition to the negative impact on the process of gas extraction, the hydrates properties make it possible to outline the following possible fields of their industrial use: obtaining ultrahigh pressures in confined spaces at the hydrate decomposition; separating hydrocarbon mixtures by successive transfer of individual components through the hydrate given the mode; obtaining cold due to heat absorption at the hydrate decomposition; elimination of the open gas fountain by means of hydrate plugs in the bore hole of the gushing gasser; seawater desalination, based on the hydrate ability to only bind water molecules into the solid state; wastewater purification; gas storage in the hydrate state; dispersion of high temperature fog and clouds by means of hydrates; water-hydrates emulsion injection into the productive strata to raise the oil recovery factor; obtaining cold in the gas processing to cool the gas, etc.

HYDRATE CORE DRILLING TESTS

Energy Technology Data Exchange (ETDEWEB)

John H. Cohen; Thomas E. Williams; Ali G. Kadaster; Bill V. Liddell

2002-11-01

The ''Methane Hydrate Production from Alaskan Permafrost'' project is a three-year endeavor being conducted by Maurer Technology Inc. (MTI), Noble, and Anadarko Petroleum, in partnership with the U.S. DOE National Energy Technology Laboratory (NETL). The project's goal is to build on previous and ongoing R&D in the area of onshore hydrate deposition. The project team plans to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope includes drilling and coring one well on Anadarko leases in FY 2003 during the winter drilling season. A specially built on-site core analysis laboratory will be used to determine some of the physical characteristics of the hydrates and surrounding rock. Prior to going to the field, the project team designed and conducted a controlled series of coring tests for simulating coring of hydrate formations. A variety of equipment and procedures were tested and modified to develop a practical solution for this special application. This Topical Report summarizes these coring tests. A special facility was designed and installed at MTI's Drilling Research Center (DRC) in Houston and used to conduct coring tests. Equipment and procedures were tested by cutting cores from frozen mixtures of sand and water supported by casing and designed to simulate hydrate formations. Tests were conducted with chilled drilling fluids. Tests showed that frozen core can be washed out and reduced in size by the action of the drilling fluid. Washing of the core by the drilling fluid caused a reduction in core diameter, making core recovery very difficult (if not impossible). One successful solution was to drill the last 6 inches of core dry (without fluid circulation). These tests demonstrated that it will be difficult to capture core when drilling in permafrost or hydrates without implementing certain safeguards. Among the coring tests was a simulated hydrate

Micro-structured Beta-Tricalcium Phosphate for Repair of the Alveolar Cleft in Cleft Lip and Palate Patients : A Pilot Study

NARCIS (Netherlands)

de Ruiter, AP; Janssen, Nard; van Es, Robert; Frank, Michael; Meijer, Gert; Koole, Ron; Rosenberg, Toine

2015-01-01

OBJECTIVES: Can a synthetic bone substitute be used to repair the alveolar cleft to bypass donor site morbidity as well as to shorten the operating time? In earlier experimental studies, micro-structured beta-tricalcium phosphate (β-TCP) provided similar bone healing when compared with grafting with

Calcium Aluminate Cement Hydration Model

Directory of Open Access Journals (Sweden)

Matusinović, T.

2011-01-01

Full Text Available Calcium aluminate cement (AC is a very versatile special cement used for specific applications. As the hydration of AC is highly temperature dependent, yielding structurally different hydration products that continuously alter material properties, a good knowledge of thermal properties at early stages of hydration is essential. The kinetics of AC hydration is a complex process and the use of single mechanisms models cannot describe the rate of hydration during the whole stage.This paper examines the influence of temperature (ϑ=5–20 °C and water-to-cement mass ratio (mH /mAC = 0.4; 0.5 and 1.0 on hydration of commercial iron-rich AC ISTRA 40 (producer: Istra Cement, Pula, Croatia, which is a part of CALUCEM group, Figs 1–3. The flow rate of heat generation of cement pastes as a result of the hydration reactions was measured with differential microcalorimeter. Chemically bonded water in the hydrated cement samples was determined by thermo-gravimetry.Far less heat is liberated when cement and water come in contact for the first time, Fig. 1, than in the case for portland cement (PC. Higher water-to-cement ratio increases the heat evolved at later ages (Fig. 3 due to higher quantity of water available for hydration. A significant effect of the water-to-cement ratio on the hydration rate and hydration degree showed the importance of water as being the limiting reactant that slows down the reaction early. A simplified stoichiometric model of early age AC hydration (eq. (8 based on reaction schemes of principal minerals, nominally CA, C12A7 and C4AF (Table 1, was employed. Hydration kinetics after the induction period (ϑ < 20 °C had been successfully described (Fig. 4 and Table 2 by a proposed model (eq. (23 which simultaneously comprised three main mechanisms: nucleation and growth, interaction at phase boundary, and mass transfer. In the proposed kinetic model the nucleation and growth is proportional to the amount of reacted minerals (eq

Effect of Mg and Si co-substitution on microstructure and strength of tricalcium phosphate ceramics.

Science.gov (United States)

García-Páez, Ismael H; Carrodeguas, Raúl García; De Aza, Antonio H; Baudín, Carmen; Pena, Pilar

2014-02-01

Magnesium and silicon co-doped tricalcium phosphate (TCP) ceramics with compositions corresponding to 0, 5 and 10wt% CaMg(SiO3)2 in the system Ca3(PO4)2-CaMg(SiO3)2 were obtained by conventional sintering of compacted mixtures of Ca3(PO4)2, MgO, SiO2 and CaCO3 powders at temperatures between 1100 and 1450°C. Microstructural analyses were performed by X-ray diffraction and field emission scanning electron microscopy with energy dispersive spectroscopy. Major phases in the obtained ceramics were β- or α+β-tricalcium phosphate containing Mg and Si in solid solution. Certain amounts of liquid were formed during sintering depending on composition and temperature. There were found significant differences in distributions of strength determined by the diametral compression of disc tests (DCDT). Failure strengths were controlled by microstructural defects associated with phase development. Mg and Si additions were found to be effective to improve densification and associated strength of TCP bioceramics due to the enhancement of sintering by the low viscosity liquids formed. The highest density and strength were obtained for the TCP ceramic containing 5wt% CaMg(SiO3)2 sintered at 1300°C. Cracking and porosity increased at higher temperatures due to grain growth and swelling. © 2013 Published by Elsevier Ltd.

A high yield process for hydrate formation

Energy Technology Data Exchange (ETDEWEB)

Giavarini, C.; Maccioni, F. [Univ. of Roma La Sapienza, Roma (Italy). Dept. of Chemical Engineering

2008-07-01

Due to the large quantities of natural gas stored in deep ocean hydrates, hydrate reservoirs are a substantial energy resource. Hydrates concentrate methane by as much as a factor of 164. As such, several natural gas transportation and storage systems using gas hydrates have been studied, and many of them are nearing practical use. In these systems, the hydrate is produced as a slurry by a spray process at approximately 7 megapascal (MPa), and then shaped into pellets. The use of a spray process, instead of a conventional stirred vessel is necessary in order to reach high hydrate concentrations in the hydrate-ice system. This paper presented a new procedure to produce a bulk of concentrated methane hydrate in a static traditional reactor at moderate pressure, controlling pressure and temperature in the interval between ice melting and the hydrate equilibrium curve. This paper discussed the experimental procedure which included formation of methane hydrate at approximately 5 MPa and 2 degrees Celsius in a reaction calorimeter at a volume of two liters. Results were also discussed. It was concluded that the procedure seemed suitable for the development of a gas hydrate storage and transport technology. It was found that the spray procedure took more time, but could be sped up and made continuous by using two vessels, one for hydrate formation and the other for hydrate concentration. The advantage was the production of a concentrated hydrate, using a simpler equipment and working at lower pressures respect to the spray process. 9 refs., 5 figs.

Amorphous silica in ultra-high performance concrete: First hour of hydration

Energy Technology Data Exchange (ETDEWEB)

Oertel, Tina, E-mail: tina.oertel@isc.fraunhofer.de [Fraunhofer-Institute for Silicate Research ISC, Neunerplatz 2, 97082 Würzburg (Germany); Chair for Inorganic Chemistry I, Universität Bayreuth, Universitätsstr. 30, 95440 Bayreuth (Germany); Hutter, Frank [Fraunhofer-Institute for Silicate Research ISC, Neunerplatz 2, 97082 Würzburg (Germany); Helbig, Uta, E-mail: uta.helbig@th-nuernberg.de [Chair for Crystallography and X-ray Methods, Technische Hochschule Nürnberg Georg Simon Ohm, Wassertorstraße 10, 90489 Nürnberg (Germany); Sextl, Gerhard [Fraunhofer-Institute for Silicate Research ISC, Neunerplatz 2, 97082 Würzburg (Germany); Chair for Chemical Technology of Advanced Materials, Julius Maximilian Universität, Röntgenring 11, 97070 Würzburg (Germany)

2014-04-01

Amorphous silica in the sub-micrometer size range is widely used to accelerate cement hydration. Investigations including properties of silica which differ from the specific surface area are rare. In this study, the reactivity of varying types of silica was evaluated based on their specific surface area, surface silanol group density, content of silanol groups and solubility in an alkaline suspension. Pyrogenic silica, silica fume and silica synthesized by hydrolysis and condensation of alkoxy silanes, so-called Stoeber particles, were employed. Influences of the silica within the first hour were further examined in pastes with water/cement ratios of 0.23 using in-situ X-ray diffraction, cryo scanning electron microscopy and pore solution analysis. It was shown that Stoeber particles change the composition of the pore solution. Na{sup +}, K{sup +}, Ca{sup 2+} and silicate ions seem to react to oligomers. The extent of this reaction might be highest for Stoeber particles due to their high reactivity.

Friction Properties of Laminated Composite Materials of Alpha-Tricalcium Phosphate–Filled Poly (Vinyl Alcohol) Hydrogels

OpenAIRE

Yamamoto, Kanae; Iwai, Tomoaki; Shoukaku, Yutaka

2015-01-01

The aim of this study was to examine the mechanical characteristics of a polyvinyl alcohol hydrogel (PVA-H) as a candidate material for artificial joint cartilage. In the study, PVA-H was filled with α-tricalcium phosphate (α-TCP) in order to improve its mechanical properties. In addition, laminated composite materials with 3 layers were prepared by laminating α-TCP–filled PVA-H and unfilled PVA-H. The samples were prepared with different numbers of repeated freeze–thaw cycles and several con...

Detection and Production of Methane Hydrate

Energy Technology Data Exchange (ETDEWEB)

George Hirasaki; Walter Chapman; Gerald Dickens; Colin Zelt; Brandon Dugan; Kishore Mohanty; Priyank Jaiswal

2011-12-31

This project seeks to understand regional differences in gas hydrate systems from the perspective of as an energy resource, geohazard, and long-term climate influence. Specifically, the effort will: (1) collect data and conceptual models that targets causes of gas hydrate variance, (2) construct numerical models that explain and predict regional-scale gas hydrate differences in 2-dimensions with minimal 'free parameters', (3) simulate hydrocarbon production from various gas hydrate systems to establish promising resource characteristics, (4) perturb different gas hydrate systems to assess potential impacts of hot fluids on seafloor stability and well stability, and (5) develop geophysical approaches that enable remote quantification of gas hydrate heterogeneities so that they can be characterized with minimal costly drilling. Our integrated program takes advantage of the fact that we have a close working team comprised of experts in distinct disciplines. The expected outcomes of this project are improved exploration and production technology for production of natural gas from methane hydrates and improved safety through understanding of seafloor and well bore stability in the presence of hydrates. The scope of this project was to more fully characterize, understand, and appreciate fundamental differences in the amount and distribution of gas hydrate and how this would affect the production potential of a hydrate accumulation in the marine environment. The effort combines existing information from locations in the ocean that are dominated by low permeability sediments with small amounts of high permeability sediments, one permafrost location where extensive hydrates exist in reservoir quality rocks and other locations deemed by mutual agreement of DOE and Rice to be appropriate. The initial ocean locations were Blake Ridge, Hydrate Ridge, Peru Margin and GOM. The permafrost location was Mallik. Although the ultimate goal of the project was to understand

Preparation and properties of β-tricalcium phosphate porous bioceramic

Institute of Scientific and Technical Information of China (English)

张士华; 熊党生; 崔崇

2004-01-01

Porous β-tricalcium phosphate bioceramic (PTCP) has important roles in surgical implants because of good biocompatibility. But the low compressive strength of the ceramic limits its application. The preparation of PTCP was improved with the adjustment of the constituents and the sintering-process. A new type of PTCP material with high compressive strength was made. The compositions, microstructure and properties of PTCP were analyzed by TG-DSC, XRD, TEM, SEM and so on. The result indicates that stearic acid burns sufficiently and gives out carbon dioxide and water vapor when slowly heated between 200 ℃ and 400 ℃ so that the porous structure like coral in β-TCP bioceramic is formed. Through crystallization at 470 ℃ and 570 ℃, more CaO-P2O5 glass-cement is converted into crystallite-glass, which is beneficial for improving the compressive strength of β-TCP bioceramic.PTCP can form a support action in bone imperfect section with good solubility.

Artificial Hydration and Nutrition

Science.gov (United States)

... Crisis Situations Pets and Animals myhealthfinder Food and Nutrition Healthy Food Choices Weight Loss and Diet Plans ... Your Health Resources Healthcare Management Artificial Hydration and Nutrition Artificial Hydration and Nutrition Share Print Patients who ...

Alcohol cosurfactants in hydrate antiagglomeration.

Science.gov (United States)

York, J Dalton; Firoozabadi, Abbas

2008-08-28

Because of availability, as well as economical and environmental considerations, natural gas is projected to be the premium fuel of the 21st century. Natural gas production involves risk of the shut down of onshore and offshore operations because of blockage from hydrates formed from coproduced water and hydrate-forming species in natural gas. Industry practice has been usage of thermodynamic inhibitors such as alcohols often in significant amounts, which have undesirable environmental and safety impacts. Thermodynamic inhibitors affect bulk-phase properties and inhibit hydrate formation. An alternative is changing surface properties through usage of polymers and surfactants, effective at 0.5 to 3 weight % of coproduced water. One group of low dosage hydrate inhibitors (LDHI) are kinetic inhibitors, which affect nucleation rate and growth. A second group of LDHI are antiagglomerants, which prevent agglomeration of small hydrate crystallites. Despite great potential, work on hydrate antiagglomeration is very limited. This work centers on the effect of small amounts of alcohol cosurfactant in mixtures of two vastly different antiagglomerants. We use a model oil, water, and tetrahydrofuran as a hydrate-forming species. Results show that alcohol cosurfactants may help with antiagglomeration when traditional antiagglomerants alone are ineffective. Specifically, as low as 0.5 wt. % methanol cosurfactant used in this study is shown to be effective in antiagglomeration. Without the cosurfactant there will be agglomeration independent of the AA concentration. To our knowledge, this is the first report of alcohol cosurfactants in hydrate antiagglomerants. It is also shown that a rhamnolipid biosurfactant is effective down to only 0.5 wt. % in such mixtures, yet a quaternary ammonium chloride salt, i. e., quat, results in hydrate slurries down to 0.01 wt. %. However, biochemical surfactants are less toxic and biodegradable, and thus their use may prove beneficial even if at

Effect of silicate module of water glass on rheological parameters of poly(sodium acrylate)/sodium silicate hydrogels

Science.gov (United States)

Mastalska-Popiawska, J.; Izak, P.

2017-01-01

The poly(sodium acrylate)/sodium silicate hydrogels were synthesized in the presence of sodium thiosulphate and potassium persulphate as the redox initiators and N,N’-methylene-bisacrylamide as the cross-linking monomer. 20 wt% aqueous solution of sodium acrylate was polymerized together with water glass with different silicate modules (M) from 1.74 to 2.29, in three mass ratio of the monomer solution to the water glass 2:1, 1:1 and 1:2. Such obtained hybrid composites were rheologically tested using the oscillation method. It allowed to designate the crossover point during polymerization, as well as to define the viscoelastic properties of the casted hydrogel samples one week after the reaction. The obtained results of the oscillation measurements showed that cross-linking reaction proceeds very quickly and the lower the silicate module is, the process starts faster. After the completion of the reaction the silicate-polymer hydrogels are strongly elastic materials and the highest elasticity characterizes systems with the mass ratio 1:2, i.e. with the highest water glass content.

40 CFR 721.9513 - Modified magnesium silicate polymer (generic).

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified magnesium silicate polymer... Specific Chemical Substances § 721.9513 Modified magnesium silicate polymer (generic). (a) Chemical... as modified magnesium silicate polymer (PMN P-98-604) is subject to reporting under this section for...

Hydration dependent dynamics in RNA

International Nuclear Information System (INIS)

Olsen, Greg L.; Bardaro, Michael F.; Echodu, Dorothy C.; Drobny, Gary P.; Varani, Gabriele

2009-01-01

The essential role played by local and collective motions in RNA function has led to a growing interest in the characterization of RNA dynamics. Recent investigations have revealed that even relatively simple RNAs experience complex motions over multiple time scales covering the entire ms-ps motional range. In this work, we use deuterium solid-state NMR to systematically investigate motions in HIV-1 TAR RNA as a function of hydration. We probe dynamics at three uridine residues in different structural environments ranging from helical to completely unrestrained. We observe distinct and substantial changes in 2 H solid-state relaxation times and lineshapes at each site as hydration levels increase. By comparing solid-state and solution state 13 C relaxation measurements, we establish that ns-μs motions that may be indicative of collective dynamics suddenly arise in the RNA as hydration reaches a critical point coincident with the onset of bulk hydration. Beyond that point, we observe smaller changes in relaxation rates and lineshapes in these highly hydrated solid samples, compared to the dramatic activation of motion occurring at moderate hydration

Investigations into surfactant/gas hydrate relationship

Energy Technology Data Exchange (ETDEWEB)

Rogers, Rudy; Zhang, Guochang; Dearman, Jennifer; Woods, Charles [Swalm School of Chemical Engineering, Mississippi State University, Mississippi State, MS 39762 (United States)

2007-03-15

Gas hydrates have unique physical properties portending useful industrial applications of gas storage, gas separation, or water desalination. When gas hydrates were found in the early 1990s to occur naturally and abundantly in seafloors, three other primary interests and concerns emerged: potential new energy source, climate threat from their greenhouse gases, and seafloor instabilities. This paper presents research showing how anionic synthetic surfactants helped develop an industrial gas hydrate storage process for natural gas and how naturally-occurring in-situ anionic biosurfactants influence the formation and placement of gas hydrates in ocean sediments. The catalytic effects, mechanisms, and surface specificities imparted by synthetic surfactants in the gas storage process and imparted by biosurfactants in porous media are discussed. The Bacillus subtilis bacterium that is indigenous to gas hydrate mounds in the Gulf of Mexico was cultured in the laboratory. Its biosurfactant was separated and found to catalyze gas hydrates in porous media. The experiments indicate that seafloor-biosurfactants can be produced rapidly in-situ to achieve threshold concentrations whereby hydrates are promoted. The biosurfactants accumulate and promote hydrate formation on specific mineral surfaces such as sodium montmorillonite. (author)

CM and CO chondrites: A common parent body or asteroidal neighbors? Insights from chondrule silicates

Science.gov (United States)

Schrader, Devin L.; Davidson, Jemma

2017-10-01

By investigating the petrology and chemical composition of type II (FeO-rich) chondrules in the Mighei-like carbonaceous (CM) chondrites we constrain their thermal histories and relationship to the Ornans-like carbonaceous (CO) chondrites. We identified FeO-rich relict grains in type II chondrules by their Fe/Mn ratios; their presence indicates chondrule recycling among type II chondrules. The majority of relict grains in type II chondrules are FeO-poor olivine grains. Consistent with previous studies, chemical similarities between CM and CO chondrite chondrules indicate that they had similar formation conditions and that their parent bodies probably formed in a common region within the protoplanetary disk. However, important differences such as mean chondrule size and the lower abundance of FeO-poor relicts in CM chondrite type II chondrules than in CO chondrites suggest CM and CO chondrules did not form together and they likely originate from distinct parent asteroids. Despite being aqueously altered, many CM chondrites contain pre-accretionary anhydrous minerals (i.e., olivine) that are among the least thermally metamorphosed materials in chondrites according to the Cr2O3 content of their ferroan olivine. The presence of these minimally altered pre-accretionary chondrule silicates suggests that samples to be returned from aqueously altered asteroids by the Hayabusa2 and OSIRIS-REx asteroid sample return missions, even highly hydrated, may contain silicates that can provide information about the pre-accretionary histories and conditions of asteroids Ryugu and Bennu, respectively.

Accelerated hydration of high silica cements

International Nuclear Information System (INIS)

Walker, Colin; Yui, Mikazu

2012-01-01

Current Japanese designs for high level radioactive waste (HLW) repositories anticipate the use of both bentonite (buffer and backfill material) and cement based materials. Using hydrated Ordinary Portland Cement (OPC) as a grouting material is undesirable because the associated high pH buffer will have an undisputed detrimental effect on the performance of the bentonite buffer and backfill and of the host rock by changing its porosity. Instead, hydrated low pH cement (LopHC) grouting materials are being developed to provide a pH inferior or equal to 11 to reduce these detrimental effects. LopHC grouting materials use mixtures of superfine OPC (SOPC) clinker and silica fume (SF), and are referred as high silica cements (HSC). The focus of the present study was to identify the development of the unhydrated and hydrated mineral assemblage and the solution chemistry during the hydration of HSC. Since hydration experiments of cementitious materials are notably slow, a ball mill was used to accelerate hydration. This was done for two reasons. Firstly, to develop a method to rapidly hydrate cement based materials without the need for higher temperatures (which can alter the mineral assemblage), and secondly, to ensure that the end point of hydration was reached in a reasonable time frame and so to realize the final mineralogy and solution chemistry of hydrated HSC

A Hydrate Database: Vital to the Technical Community

Directory of Open Access Journals (Sweden)

D Sloan

2007-06-01

Full Text Available Natural gas hydrates may contain more energy than all the combined other fossil fuels, causing hydrates to be a potentially vital aspect of both energy and climate change. This article is an overview of the motivation, history, and future of hydrate data management using a CODATA vehicle to connect international hydrate databases. The basis is an introduction to the Gas Hydrate Markup Language (GHML to connect various hydrate databases. The accompanying four articles on laboratory hydrate data by Smith et al., on field hydrate data by L?wner et al., on hydrate modeling by Wang et al., and on construction of a Chinese gas hydrate system by Xiao et al. provide details of GHML in their respective areas.

Lattice thermal conductivity of silicate glasses at high pressures

Science.gov (United States)

Chang, Y. Y.; Hsieh, W. P.

2016-12-01

Knowledge of the thermodynamic and transport properties of magma holds the key to understanding the thermal evolution and chemical differentiation of Earth. The discovery of the remnant of a deep magma ocean above the core mantle boundary (CMB) from seismic observations suggest that the CMB heat flux would strongly depend on the thermal conductivity, including lattice (klat) and radiative (krad) components, of dense silicate melts and major constituent minerals around the region. Recent measurements on the krad of dense silicate glasses and lower-mantle minerals show that krad of dense silicate glasses could be significantly smaller than krad of the surrounding solid mantle phases, and therefore the dense silicate melts would act as a thermal insulator in deep lower mantle. This conclusion, however, remains uncertain due to the lack of direct measurements on the lattice thermal conductivity of silicate melts under relevant pressure-temperature conditions. Besides the CMB, magmas exist in different circumstances beneath the surface of the Earth. Chemical compositions of silicate melts vary with geological and geodynamic settings of the melts and have strong influences on their thermal properties. In order to have a better view of heat transport within the Earth, it is important to study compositional and pressure dependences of thermal properties of silicate melts. Here we report experimental results on lattice thermal conductivities of silicate glasses with basaltic and rhyolitic compositions up to Earth's lower mantle pressures using time-domain thermoreflectance coupled with diamond-anvil cell techniques. This study not only provides new data for the thermal conductivity of silicate melts in the Earth's deep interior, but is crucial for further understanding of the evolution of Earth's complex internal structure.

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

Donn McGuire; Steve Runyon; Richard Sigal; Bill Liddell; Thomas Williams; George Moridis

2005-02-01

Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. Hot Ice No. 1 was planned to test the Ugnu and West Sak sequences for gas hydrates and a concomitant free gas accumulation on Anadarko's 100% working interest acreage in section 30 of Township 9N, Range 8E of the Harrison Bay quadrangle of the North Slope of Alaska. The Ugnu and West Sak intervals are favorably positioned in the hydrate-stability zone over an area extending from Anadarko's acreage westward to the vicinity of the aforementioned gas-hydrate occurrences. This suggests that a large, north-to-south trending gas-hydrate accumulation may exist in that area. The presence of gas shows in the Ugnu and West Sak reservoirs in wells situated eastward and down dip of the Hot Ice location indicate that a free-gas accumulation may be trapped by gas hydrates. The Hot Ice No. 1 well was designed to core from the surface to the base of the West Sak interval using the

Hard tissue deposition in dental pulp canal by {alpha}-tricalcium phosphate cement

Energy Technology Data Exchange (ETDEWEB)

Yoshikawa, M.; Toda, T. [Osaka Dental Univ. (Japan). Dept. of Endodontics; Mandai, Y. [Bio-Chemical Lab. of Nitta Gelatin Inc., Yao (Japan); Oonishi, H. [Osaka Minami National Hospital, Kawachi (Japan). Dept. of Orthopaedic Surgery

2001-07-01

Canal closure by hard tissue proliferation in the pulp canal and/or apical foramen is the most ideal healing after pulp removal. Generally, Ca(OH){sub 2} may induce secondary dentine or dentine-bridge on the amputated pulp surface. However, Ca(OH){sub 2} shows strong alkalinity and may cause severe inflammatory responses in the residual pulp. Moreover, completely formed dentine-bridge at the orifice will disturb further treatment of residual pulp because of the difficulty in localizing the pathway. The purpose of this study was to see hard tissue induction using newly developed {alpha}-tricalcium phosphate cement and to recognize the morphological difference of hard tissue from that of Ca(OH){sub 2}. (orig.)

Storage capacity of hydrogen in gas hydrates

International Nuclear Information System (INIS)

Tsuda, Takaaki; Ogata, Kyohei; Hashimoto, Shunsuke; Sugahara, Takeshi; Sato, Hiroshi; Ohgaki, Kazunari

2010-01-01

The storage capacity of H 2 in the THF, THT, and furan hydrates was studied by p-V-T measurements. We confirmed that the storage and release processes of H 2 in all hydrates could be performed reversibly by pressure swing without destroying of hydrate cages. H 2 absorption in both THT and furan hydrates is much faster than THF hydrate in spite of same unit-cell structure. On the other hand, the storage amounts of H 2 are coincident in the all additive hydrates and would reach at about 1.0 mass% asymptotically.

Properties of samples containing natural gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well, determined using Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI)

Science.gov (United States)

Winters, W.J.

1999-01-01

As part of an ongoing laboratory study, preliminary acoustic, strength, and hydraulic conductivity results are presented from a suite of tests conducted on four natural-gas-hydrate-containing samples from the Mackenzie Delta JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well. The gas hydrate samples were preserved in pressure vessels during transport from the Northwest Territories to Woods Hole, Massachusetts, where multistep tests were performed using GHASTLI (Gas Hydrate And Sediment Test Laboratory Instrument), which recreates pressure and temperature conditions that are stable for gas hydrate. Properties and changes in sediment behaviour were measured before, during, and after controlled gas hydrate dissociation. Significant amounts of gas hydrate occupied the sample pores and substantially increased acoustic velocity and shear strength.

Relation between reactivity and electronic structure for α'_L-, β- and γ-dicalcium silicate: A first-principles study

Energy Technology Data Exchange (ETDEWEB)

Wang, Qianqian, E-mail: qqwangnj@gmail.com [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing University of Technology, Nanjing, 210009 (China); Li, Feng [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing University of Technology, Nanjing, 210009 (China); Shen, Xiaodong, E-mail: xdshen@njut.edu.cn [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing University of Technology, Nanjing, 210009 (China); Shi, Wujun [National Laboratory of Solid State Microstructures and Department of Physics, Nanjing University, Nanjing, 210093 (China); Li, Xuerun; Guo, Yanhua [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing University of Technology, Nanjing, 210009 (China); Xiong, Shijie [National Laboratory of Solid State Microstructures and Department of Physics, Nanjing University, Nanjing, 210093 (China); Zhu, Qing [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing University of Technology, Nanjing, 210009 (China); Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261 (United States)

2014-03-01

The effect of the electronic structures of α'_L-, β-, and γ-dicalcium silicate (α'_L-, β- and γ-C₂S, C = CaO, S = SiO₂) on hydration reactivity have been investigated by first-principles calculations. Active O atoms with larger charge densities are found in α'_L- and β-C₂S, while they are absent in γ-C₂S. The local density of states of valence band maximum in α'_L- and β-C₂S is highly localized around active O atoms, whereas that in γ-C₂S is homogeneously dispersed. For the active O-2p orbital in α'_L- and β-C₂S, the highest orbital energy in the partial density of states is about 0.31 eV higher than that of the inactive O in γ-C₂S. These differences make the active O atoms of α'_L- and β-C₂S more susceptible to electrophilic attack and result in higher hydration reactivity for α'_L- and β-C₂S.

High Pressure/Temperature Metal Silicate Partitioning of Tungsten

Science.gov (United States)

Shofner, G. A.; Danielson, L.; Righter, K.; Campbell, A. J.

2010-01-01

The behavior of chemical elements during metal/silicate segregation and their resulting distribution in Earth's mantle and core provide insight into core formation processes. Experimental determination of partition coefficients allows calculations of element distributions that can be compared to accepted values of element abundances in the silicate (mantle) and metallic (core) portions of the Earth. Tungsten (W) is a moderately siderophile element and thus preferentially partitions into metal versus silicate under many planetary conditions. The partitioning behavior has been shown to vary with temperature, silicate composition, oxygen fugacity, and pressure. Most of the previous work on W partitioning has been conducted at 1-bar conditions or at relatively low pressures, i.e. pressure. Predictions based on extrapolation of existing data and parameterizations suggest an increased pressured dependence on metal/ silicate partitioning of W at higher pressures 5. However, the dependence on pressure is not as well constrained as T, fO2, and silicate composition. This poses a problem because proposed equilibration pressures for core formation range from 27 to 50 GPa, falling well outside the experimental range, therefore requiring exptrapolation of a parametereized model. Higher pressure data are needed to improve our understanding of W partitioning at these more extreme conditions.

Well log characterization of natural gas-hydrates

Science.gov (United States)

Collett, Timothy S.; Lee, Myung W.

2012-01-01

In the last 25 years there have been significant advancements in the use of well-logging tools to acquire detailed information on the occurrence of gas hydrates in nature: whereas wireline electrical resistivity and acoustic logs were formerly used to identify gas-hydrate occurrences in wells drilled in Arctic permafrost environments, more advanced wireline and logging-while-drilling (LWD) tools are now routinely used to examine the petrophysical nature of gas-hydrate reservoirs and the distribution and concentration of gas hydrates within various complex reservoir systems. Resistivity- and acoustic-logging tools are the most widely used for estimating the gas-hydrate content (i.e., reservoir saturations) in various sediment types and geologic settings. Recent integrated sediment coring and well-log studies have confirmed that electrical-resistivity and acoustic-velocity data can yield accurate gas-hydrate saturations in sediment grain-supported (isotropic) systems such as sand reservoirs, but more advanced log-analysis models are required to characterize gas hydrate in fractured (anisotropic) reservoir systems. New well-logging tools designed to make directionally oriented acoustic and propagation-resistivity log measurements provide the data needed to analyze the acoustic and electrical anisotropic properties of both highly interbedded and fracture-dominated gas-hydrate reservoirs. Advancements in nuclear magnetic resonance (NMR) logging and wireline formation testing (WFT) also allow for the characterization of gas hydrate at the pore scale. Integrated NMR and formation testing studies from northern Canada and Alaska have yielded valuable insight into how gas hydrates are physically distributed in sediments and the occurrence and nature of pore fluids(i.e., free water along with clay- and capillary-bound water) in gas-hydrate-bearing reservoirs. Information on the distribution of gas hydrate at the pore scale has provided invaluable insight on the mechanisms

Influence of fluorosurfactants on hydrate formation rates

Energy Technology Data Exchange (ETDEWEB)

Kim, C.U.; Jeong, K.E.; Chae, H.J.; Jeong, S.Y. [Korea Reasearch Inst. of Chemical Technology, Alternative Chemicals/Fuel Research Center, Yuseong-Gu, Daejon (Korea, Republic of)

2008-07-01

Gas hydrates, or clathrates, are ice-like solids that forms when natural gas is in contact with liquid water or ice under high pressure and low temperature. There is significant interest in studying the storage and transportation of gas in the form of hydrates. However, a critical problem impacting the industrial application of gas hydrates for storage and transportation of natural gas is the slow formation rate of natural gas hydrate. Researchers have previously reported on the promotion effect of some additives on gas hydrate formation and hydrate gas content. Fluorosurfactants are significantly superior to nonfluorinated surfactants in wetting action, as well as stability in harsh environments, both thermal and chemical. This paper discussed an experimental investigation into the effects of fluorosurfactants with different ionic types on the formation of methane hydrate. The surfactants used were FSN-100 of DuPont Zonyl as non-ionic surfactant and FC-143 of DuPont as anionic surfactant. The paper discussed the experimental apparatus for methane hydrate formation. It also discussed hydrate formation kinetics and the series of hydrate formation experiments that were conducted in the presence of fluorosurfactants. Last, the paper explored the results of the study. It was concluded that anionic fluorosurfactant of FC-143 had a better promoting effect on methane hydrate formation compared with nonionic surfactant of FSN-100. 8 refs., 2 tabs., 2 figs.

Physical Properties of Gas Hydrates: A Review

Energy Technology Data Exchange (ETDEWEB)

Gabitto, Jorge [Prairie View A& M University; Tsouris, Costas [ORNL

2010-01-01

Methane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 1016?m3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.

Suppressive effects of a polymer sodium silicate solution on ...

African Journals Online (AJOL)

Sodium silicate was dissolved in water in either a monomer form or polymer form; the effects of both forms of sodium silicate aqueous solution on rose powdery mildew and root rot diseases of miniature rose were examined. Both forms of sodium silicate aqueous solution were applied to the roots of the miniature rose.

Spectral properties of porphyrins in the systems with layered silicates

International Nuclear Information System (INIS)

Ceklovsky, A.

2009-03-01

This work is focused on investigation of hybrid materials based on layered silicates, representing host inorganic component, and porphyrin dyes as organic guest. Aqueous colloidal dispersions, as well as thin solid films of layered silicate/porphyrin systems were studied. Modification of photophysical properties, such as absorption and fluorescence of molecules, adsorbed or incorporated in layered silicate hosts, were studied mainly to spread the knowledge about the environments suitable for incorporating aromatic compounds, providing photoactive properties of potential technological interest. TMPyP cations interact with the surfaces of layered silicates via electrostatic interactions. The extent of dye adsorption on colloidal particles of the silicates is influenced by the CEC values and swelling ability of silicates. Interaction of porphyrins with layered silicate hosts leads to significant changes of dye spectral properties. One of the key parameters that has a crucial impact on this interaction is the layer charge of silicate template. Other factors influence the resulting spectral properties of hybrid systems, such as the method of hybrid material preparation, the material's type (colloid, film), and the modification of the silicate host. Molecular orientation studies using linearly-polarized spectroscopies in VIS and IR regions revealed that TMPyP molecules were oriented in almost parallel fashion with respect to the silicate surface plane. Slightly higher values of the orientation angle of TMPyP transition moment were observed for the TMPyP/FHT system. Thus, flattening of the guest TMPyP molecules is the next important factor (mainly in the systems with lower layer charge), influencing its spectral properties upon the interaction with layered silicates. Fluorescence was effectively quenched in the systems based on solid films prepared from the high concentration of the dye (10-3 mol.dm-3). The quenching is most probably related to the structure of the

Clathrate Hydrates for Thermal Energy Storage in Buildings: Overview of Proper Hydrate-Forming Compounds

Directory of Open Access Journals (Sweden)

Beatrice Castellani

2014-09-01

Full Text Available Increasing energy costs are at the origin of the great progress in the field of phase change materials (PCMs. The present work aims at studying the application of clathrate hydrates as PCMs in buildings. Clathrate hydrates are crystalline structures in which guest molecules are enclosed in the crystal lattice of water molecules. Clathrate hydrates can form also at ambient pressure and present a high latent heat, and for this reason, they are good candidates for being used as PCMs. The parameter that makes a PCM suitable to be used in buildings is, first of all, a melting temperature at about 25 °C. The paper provides an overview of groups of clathrate hydrates, whose physical and chemical characteristics could meet the requirements needed for their application in buildings. Simulations with a dynamic building simulation tool are carried out to evaluate the performance of clathrate hydrates in enhancing thermal comfort through the moderation of summer temperature swings and, therefore, in reducing energy consumption. Simulations suggest that clathrate hydrates have a potential in terms of improvement of indoor thermal comfort and a reduction of energy consumption for cooling. Cooling effects of 0.5 °C and reduced overheating hours of up to 1.1% are predicted.

The kinetic fragility of natural silicate melts

International Nuclear Information System (INIS)

Giordano, Daniele; Dingwell, Donald B

2003-01-01

Newtonian viscosities of 19 multicomponent natural and synthetic silicate liquids, with variable contents of SiO 2 (41-79 wt%), Al 2 O 3 (10-19 wt%), TiO 2 (0-3 wt%), FeO tot (0-11 wt%); alkali oxides (5-17 wt%), alkaline-earth oxides (0-35 wt%), and minor oxides, obtained at ambient pressure using the high-temperature concentric cylinder, the low-temperature micropenetration, and the parallel plates techniques, have been analysed. For each silicate liquid, regression of the experimentally determined viscosities using the well known Vogel-Fulcher-Tammann (VFT) equation allowed the viscosity of all these silicates to be accurately described. The results of these fits, which provide the basis for the subsequent analysis here, permit qualitative and quantitative correlations to be made between the VFT adjustable parameters (A VFT , B VFT , and T 0 ). The values of B VFT and T 0 , calibrated via the VFT equation, are highly correlated. Kinetic fragility appears to be correlated with the number of non-bridging oxygens per tetrahedrally coordinated cation (NBO/T). This is taken to infer that melt polymerization controls melt fragility in liquid silicates. Thus NBO/T might form an useful ingredient of a structure-based model of non-Arrhenian viscosity in multicomponent silicate melts

Synthesis of non-siliceous mesoporous oxides.

Science.gov (United States)

Gu, Dong; Schüth, Ferdi

2014-01-07

Mesoporous non-siliceous oxides have attracted great interest due to their unique properties and potential applications. Since the discovery of mesoporous silicates in 1990s, organic-inorganic assembly processes by using surfactants or block copolymers as soft templates have been considered as a feasible path for creating mesopores in metal oxides. However, the harsh sol-gel conditions and low thermal stabilities have limited the expansion of this method to various metal oxide species. Nanocasting, using ordered mesoporous silica or carbon as a hard template, has provided possibilities for preparing novel mesoporous materials with new structures, compositions and high thermal stabilities. This review concerns the synthesis, composition, and parameter control of mesoporous non-siliceous oxides. Four synthesis routes, i.e. soft-templating (surfactants or block copolymers as templates), hard-templating (mesoporous silicas or carbons as sacrificial templates), colloidal crystal templating (3-D ordered colloidal particles as a template), and super lattice routes, are summarized in this review. Mesoporous metal oxides with different compositions have different properties. Non-siliceous mesoporous oxides are comprehensively described, including a discussion of constituting elements, synthesis, and structures. General aspects concerning pore size control, atomic scale crystallinity, and phase control are also reviewed.

Clinker mineral hydration at reduced relative humidities

DEFF Research Database (Denmark)

Jensen, Ole Mejlhede; Hansen, Per Freiesleben; Lachowski, Eric E.

1999-01-01

and experimental data are presented showing that C(3)A can hydrate at lower humidities than either C3S or C2S. It is suggested that the initiation of hydration during exposure to water vapour is nucleation controlled. When C(3)A hydrates at low humidity, the characteristic hydration product is C(3)AH(6......Vapour phase hydration of purl cement clinker minerals at reduced relative humidities is described. This is relevant to modern high performance concrete that may self-desiccate during hydration and is also relevant to the quality of the cement during storage. Both the oretical considerations...

Hydration and nutrition knowledge in adolescent swimmers. Does water intake affect urine hydration markers after swimming?

Directory of Open Access Journals (Sweden)

Cesare Altavilla

2017-12-01

Full Text Available Little data exists regarding nutritional knowledge and hydration in adolescent swimmers. The aim of this study was to assess the level of nutrition and hydration knowledge and to describe the fluid balance in adolescent swimmers during training. A study was carried out with a cross-sectional descriptive part and a longitudinal part with repeated measurements over five swimming sessions. Eighty-six adolescent swimmers completed a questionnaire to assess their sport nutrition and hydration knowledge. Fluid balance and urine hydration markers were studied during training. Swimmers showed a limited nutrition knowledge (33.26 % ± SD 12.59 and meagre hydration knowledge (28.61 % ± SD 28.59. Females showed lower scores than male swimmers in nutrition and hydration knowledge. Based on urine specific gravity, swimmers started the training close to the euhydrated threshold (1.019 g/mL ± SD 0.008. Although urine specific gravity and urine colour were reduced after the training, there were minimal changes in body mass (-0.12 Kg ± SD 0.31. Sweat loss (2.67 g/min ± SD 3.23 and the net changes in the fluid balance (-0.22 % ± SD 0.59 were low. The poor knowledge in nutrition and hydration encountered in the swimmers can justify the development of a strategy to incorporate nutritional education programmes for this group. Body water deficit from swimming activity seems to be easily replaced with the water intake to maintain hydration. After the training, the urine of swimmers was diluted regardless of their water intake. Dilution of urine did not reflect real hydration state in swimming.

Extraction and characterisation of apatite- and tricalcium phosphate-based materials from cod fish bones

International Nuclear Information System (INIS)

Piccirillo, C.; Silva, M.F.; Pullar, R.C.; Braga da Cruz, I.; Jorge, R.; Pintado, M.M.E.; Castro, P.M.L.

2013-01-01

Apatite- and tricalcium phosphate-based materials were produced from codfish bones, thus converting a waste by-product from the food industry into high added-valued compounds. The bones were annealed at temperatures between 900 and 1200 °C, giving a biphasic material of hydroxyapatite and tricalcium phosphate (Ca 10 (PO 4 ) 6 (OH) 2 and β-Ca(PO 4 ) 3 ) with a molar proportion of 75:25, a material widely used in biomedical implants. The treatment of the bones in solution prior to their annealing changed the composition of the material. Single phase hydroxyapatite, chlorapatite (Ca 10 (PO 4 ) 6 Cl 2 ) and fluorapatite (Ca 10 (PO 4 ) 6 F 2 ) were obtained using CaCl 2 and NaF solutions, respectively. The samples were analysed by several techniques (X-ray diffraction, infrared spectroscopy, scanning electron microscopy and differential thermal/thermogravimetric analysis) and by elemental analyses, to have a more complete understanding of the conversion process. Such compositional modifications have never been performed before for these materials of natural origin to tailor the relative concentrations of elements. This paper shows the great potential for the conversion of this by-product into highly valuable compounds for biomedical applications, using a simple and effective valorisation process. - Highlights: ► Apatite and calcium phosphate compounds extraction from cod fish bones ► Bone calcination: biphasic material hydroxyapatite-calcium phosphate production ► Bone pre-treatments in solution change the material composition. ► Single phase materials (hydroxy-, chloro- or fluoroapatite) are obtained. ► Concentration of other elements (Na, F, Cl) suitable for biomedical applications

Methane hydrates in nature - Current knowledge and challenges

Science.gov (United States)

Collett, Timothy S.

2014-01-01

Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance

Geologic implications of gas hydrates in the offshore of India: results of the National Gas Hydrate Program Expedition 01

Science.gov (United States)

Collett, Timothy S.; Boswell, Ray; Cochran, J.R.; Kumar, Pushpendra; Lall, Malcolm; Mazumdar, Aninda; Ramana, Mangipudi Venkata; Ramprasad, Tammisetti; Riedel, Michael; Sain, Kalachand; Sathe, Arun Vasant; Vishwanath, Krishna

2014-01-01

The Indian National Gas Hydrate Program Expedition 01 (NGHP-01) is designed to study the occurrence of gas hydrate along the passive continental margin of the Indian Peninsula and in the Andaman convergent margin, with special emphasis on understanding the geologic and geochemical controls on the occurrence of gas hydrate in these two diverse settings. The NGHP-01 expedition established the presence of gas hydrates in the Krishna-Godavari and Mahanadi Basins, and the Andaman Sea. The expedition discovered in the Krishna-Godavari Basin one of the thickest gas hydrate accumulations ever documented, in the Andaman Sea one of the thickest and deepest gas hydrate stability zones in the world, and established the existence of a fully developed gas hydrate petroleum system in all three basins.

Spatial resolution of gas hydrate and permeability changes from ERT data in LARS simulating the Mallik gas hydrate production test

Science.gov (United States)

Priegnitz, Mike; Thaler, Jan; Spangenberg, Erik; Schicks, Judith M.; Abendroth, Sven

2014-05-01

The German gas hydrate project SUGAR studies innovative methods and approaches to be applied in the production of methane from hydrate-bearing reservoirs. To enable laboratory studies in pilot scale, a large reservoir simulator (LARS) was realized allowing for the formation and dissociation of gas hydrates under simulated in-situ conditions. LARS is equipped with a series of sensors. This includes a cylindrical electrical resistance tomography (ERT) array composed of 25 electrode rings featuring 15 electrodes each. The high-resolution ERT array is used to monitor the spatial distribution of the electrical resistivity during hydrate formation and dissociation experiments over time. As the present phases of poorly conducting sediment, well conducting pore fluid, non-conducting hydrates, and isolating free gas cover a wide range of electrical properties, ERT measurements enable us to monitor the spatial distribution of these phases during the experiments. In order to investigate the hydrate dissociation and the resulting fluid flow, we simulated a hydrate production test in LARS that was based on the Mallik gas hydrate production test (see abstract Heeschen et al., this volume). At first, a hydrate phase was produced from methane saturated saline water. During the two months of gas hydrate production we measured the electrical properties within the sediment sample every four hours. These data were used to establish a routine estimating both the local degrees of hydrate saturation and the resulting local permeabilities in the sediment's pore space from the measured resistivity data. The final gas hydrate saturation filled 89.5% of the total pore space. During hydrate dissociation, ERT data do not allow for a quantitative determination of free gas and remaining gas hydrates since both phases are electrically isolating. However, changes are resolved in the spatial distribution of the conducting liquid and the isolating phase with gas being the only mobile isolating phase

Simulation and Characterization of Methane Hydrate Formation

Science.gov (United States)

Dhakal, S.; Gupta, I.

2017-12-01

The ever rising global energy demand dictates human endeavor to explore and exploit new and innovative energy sources. As conventional oil and gas reserves deplete, we are constantly looking for newer sources for sustainable energy. Gas hydrates have long been discussed as the next big energy resource to the earth. Its global occurrence and vast quantity of natural gas stored is one of the main reasons for such interest in its study and exploration. Gas hydrates are solid crystalline substances with trapped molecules of gas inside cage-like crystals of water molecules. Gases such as methane, ethane, propane and carbon dioxide can form hydrates but in natural state, methane hydrates are the most common. Subsurface geological conditions with high pressure and low temperature favor the formation and stability of gas hydrates. While the occurrence and potential of gas hydrates as energy source has long been studied, there are still gaps in knowledge, especially in the quantitative research of gas hydrate formation and reservoir characterization. This study is focused on exploring and understanding the geological setting in which gas hydrates are formed and the subsequent changes in rock characteristics as they are deposited. It involves the numerical simulation of methane gas flow through fault to form hydrates. The models are representative of the subsurface geologic setting of Gulf of Mexico with a fault through layers of shale and sandstone. Hydrate formation simulated is of thermogenic origin. The simulations are conducted using TOUGH+HYDRATE, a numerical code developed at the Lawrence Berkley National Laboratory for modeling multiphase flow through porous medium. Simulation results predict that as the gas hydrates form in the pores of the model, the porosity, permeability and other rock properties are altered. Preliminary simulation results have shown that hydrates begin to form in the fault zone and gradually in the sandstone layers. The increase in hydrate

Variation in Surficial Hydrated Minerals on Large Low-Albedo Asteroids

Science.gov (United States)

Rivkin, Andrew S.; Emery, Joshua P.; Howell, Ellen S.

2017-10-01

Observations of asteroids in the 3-µm spectral region, where absorptions diagnostic for hydrated minerals are found, show low-albedo asteroid spectra can be classified into at least 3 groups (Takir et al. 2013, Rivkin et al. 2015). While definitions of these groups vary between authors, they hold in common a group with spectra like what we see for CM/CI meteorites, one group with spectra like that of Ceres, and a group with spectra that have been interpreted as ice frost. The relationship between these groups is not yet clear. One possibility is that the spectrum reflects (no pun intended) the formation location for the asteroids and that a given object is undifferentiated and homogeneous in the composition of its hydrated minerals. However, models of the thermal and chemical evolution of large, low-albedo asteroids suggests that differentiation may be more common than we had thought, and impacts could exhume once-deep layers or expose complicated mixes of salts and silicates (for instance, Castillo-Rogez et al. LPSC 2017 model of Ceres). In this case, we might expect variation in the 3-µm spectral region to be seen on the surfaces of some objects as they rotate. We will present evidence for such variation in the spectrum of two large asteroids, 704 Interamnia (306 km diameter) and 324 Bamberga (220 km diameter). In the first case, Interamnia’s spectrum seems to have a combination of Ceres- and CM/CI-like features and has aspects where one or another component is dominant, while Bamberga’s spectrum is not easily placed in previously-defined groups.

Seismic reflections associated with submarine gas hydrates

Energy Technology Data Exchange (ETDEWEB)

Andreassen, K

1996-12-31

Gas hydrates are often suggested as a future energy resource. This doctoral thesis improves the understanding of the concentration and distribution of natural submarine gas hydrates. The presence of these hydrates are commonly inferred from strong bottom simulating reflection (BSR). To investigate the nature of BSR, this work uses seismic studies of hydrate-related BSRs at two different locations, one where gas hydrates are accepted to exist and interpreted to be very extensive (in the Beaufort Sea), the other with good velocity data and downhole logs available (offshore Oregon). To ascertain the presence of free gas under the BSR, prestack offset data must supplement near-vertical incidence seismic data. A tentative model for physical properties of sediments partially saturated with gas hydrate and free gas is presented. This model, together with drilling information and seismic data containing the BSR beneath the Oregon margin and the Beaufort Sea, made it possible to better understand when to apply the amplitude-versus-offset (AVO) method to constrain BSR gas hydrate and gas models. Distribution of natural gas hydrates offshore Norway and Svalbard is discussed and interpreted as reflections from the base of gas hydrate-bearing sediments, overlying sediments containing free gas. Gas hydrates inferred to exist at the Norwegian-Svalbard continental margin correlate well with Cenozoic depocenters, and the associated gas is assumed to be mainly biogenic. Parts of that margin have a high potential for natural gas hydrates of both biogenic and thermogenic origin. 235 refs., 86 figs., 4 tabs.

Seismic reflections associated with submarine gas hydrates

Energy Technology Data Exchange (ETDEWEB)

Andreassen, K.

1995-12-31

Gas hydrates are often suggested as a future energy resource. This doctoral thesis improves the understanding of the concentration and distribution of natural submarine gas hydrates. The presence of these hydrates are commonly inferred from strong bottom simulating reflection (BSR). To investigate the nature of BSR, this work uses seismic studies of hydrate-related BSRs at two different locations, one where gas hydrates are accepted to exist and interpreted to be very extensive (in the Beaufort Sea), the other with good velocity data and downhole logs available (offshore Oregon). To ascertain the presence of free gas under the BSR, prestack offset data must supplement near-vertical incidence seismic data. A tentative model for physical properties of sediments partially saturated with gas hydrate and free gas is presented. This model, together with drilling information and seismic data containing the BSR beneath the Oregon margin and the Beaufort Sea, made it possible to better understand when to apply the amplitude-versus-offset (AVO) method to constrain BSR gas hydrate and gas models. Distribution of natural gas hydrates offshore Norway and Svalbard is discussed and interpreted as reflections from the base of gas hydrate-bearing sediments, overlying sediments containing free gas. Gas hydrates inferred to exist at the Norwegian-Svalbard continental margin correlate well with Cenozoic depocenters, and the associated gas is assumed to be mainly biogenic. Parts of that margin have a high potential for natural gas hydrates of both biogenic and thermogenic origin. 235 refs., 86 figs., 4 tabs.

Comparison of silicon nanoparticles and silicate treatments in fenugreek.

Science.gov (United States)

Nazaralian, Sanam; Majd, Ahmad; Irian, Saeed; Najafi, Farzaneh; Ghahremaninejad, Farrokh; Landberg, Tommy; Greger, Maria

2017-06-01

Silicon (Si) fertilization improves crop cultivation and is commonly added in the form of soluble silicates. However, most natural plant-available Si originates from plant formed amorphous SiO 2 particles, phytoliths, similar to SiO 2 -nanoparticles (SiNP). In this work we, therefore, compared the effect by sodium silicate and that of SiNP on Si accumulation, activity of antioxidative stress enzymes catalase, peroxidase, superoxide dismutase, lignification of xylem cell walls and activity of phenylalanine ammonia-lyase (PAL) as well as expression of genes for the putative silicon transporter (PST), defensive (Tfgd 1) and phosphoenolpyruvate carboxykinase (PEPCK) and protein in fenugreek (Trigonella foenum-graecum L.) grown in hydroponics. The results showed that Si was taken up from both silicate and SiNP treatments and increasing sodium silicate addition increased the translocation of Si to the shoot, while this was not shown with increasing SiNP addition. The silicon transporter PST was upregulated at a greater level when sodium silicate was added compared with SiNP addition. There were no differences in effects between sodium silicate and SiNP treatments on the other parameters measured. Both treatments increased the uptake and accumulation of Si, xylem cell wall lignification, cell wall thickness, PAL activity and protein concentration in seedlings, while there was no effect on antioxidative enzyme activity. Tfgd 1 expression was strongly downregulated in leaves at Si addition. The similarity in effects by silicate and SiNP would be due to that SiNP releases silicate, which may be taken up, shown by a decrease in SiNP particle size with time in the medium. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Influence of temperature on the synthesis of calcining cement α--tricalcium phosphate

International Nuclear Information System (INIS)

Vieira, R.S.; Thurmer, M.B.; Coelho, W.T.; Fernandes, J.M.; Santos, L.A.

2011-01-01

The calcium phosphate cement (CFCs) bone substitutes are of great potential use in medical and dental. However, one of the great difficulties of using this type of cement is its low mechanical strength due to the presence of undesirable phases, such as beta-tricalcium phosphate. The step of obtaining this compound is done at high temperature by solid state reaction. With the aim of obtaining calcium phosphate cements more resistant, we studied the conditions for obtaining an alpha-TCP at temperatures of 1300, 1400 and 1500 ° C with time 2h calcination. The samples were analyzed for crystalline phases, density, porosity and mechanical strength. The results show that the synthesis parameters studied strongly influence the obtained phases and the mechanical properties of cement. (author)

Silicate enamel for alloyed steel

International Nuclear Information System (INIS)

Ket'ko, K.K.

1976-01-01

The use of silicate enamels in the metallurgical industry is discussed. Presented are the composition and the physico-chemical properties of the silicate enamel developed at the factory 'Krasnyj Oktyabr'. This enamel can be used in the working conditions both in the liquid and the solid state. In so doing the enamel is melted at 1250 to 1300 deg C, granulated and then reduced to a fraction of 0.3 to 0.5 mm. The greatest homogeneity is afforded by a granulated enamel. The trials have shown that the conversion of the test ingots melted under a layer of enamel leads to the smaller number of the ingots rejected for surface defect reasons and the lower metal consumption for slab cleaning. The cost of the silicate enamel is somewhat higher than that of synthetic slags but its application to the melting of stainless steels is still economically beneficial and technologically reasonable. Preliminary calculations only for steel EhI4IEh have revealed that the use of this enamel saves annually over 360000 roubles [ru

Gas Hydrate Storage of Natural Gas

Energy Technology Data Exchange (ETDEWEB)

Rudy Rogers; John Etheridge

2006-03-31

Environmental and economic benefits could accrue from a safe, above-ground, natural-gas storage process allowing electric power plants to utilize natural gas for peak load demands; numerous other applications of a gas storage process exist. A laboratory study conducted in 1999 to determine the feasibility of a gas-hydrates storage process looked promising. The subsequent scale-up of the process was designed to preserve important features of the laboratory apparatus: (1) symmetry of hydrate accumulation, (2) favorable surface area to volume ratio, (3) heat exchanger surfaces serving as hydrate adsorption surfaces, (4) refrigeration system to remove heat liberated from bulk hydrate formation, (5) rapid hydrate formation in a non-stirred system, (6) hydrate self-packing, and (7) heat-exchanger/adsorption plates serving dual purposes to add or extract energy for hydrate formation or decomposition. The hydrate formation/storage/decomposition Proof-of-Concept (POC) pressure vessel and supporting equipment were designed, constructed, and tested. This final report details the design of the scaled POC gas-hydrate storage process, some comments on its fabrication and installation, checkout of the equipment, procedures for conducting the experimental tests, and the test results. The design, construction, and installation of the equipment were on budget target, as was the tests that were subsequently conducted. The budget proposed was met. The primary goal of storing 5000-scf of natural gas in the gas hydrates was exceeded in the final test, as 5289-scf of gas storage was achieved in 54.33 hours. After this 54.33-hour period, as pressure in the formation vessel declined, additional gas went into the hydrates until equilibrium pressure/temperature was reached, so that ultimately more than the 5289-scf storage was achieved. The time required to store the 5000-scf (48.1 hours of operating time) was longer than designed. The lower gas hydrate formation rate is attributed to a

Distinguishing between hydrated, partially hydrated or unhydrated clinker in hardened concrete using microscopy

NARCIS (Netherlands)

Valcke, S.L.A.; Rooij, M.R. de; Visser, J.H.M.; Nijland, T.G.

2010-01-01

Hydration of clinker particles is since long a topic of interest in both designing and optimizing cement composition and its quantity used in concrete. The interest for carefully observing and also quantifying the type or stage of clinker hydration in hardened cement paste is twofold. Firstly, the

THERMODYNAMIC MODEL OF GAS HYDRATES

OpenAIRE

Недоступ, В. И.; Недоступ, О. В.

2015-01-01

The interest to gas hydrates grows last years. Therefore working out of reliable settlement-theoretical methods of definition of their properties is necessary. The thermodynamic model of gas hydrates in which the central place occupies a behaviour of guest molecule in cell is described. The equations of interaction of molecule hydrate formative gas with cell are received, and also an enthalpy and energy of output of molecule from a cell are determined. The equation for calculation of thermody...

Gas hydrate cool storage system

Science.gov (United States)

Ternes, M.P.; Kedl, R.J.

1984-09-12

The invention presented relates to the development of a process utilizing a gas hydrate as a cool storage medium for alleviating electric load demands during peak usage periods. Several objectives of the invention are mentioned concerning the formation of the gas hydrate as storage material in a thermal energy storage system within a heat pump cycle system. The gas hydrate was formed using a refrigerant in water and an example with R-12 refrigerant is included. (BCS)

Indian National Gas Hydrate Program Expedition 01 report

Science.gov (United States)

Collett, Timothy S.; Riedel, M.; Boswell, R.; Presley, J.; Kumar, P.; Sathe, A.; Sethi, A.; Lall, M.V.; ,

2015-01-01

Gas hydrate is a naturally occurring “ice-like” combination of natural gas and water that has the potential to serve as an immense resource of natural gas from the world’s oceans and polar regions. However, gas-hydrate recovery is both a scientific and a technical challenge and much remains to be learned about the geologic, engineering, and economic factors controlling the ultimate energy resource potential of gas hydrate. The amount of natural gas contained in the world’s gas-hydrate accumulations is enormous, but these estimates are speculative and range over three orders of magnitude from about 2,800 to 8,000,000 trillion cubic meters of gas. By comparison, conventional natural gas accumulations (reserves and undiscovered, technically recoverable resources) for the world are estimated at approximately 440 trillion cubic meters. Gas recovery from gas hydrate is hindered because the gas is in a solid form and because gas hydrate commonly occurs in remote Arctic and deep marine environments. Proposed methods of gas recovery from gas hydrate generally deal with disassociating or “melting” in situ gas hydrate by heating the reservoir beyond the temperature of gas-hydrate formation, or decreasing the reservoir pressure below hydrate equilibrium. The pace of energy-related gas hydrate assessment projects has accelerated over the past several years.

Anti-Agglomerator of Tetra-n-Butyl Ammonium Bromide Hydrate and Its Effect on Hydrate-Based CO2 Capture

Directory of Open Access Journals (Sweden)

Rong Li

2018-02-01

Full Text Available Tetra-n-butyl ammonium bromide (TBAB was widely used in the research fields of cold storage and CO2 hydrate separation due to its high phase change latent heat and thermodynamic promotion for hydrate formation. Agglomeration always occurred in the process of TBAB hydrate generation, which led to the blockage in the pipeline and the separation apparatus. In this work, we screened out a kind of anti-agglomerant that can effectively solve the problem of TBAB hydrate agglomeration. The anti-agglomerant (AA is composed of 90% cocamidopropyl dimethylamine and 10% glycerol, which can keep TBAB hydrate of 19.3–29.0 wt. % in a stable state of slurry over 72 h. The microscopic observation of the morphology of the TBAB hydrate particles showed that the addition of AA can greatly reduce the size of the TBAB hydrate particles. CO2 gas separation experiments found that the addition of AA led to great improvement on gas storage capacity, CO2 split fraction and separation factor, due to the increasing of contact area between gas phase and hydrate particles. The CO2 split fraction and separation factor with AA addition reached up to 70.3% and 42.8%, respectively.

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

Thomas E. Williams; Keith Millheim; Bill Liddell

2005-03-01

Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Oil-field engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in Arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored the HOT ICE No. 1 on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was designed, constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. Unfortunately, no gas hydrates were encountered in this well; however, a wealth of information was generated

Heterogeneous nucleation of protein crystals on fluorinated layered silicate.

Directory of Open Access Journals (Sweden)

Keita Ino

Full Text Available Here, we describe an improved system for protein crystallization based on heterogeneous nucleation using fluorinated layered silicate. In addition, we also investigated the mechanism of nucleation on the silicate surface. Crystallization of lysozyme using silicates with different chemical compositions indicated that fluorosilicates promoted nucleation whereas the silicates without fluorine did not. The use of synthesized saponites for lysozyme crystallization confirmed that the substitution of hydroxyl groups contained in the lamellae structure for fluorine atoms is responsible for the nucleation-inducing property of the nucleant. Crystallization of twelve proteins with a wide range of pI values revealed that the nucleation promoting effect of the saponites tended to increase with increased substitution rate. Furthermore, the saponite with the highest fluorine content promoted nucleation in all the test proteins regardless of their overall net charge. Adsorption experiments of proteins on the saponites confirmed that the density of adsorbed molecules increased according to the substitution rate, thereby explaining the heterogeneous nucleation on the silicate surface.

Synthesis and characterization of tricalcium phosphate ceramics doped with zinc

International Nuclear Information System (INIS)

Kai, K.C.; Marchi, J.; Ussui, V.; Bressiani, A.H.A.

2011-01-01

Due to its biocompatibility, the tricalcium phosphate (TCP) is used as a biomaterial for bone replacement and reconstruction. Zinc (Zn) can replace calcium in the crystal structure of TCP to be added in small quantities, can result in stimulatory effects on bone formation in vitro and in vivo. In this work, pure TCP and Zn-TCP, with general formula (Ca_1_-_xZn_x)_3 (PO_4)_2 and 0 ≤ x ≤ 0.0225, were prepared by wet synthesis, from precursors Ca(OH)_2, H_3PO_4 and ZnO, after calcinated at 800 deg C and characterized by X-ray diffraction, specific surface area, agglomerate size distribution, differential thermal analysis and scanning electron microscopy. The results showed that the addition of small amounts of Zn resulted in TCP with suitable densification and higher specific surface area, may be promising as biomaterial due to the stimulatory effects of zinc associated with suitable mechanical properties of the final material. (author)

Wind-eroded silicate as a source of hydrogen peroxide on Mars

DEFF Research Database (Denmark)

Bak, Ebbe Norskov; Merrison, Jonathan P.; Jensen, Svend Knak

-sists of silicates [4] that due to wind erosion has a very fine grained texture. Based on the composition of the surface material and investigations showing that crushing of silicates can give rise to reactive oxygen species [5], we hypothesized that wind erosion of silicates can explain the reactivity of Martian...... soil. Wind-erosion of silicate could thus be one of several causes of the soil’s reactivity. As our experiments show, the globally distributed wind eroded silicate dust can lead to the production of hydrogen peroxide which might explain the reactivity of the Martian soil. The reactivity of eroded...

FY1995 molecular control technology for mining of methane-gas-hydrate; 1995 nendo methane hydrate no bunshi seigyo mining

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-03-01

The objectives of the investigation are as follows: 1) developing a method to control formation/dissociation of methane-gas-hydrate, 2) developing a technology to displace methane gas by CO{sub 2} in methane-gas-hydrate deposit, 3) developing a technology to produce methane gas from the deposit efficiently. The final purpose of the project is to create new mining industry that solves both the problems of energy and global environment. 1) Clustering of water molecules is found to play the key role in the methane gas hydrate formation. 2) Equilibrium properties and kinetics of gas hydrates formation and dissociation in bulk-scale gas-hydrate are clarified in the practical environmental conditions. 3) Particle size of hydrate deposit influences the formation and dissociation of bulk-scale gas-hydrate crystal. 4) Mass transfer between gas and liquid phase in turbulent bubbly flow is a function of bubble diameter. The mass transfer depends on interfacial dynamics. (NEDO)

Changes in structure and preferential cage occupancy of ethane hydrate and ethane-methane mixed gas hydrate under high pressure

International Nuclear Information System (INIS)

Hirai, H; Takahara, N; Kawamura, T; Yamamoto, Y; Yagi, T

2010-01-01

Structural changes and preferential cage occupancies were examined for ethane hydrate and ethane-methane mixed gas hydrates with five compositions in a pressure range of 0.2 to 2.8 GPa at room temperature. X-ray diffractometry and Raman spectroscopy showed the following structural changes. The initial structure, structure I (sI), of ethane hydrate was retained up to 2.1 GPa without any structural change. For the mixed hydrates, sI was widely distributed throughout the region examined except for the methane-rich and lower pressure regions, where sII and sH appeared. Above 2.1 GPa ethane hydrate and all of the mixed hydrates decomposed into ice VI and ethane fluid or methane-ethane fluid, respectively. The Raman study revealed that occupation of the small cages by ethane molecules occurred above 0.1 GPa in ethane hydrate and continued up to decomposition at 2.1 GPa, although it was thought that ethane molecules were contained only in the large cage.

Peculiarities of the processes of hydration of binding substances in the arbolite mixture

Science.gov (United States)

Innokentieva, L. S.; Egorova, A. D.; Emelianova, Z. V.

2017-09-01

Cement and sand solution is traditionally used for production of wood concrete. But it is known that impact of water-soluble substances of wood on the hardening cement is shown in the stabilizing effect. The "Cement poisons" consisting generally of the HOCH carbohydrate groups, sedimented on a surface of particles of minerals of cement 3CaO.SiO2 (three-calcic silicate) and 3CaO.Al2O3 (three-calcic aluminate) form the thinnest covers which complicate the course of processes of hydration of cement. Plaster in comparison with cement is less sensitive to extractive substances of wood therefore their combination to wood (including waste of logging and a woodworking) both coniferous and deciduous species is allowed. Composite plaster binding with hongurin as active mineral additive agent are applied at selection of composition of arbolite, at the same time dependences of their physicomechanical properties on characteristics of filler are received.

Recycling of porcelain tile polishing residue in portland cement: hydration efficiency.

Science.gov (United States)

Pelisser, Fernando; Steiner, Luiz Renato; Bernardin, Adriano Michael

2012-02-21

Ceramic tiles are widely used by the construction industry, and the manufacturing process of ceramic tiles generates as a major residue mud derived from the polishing step. This residue is too impure to be reused in the ceramic process and is usually discarded as waste in landfills. But the analysis of the particle size and concentration of silica of this residue shows a potential use in the manufacture of building materials based on portland cement. Tests were conducted on cement pastes and mortars using the addition of 10% and 20% (mass) of the residue. The results of compressive strength in mortars made up to 56 days showed a significant increase in compressive strength greater than 50%. The result of thermogravimetry shows that portlandite is consumed by the cement formed by the silica present in the residue in order to form calcium silicate hydrate and featuring a pozzolanic reaction. This effect improves the performance of cement, contributes to research and application of supplementary cementitious materials, and optimizes the use of portland cement, reducing the environmental impacts of carbon dioxide emissions from its production.

Impact of Compound Hydrate Dynamics on Phase Boundary Changes

Science.gov (United States)

Osegovic, J. P.; Max, M. D.

2006-12-01

Compound hydrate reactions are affected by the local concentration of hydrate forming materials (HFM). The relationship between HFM composition and the phase boundary is as significant as temperature and pressure. Selective uptake and sequestration of preferred hydrate formers (PF) has wide ranging implications for the state and potential use of natural hydrate formation, including impact on climate. Rising mineralizing fluids of hydrate formers (such as those that occur on Earth and are postulated to exist elsewhere in the solar system) will sequester PF before methane, resulting in a positive relationship between depth and BTU content as ethane and propane are removed before methane. In industrial settings the role of preferred formers can separate gases. When depressurizing gas hydrate to release the stored gas, the hydrate initial composition will set the decomposition phase boundary because the supporting solution takes on the composition of the hydrate phase. In other settings where hydrate is formed, transported, and then dissociated, similar effects can control the process. The behavior of compound hydrate systems can primarily fit into three categories: 1) In classically closed systems, all the material that can form hydrate is isolated, such as in a sealed laboratory vessel. In such systems, formation and decomposition are reversible processes with observed hysteresis related to mass or heat transfer limitations, or the order and magnitude in which individual hydrate forming gases are taken up from the mixture and subsequently released. 2) Kinetically closed systems are exposed to a solution mass flow across a hydrate mass. These systems can have multiple P-T phase boundaries based on the local conditions at each face of the hydrate mass. A portion of hydrate that is exposed to fresh mineralizing solution will contain more preferred hydrate formers than another portion that is exposed to a partially depleted solution. Examples of kinetically closed

PETROLOGY AND GEOCHEMISTRY OF CALC-SILICATE SCHISTS ...

African Journals Online (AJOL)

DR OKONKOWO

2012-02-29

silicate reaction bands have higher contents of CaO and Sr and lower concentrations of K2O, Rb, Ni, and Ba relative to the calc-silicate schists; and relatively higher SiO2, TiO2, Al2O3, Fe2O3, MgO, Na2O, K2O and P2O5 and lower ...

Natural gas hydrates. Experimental techniques and their applications

Energy Technology Data Exchange (ETDEWEB)

Ye, Yuguang; Liu, Changling (eds.) [Qingdao Institute of Marine Geology (China). Gas Hydrate Laboratory

2013-07-01

Focuses on gas hydrate experiment in laboratory. Intends to provide practical significant parameters for gas hydrate exploration and exploitation in the oceanic and permafrost environments. Consists of different themes that present up-to-date information on hydrate experiments. ''Natural Gas Hydrates: Experimental Techniques and Their Applications'' attempts to broadly integrate the most recent knowledge in the fields of hydrate experimental techniques in the laboratory. The book examines various experimental techniques in order to provide useful parameters for gas hydrate exploration and exploitation. It provides experimental techniques for gas hydrates, including the detection techniques, the thermo-physical properties, permeability and mechanical properties, geochemical abnormalities, stability and dissociation kinetics, exploitation conditions, as well as modern measurement technologies etc.

The application of silicon and silicates in dentistry: a review.

Science.gov (United States)

Lührs, A-K; Geurtsen, Werner

2009-01-01

Silicates and silicate-based compounds are frequently used materials in dentistry. One of their major applications is their use as fillers in different dental filling materials such as glass-ionomer cements, compomers, composites, and adhesive systems. In these materials, the fillers react with acids during the setting process or they improve the mechanical properties by increasing physical resistance, thermal expansion coefficient and radiopacity in acrylic filling materials. They also reduce polymerization shrinkage, and increase esthetics as well as handling properties. Furthermore, silicates are used for the tribochemical silication of different surfaces such as ceramics or alloys. The silicate layer formed in this process is the chemical basis for silanes that form a bond between this layer and the organic composite matrix. It also provides a micromechanical bond between the surface of the material and the composite matrix. Silicates are also a component of dental ceramics, which are frequently used in dentistry, for instance for veneers, inlays, and onlays, for denture teeth, and for full-ceramic crowns or as crown veneering materials.

Rheological properties of hydrate suspensions in asphaltenic crude oils; Proprietes rheologiques de suspensions d'hydrate dans des bruts asphalteniques

Energy Technology Data Exchange (ETDEWEB)

Marques de Toledo Camargo, R.

2001-03-01

The development of offshore oil exploitation under increasing water depths has forced oil companies to increase their understanding of gas hydrate formation and transportation in multiphase flow lines in which a liquid hydrocarbon phase is present. This work deals with the flow behaviour of hydrate suspensions in which a liquid hydrocarbon is the continuous phase. Three different liquid hydrocarbons are used: an asphaltenic crude oil, a condensate completely free of asphaltenes and a mixture between the asphaltenic oil and heptane. The rheological characterisation of hydrate suspensions is the main tool employed. Two original experimental devices are used: a PVT cell adapted to operate as a Couette type rheometer and a semi-industrial flow loop. Hydrate suspensions using the asphaltenic oil showed shear-thinning behaviour and thixotropy. This behaviour is typically found in flocculated systems, in which the particles attract each other forming flocs of aggregated particles at low shear rates. The suspensions using the condensate showed Newtonian behaviour. Their relative viscosities were high, which suggests that an aggregation process between hydrate particles takes. place during hydrate formation. Finally, hydrate suspensions using the mixture asphaltenic oil-heptane showed shear-thinning behaviour, thixotropy and high relative viscosity. From these results it can be inferred that, after the achievement of the hydrate formation process, the attractive forces between hydrate particles are weak. making unlikely pipeline obstruction by an aggregation process. Nevertheless, during the hydrate formation, these attractive forces can be sufficiently high. It seems that the hydrate surface wettability is an important parameter in this phenomena. (author)

Surface charges and Np(V) sorption on amorphous Al- and Fe- silicates

International Nuclear Information System (INIS)

Del Nero, M.; Assada, A.; Barillon, R.; Duplatre, G.; Made, B.

2005-01-01

Full text of publication follows: Sorption onto Si-rich alteration layers of crystalline minerals and nuclear glasses, and onto amorphous secondary silicates of rocks and soils, are expected to retard the migration of actinides in the near- and far-field of HLW repositories. We present experimental and modeling studies on the effects of silicate structure and bulk chemistry, and of solution chemistry, on charges and adsorption of neptunyl ions at surfaces of synthetic, amorphous or poorly ordered silica, Al-silicates and Fe-silicates. The Al-silicates display similar pH-dependent surface charges characterized by predominant Si-O - Si sites, and similar surface affinities for neptunyl ions, irrespective to their Si/Al molar ratio (varying from 10 to 4.3). Such experimental features are explained by incorporation of Al atoms in tetrahedral position in the silicate lattice, leading to only trace amounts of high-affinity Al-OH surface groups due to octahedral Al. By contrast, the structure of the Fe-silicates ensures the occurrence of high-affinity Fe-OH surface groups, whose concentration is shown by proton adsorption measurements to increase with decreasing of the silicate Si/Fe molar ratio (from 10 to 2.3). Nevertheless, experimental data of the adsorption of neptunyl and electrolyte ions show unexpectedly weak effect of the Si/Fe ratio, and suggest predominant Si-OH surface groups. A possible explanation is that aqueous silicate anions, released by dissolution, adsorb at OH Fe - surface groups and / or precipitate as silica gel coatings, because experimental solutions were found at near-equilibrium with respect to amorphous silica. Therefore, the environmental sorption of Np(V) onto Si-rich, amorphous or poorly ordered Al-silicates may primarily depend on pH and silicate specific surface areas, given the low overall chemical affinity of such phases for dissolved metals. By contrast, the sorption of Np(V) on natural, amorphous or poorly ordered Fe-silicates may be a

Experimental Determination of Refractive Index of Gas Hydrates

DEFF Research Database (Denmark)

Bylov, Martin; Rasmussen, Peter

1997-01-01

. For methane hydrate (structure I) the refractive index was found to be 1.346 and for natural gas hydrate (structure II) it was found to be 1.350. The measurements further suggest that the gas hydrate growth rate increases if the water has formed hydrates before. The induction time, on the other hand, seems......The refractive indexes of methane hydrate and natural gas hydrate have been experimentally determined. The refractive indexes were determined in an indirect manner making use of the fact that two non-absorbing materials will have the same refractive index if they cannot be distinguished visually...

METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

Energy Technology Data Exchange (ETDEWEB)

Ali Kadaster; Bill Liddell; Tommy Thompson; Thomas Williams; Michael Niedermayr

2005-02-01

Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project was a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope included drilling and coring a well (Hot Ice No. 1) on Anadarko leases beginning in FY 2003 and completed in 2004. During the first drilling season, operations were conducted at the site between January 28, 2003 to April 30, 2003. The well was spudded and drilled to a depth of 1403 ft. Due to the onset of warmer weather, work was then suspended for the season. Operations at the site were continued after the tundra was re-opened the following season. Between January 12, 2004 and March 19, 2004, the well was drilled and cored to a final depth of 2300 ft. An on-site core analysis laboratory was built and implemented for determining physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. Final efforts of the project are to correlate geology, geophysics, logs, and drilling and

Raman studies of methane-ethane hydrate metastability.

Science.gov (United States)

Ohno, Hiroshi; Strobel, Timothy A; Dec, Steven F; Sloan, E Dendy; Koh, Carolyn A

2009-03-05

The interconversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. sI and sII hydrates were synthesized from methane-ethane gas mixtures of 65% or 93% methane in ethane and water, both with and without the kinetic hydrate inhibitor, poly(N-vinylcaprolactam). The observed faster structural conversion rate in the higher methane concentration atmosphere can be explained in terms of the differences in driving force (difference in chemical potential of water in sI and sII hydrates) and kinetics (mass transfer of gas and water rearrangement). The kinetic hydrate inhibitor increased the conversion rate at 65% methane in ethane (sI is thermodynamically stable) but retards the rate at 93% methane in ethane (sII is thermodynamically stable), implying there is a complex interaction between the polymer, water, and hydrate guests at crystal surfaces.

Methane Hydrate Field Program: Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

Energy Technology Data Exchange (ETDEWEB)

Myers, Greg [Consortium for Ocean Leadership, Washington, DC (United States)

2014-02-01

This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report: Historical Methane Hydrate Project Review Report; Methane Hydrate Workshop Report; Topical Report: Marine Methane Hydrate Field Research Plan; and Final Scientific/Technical Report.

An effective medium inversion algorithm for gas hydrate quantification and its application to laboratory and borehole measurements of gas hydrate-bearing sediments

Science.gov (United States)

Chand, S.; Minshull, T.A.; Priest, J.A.; Best, A.I.; Clayton, C.R.I.; Waite, W.F.

2006-01-01

The presence of gas hydrate in marine sediments alters their physical properties. In some circumstances, gas hydrate may cement sediment grains together and dramatically increase the seismic P- and S-wave velocities of the composite medium. Hydrate may also form a load-bearing structure within the sediment microstructure, but with different seismic wave attenuation characteristics, changing the attenuation behaviour of the composite. Here we introduce an inversion algorithm based on effective medium modelling to infer hydrate saturations from velocity and attenuation measurements on hydrate-bearing sediments. The velocity increase is modelled as extra binding developed by gas hydrate that strengthens the sediment microstructure. The attenuation increase is modelled through a difference in fluid flow properties caused by different permeabilities in the sediment and hydrate microstructures. We relate velocity and attenuation increases in hydrate-bearing sediments to their hydrate content, using an effective medium inversion algorithm based on the self-consistent approximation (SCA), differential effective medium (DEM) theory, and Biot and squirt flow mechanisms of fluid flow. The inversion algorithm is able to convert observations in compressional and shear wave velocities and attenuations to hydrate saturation in the sediment pore space. We applied our algorithm to a data set from the Mallik 2L–38 well, Mackenzie delta, Canada, and to data from laboratory measurements on gas-rich and water-saturated sand samples. Predictions using our algorithm match the borehole data and water-saturated laboratory data if the proportion of hydrate contributing to the load-bearing structure increases with hydrate saturation. The predictions match the gas-rich laboratory data if that proportion decreases with hydrate saturation. We attribute this difference to differences in hydrate formation mechanisms between the two environments.

Morphology studies on gas hydrates interacting with silica gel

Energy Technology Data Exchange (ETDEWEB)

Beltran, J.; Servio, P. [McGill Univ., Montreal, PQ (Canada). Dept. of Chemical Engineering

2008-07-01

Clathrate hydrates or gas hydrates are non-stoichiometric, crystalline compounds that form when small molecules come in contact with water at certain temperatures and pressures. Natural gas hydrates are found in the ocean bottom and in permafrost regions. It is thought that the amount of energy stored in natural hydrates is at least twice that of all other fossil fuels combined. In addition, trapping carbon dioxide as a hydrate in the bottom of the ocean has been suggested as an alternative means of reducing atmospheric carbon dioxide levels. Naturally occurring clathrates are found in close interaction with fine grained particles of very small mean pore diameters. Even though an increasing amount of hydrate equilibrium data for small diameter porous media has become available, the morphological behavior of hydrates subject to such conditions is yet to be explored. This paper presented a study that visually examined hydrate formation and decomposition of gas hydrates while interacting with fine grains of silica gel. The study showed still frames from high-resolution video recordings for hydrate formation and decomposition. The paper discussed the experiment including the apparatus as well as the results of hydrate formation and hydrate dissociation. This study enabled for the first time to observe clathrate morphology while hydrates interacted closely with fine grain particles with small mean pore diameters. 9 refs., 8 figs.

Hydrate bearing clayey sediments: Formation and gas production concepts

KAUST Repository

Jang, Jaewon; Santamarina, Carlos

2016-01-01

Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO2single bondCH4 replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.

Hydrate bearing clayey sediments: Formation and gas production concepts

KAUST Repository

Jang, Jaewon

2016-06-20

Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO2single bondCH4 replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.

Silicic magma generation at Askja volcano, Iceland

Science.gov (United States)

Sigmarsson, O.

2009-04-01

Rate of magma differentiation is an important parameter for hazard assessment at active volcanoes. However, estimates of these rates depend on proper understanding of the underlying magmatic processes and magma generation. Differences in isotope ratios of O, Th and B between silicic and in contemporaneous basaltic magmas have been used to emphasize their origin by partial melting of hydrothermally altered metabasaltic crust in the rift-zones favoured by a strong geothermal gradient. An alternative model for the origin of silicic magmas in the Iceland has been proposed based on U-series results. Young mantle-derived mafic protolith is thought to be metasomatized and partially melted to form the silicic end-member. However, this model underestimates the compositional variations of the hydrothermally-altered basaltic crust. New data on U-Th disequilibria and O-isotopes in basalts and dacites from Askja volcano reveal a strong correlation between (230Th/232Th) and delta 18O. The 1875 AD dacite has the lowest Th- and O isotope ratios (0.94 and -0.24 per mille, respectively) whereas tephra of evolved basaltic composition, erupted 2 months earlier, has significantly higher values (1.03 and 2.8 per mille, respectively). Highest values are observed in the most recent basalts (erupted in 1920 and 1961) inside the Askja caldera complex and out on the associated fissure swarm (Sveinagja basalt). This correlation also holds for older magma such as an early Holocene dacites, which eruption may have been provoked by rapid glacier thinning. Silicic magmas at Askja volcano thus bear geochemical signatures that are best explained by partial melting of extensively hydrothermally altered crust and that the silicic magma source has remained constant during the Holocene at least. Once these silicic magmas are formed they appear to erupt rapidly rather than mixing and mingling with the incoming basalt heat-source that explains lack of icelandites and the bi-modal volcanism at Askja

COMPARISON OF SOL-GEL SILICATE COATINGS ON Ti SUBSTRATE

Directory of Open Access Journals (Sweden)

DIANA HORKAVCOVÁ

2012-12-01

Full Text Available The objective of the submitted work was to prepare and to characterize two types of silicate coatings prepared by the sol-gel method using the dip-coating technique on a titanium substrate. Efforts have been made to use mechanical properties of bio-inert titanium and bioactive properties of a silicate layer enriched with an admixture of compounds identified below. The first group consisted of silicate coatings containing silver, brushite and monetite. The other group of silicate coatings contained calcium nitrate and triethyl phosphate. Mechanically and chemically treated titanium substrates were dipped into sols and dried and fired. Silicate coatings from the first group were also chemically treated in 10 mol.l-1 solution of sodium hydroxide. All coatings were measured to determine their adhesive and bioactive properties and furthermore the antibacterial properties were tested in the case of first group. Surfaces of the coated substrates were investigated after the firing and after the individual tests with optical and electron microscopy and X-ray microdiffraction. A tape test demonstrated excellent adhesive property of all coatings to the substrate, classified with degree 5. A static in vitro test demonstrated bioactivity of nearly all the coatings. The basic silicate coating from the first group and one type of coating from the second group were identified as inert. Antibacterial properties of silicate coatings containing silver showed to be different when tested against Escherichia coli bacteria. A complete inhibition of the growth of bacteria under our experimental conditions was observed for the coating containing silver and monetite and a partial inhibition of the growth of bacteria for coatings containing silver and silver in combination with brushite.

Low temperature preparation of α-tricalcium phosphate and its mechanical properties

Directory of Open Access Journals (Sweden)

Song Wang

2017-06-01

Full Text Available In this work, α-tricalcium phosphate (α-TCP was successfully prepared by the thermal transformation of amorphous calcium phosphate (ACP precursor. β-cyclodextrin (β-CD was used for preparation of ACP precursor and played an important role in designing its special structure. The phase composition and microstructures of the obtained α-TCP at different annealing temperature were analysed by X-ray diffraction and scanning electron microscope, and confirmed that α-TCP can be prepared at 650°C for 3 h using ACP as precursor, which is much lower than the phase transition temperature of α-TCP. Mechanical properties were tested 24 h after mixing the obtained α-TCP with 30 wt.% of deionised water. The compressive strength and the flexural strength were 26.4MPa and 12.0MPa, respectively. The flexural strength was higher than that of α-TCP prepared by other methods.

Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

Science.gov (United States)

Braun, Doris E.; Griesser, Ulrich J.

2018-01-01

The observed moisture- and temperature dependent transformations of the dapsone (4,4′-diaminodiphenyl sulfone, DDS) 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis), gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations). Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (de)hydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules) and (form III) differ only by ~1 kJ mol−1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products. PMID:29520359

Methane hydrate stability and anthropogenic climate change

Directory of Open Access Journals (Sweden)

D. Archer

2007-07-01

Full Text Available Methane frozen into hydrate makes up a large reservoir of potentially volatile carbon below the sea floor and associated with permafrost soils. This reservoir intuitively seems precarious, because hydrate ice floats in water, and melts at Earth surface conditions. The hydrate reservoir is so large that if 10% of the methane were released to the atmosphere within a few years, it would have an impact on the Earth's radiation budget equivalent to a factor of 10 increase in atmospheric CO₂.

Hydrates are releasing methane to the atmosphere today in response to anthropogenic warming, for example along the Arctic coastline of Siberia. However most of the hydrates are located at depths in soils and ocean sediments where anthropogenic warming and any possible methane release will take place over time scales of millennia. Individual catastrophic releases like landslides and pockmark explosions are too small to reach a sizable fraction of the hydrates. The carbon isotopic excursion at the end of the Paleocene has been interpreted as the release of thousands of Gton C, possibly from hydrates, but the time scale of the release appears to have been thousands of years, chronic rather than catastrophic.

The potential climate impact in the coming century from hydrate methane release is speculative but could be comparable to climate feedbacks from the terrestrial biosphere and from peat, significant but not catastrophic. On geologic timescales, it is conceivable that hydrates could release as much carbon to the atmosphere/ocean system as we do by fossil fuel combustion.

Elastic wave speeds and moduli in polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate

Science.gov (United States)

Helgerud, M.B.; Waite, W.F.; Kirby, S.H.; Nur, A.

2009-01-01

We used ultrasonic pulse transmission to measure compressional, P, and shear, S, wave speeds in laboratory-formed polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate. From the wave speed's linear dependence on temperature and pressure and from the sample's calculated density, we derived expressions for bulk, shear, and compressional wave moduli and Poisson's ratio from -20 to 15??C and 22.4 to 32.8 MPa for ice Ih, -20 to 15??C and 30.5 to 97.7 MPa for si methane hydrate, and -20 to 10??C and 30.5 to 91.6 MPa for sll methane-ethane hydrate. All three materials had comparable P and S wave speeds and decreasing shear wave speeds with increasing applied pressure. Each material also showed evidence of rapid intergranular bonding, with a corresponding increase in wave speed, in response to pauses in sample deformation. There were also key differences. Resistance to uniaxial compaction, indicated by the pressure required to compact initially porous samples, was significantly lower for ice Ih than for either hydrate. The ice Ih shear modulus decreased with increasing pressure, in contrast to the increase measured in both hydrates ?? 2009.

Fabrication and Properties of Silica Gel/Calcium Sulfate/Strontium-doped β-tricalcium Phosphate Composite Porous Scaffolds for Bone Tissue Engineering

Directory of Open Access Journals (Sweden)

QIN Xiao-su

2018-03-01

Full Text Available The calcium sulfate/strontium-doped β-tricalcium phosphate composite spherical pellets was fabricated, using the calcium sulfate/strontium-doped β-TCP as raw material, and through the stirring spray drying method, and then composite spherical pellets were combined with silica gel, porous silica gel/calcium sulfate/strontium-doped β-tricalcium phosphate scaffold was obtained by stacking aggregation method in the mould. The XRD, SEM and FT-IR, etc are employed to examine the chemical composition, composite morphology and structure characteristics, and the degradability, porosity, mechanical properties and cytotoxicity of the scaffolds materials were studied. The results reveal that the composite porous scaffolds have irregular pore structure with pore size between 0.2-1.0mm, and they have a large number of micropores on each of the composite spherical pellets, with the aperture between 50-200μm. Moreover, the porosity of the composite scaffolds is about 62%, which can meet the requirements of scaffolds for bone tissue engineering in porosity; the cytotoxicity tests show the composite scaffolds have no cytotoxic effect and it has good degradation. Therefore, it has good application prospect in bone tissue engineering of the bone defect repair of non-bearing site.

Gas hydrate exploration activities in Korea

Energy Technology Data Exchange (ETDEWEB)

Keun-Pil Park, K.P. [Korea Inst. of Geoscience and Mineral Resources, Gas Hydrate R and D Organization, Ministry of Knowledge Economy, Yuseong-gu, Daejeon (Korea, Republic of)

2008-07-01

Korea's first gas hydrate research project was launched in 1996 to study the gas hydrate potential in the Ulleung Basin of the East Sea. It involved a series of laboratory experiments followed by a preliminary offshore seismic survey and regional reconnaissance geophysical and marine geological surveys. The bottom simulating reflector (BSR) was interpreted to show wide area distribution in the southern part of the Ulleung Basin, and its average burial depth was 187 m below the sea floor in the East Sea. A three-phase 10-year National Gas Hydrate Development Program was launched in 2004 to estimate the potential reserves in the East Sea. It will involve drilling to identify natural gas hydrates and to determine the most optimized production methods. Drilling sites were proposed based on five indicators that imply gas hydrate occurrence, notably BSR, gas vent, enhanced seismic reflection, acoustic blanking and gas seeping structure. The UBGH-X-01 gas hydrate expedition in the East Sea Ulleung Basin involved 5 logging while drilling (LWD) surveys at three high priority sites. One wire line logging was implemented at the site of the UBGH09. A total 334 m of non-pressurized conventional cores and 16 pressure cores were obtained in late 2007. The UBGH-X-01 was successfully completed, recovering many natural samples of gas hydrate from 3 coring sites in the East Sea. 7 refs., 12 figs.

Seismic-Scale Rock Physics of Methane Hydrate

Energy Technology Data Exchange (ETDEWEB)

Amos Nur

2009-01-08

We quantify natural methane hydrate reservoirs by generating synthetic seismic traces and comparing them to real seismic data: if the synthetic matches the observed data, then the reservoir properties and conditions used in synthetic modeling might be the same as the actual, in-situ reservoir conditions. This approach is model-based: it uses rock physics equations that link the porosity and mineralogy of the host sediment, pressure, and hydrate saturation, and the resulting elastic-wave velocity and density. One result of such seismic forward modeling is a catalogue of seismic reflections of methane hydrate which can serve as a field guide to hydrate identification from real seismic data. We verify this approach using field data from known hydrate deposits.

Methane Hydrate Field Program. Development of a Scientific Plan for a Methane Hydrate-Focused Marine Drilling, Logging and Coring Program

Energy Technology Data Exchange (ETDEWEB)

Collett, Tim [U.S. Geological Survey, Boulder, CO (United States); Bahk, Jang-Jun [Korea Inst. of Geoscience and Mineral Resources, Daejeon (Korea); Frye, Matt [U.S. Bureau of Ocean Energy Management, Sterling, VA (United States); Goldberg, Dave [Lamont-Doherty Earth Observatory, Palisades, NY (United States); Husebo, Jarle [Statoil ASA, Stavenger (Norway); Koh, Carolyn [Colorado School of Mines, Golden, CO (United States); Malone, Mitch [Texas A & M Univ., College Station, TX (United States); Shipp, Craig [Shell International Exploration and Production Inc., Anchorage, AK (United States); Torres, Marta [Oregon State Univ., Corvallis, OR (United States); Myers, Greg [Consortium For Ocean Leadership Inc., Washington, DC (United States); Divins, David [Consortium For Ocean Leadership Inc., Washington, DC (United States); Morell, Margo [Consortium For Ocean Leadership Inc., Washington, DC (United States)

2013-12-31

This topical report represents a pathway toward better understanding of the impact of marine methane hydrates on safety and seafloor stability and future collection of data that can be used by scientists, engineers, managers and planners to study climate change and to assess the feasibility of marine methane hydrate as a potential future energy resource. Our understanding of the occurrence, distribution and characteristics of marine methane hydrates is incomplete; therefore, research must continue to expand if methane hydrates are to be used as a future energy source. Exploring basins with methane hydrates has been occurring for over 30 years, but these efforts have been episodic in nature. To further our understanding, these efforts must be more regular and employ new techniques to capture more data. This plan identifies incomplete areas of methane hydrate research and offers solutions by systematically reviewing known methane hydrate “Science Challenges” and linking them with “Technical Challenges” and potential field program locations.

Conversion of rice hull ash into soluble sodium silicate

Directory of Open Access Journals (Sweden)

Edson Luiz Foletto

2006-09-01

Full Text Available Sodium silicate is used as raw material for several purposes: silica gel production, preparation of catalysts, inks, load for medicines, concrete hardening accelerator, component of detergents and soaps, refractory constituent and deflocculant in clay slurries. In this work sodium silicate was produced by reacting rice hull ash (RHA and aqueous sodium hydroxide, in open and closed reaction systems. The studied process variables were time, temperature of reaction and composition of the reaction mixture (expressed in terms of molar ratios NaOH/SiO2 and H2O/SiO2. About 90% silica conversion contained in the RHA into sodium silicate was achieved in closed system at 200 °C. The results showed that sodium silicate production from RHA can generate aggregate value to this residue.

Energy from gas hydrates - assessing the opportunities and challenges for Canada: report of the expert panel on gas hydrates

International Nuclear Information System (INIS)

2008-09-01

Gas hydrates form when water and natural gas combine at low temperatures and high pressures in regions of permafrost and in marine subseafloor sediments. Estimates suggest that the total amount of natural gas bound in hydrate form may exceed all conventional gas resources, or even the amount of all combined hydrocarbon energy. Gas from gas hydrate could provide a potentially vast new source of energy to offset declining supplies of conventional natural gas in North America and to provide greater energy security for countries such as Japan and India that have limited domestic sources. However, complex issues would need to be addressed if gas hydrate were to become a large part of the energy future of Canada. Natural Resources Canada asked the Council of Canadian Academies to assemble a panel of experts to examine the challenges for an acceptable operational extraction of gas hydrates in Canada. This report presented an overview of relevant contextual background, including some basic science; the medium-term outlook for supply and demand in markets for natural gas; broad environmental issues related to gas hydrate in its natural state and as a fuel; and an overview of Canada's contribution to knowledge about gas hydrate in the context of ongoing international research activity. The report also presented current information on the subject and what would be required to delineate and quantify the resource. Techniques for extracting gas from gas hydrate were also outlined. The report also addressed safety issues related to gas hydrate dissociation during drilling operations or release into the atmosphere; the environmental issues associated with potential leakage of methane into the atmosphere and with the large volumes of water produced during gas hydrate dissociation; and jurisdictional and local community issues that would need to be resolved in order to proceed with the commercial exploitation of gas hydrate. It was concluded that there does not appear to be

Gas Hydrates Research Programs: An International Review

Energy Technology Data Exchange (ETDEWEB)

Jorge Gabitto; Maria Barrufet

2009-12-09

Gas hydrates sediments have the potential of providing a huge amount of natural gas for human use. Hydrate sediments have been found in many different regions where the required temperature and pressure conditions have been satisfied. Resource exploitation is related to the safe dissociation of the gas hydrate sediments. Basic depressurization techniques and thermal stimulation processes have been tried in pilot efforts to exploit the resource. There is a growing interest in gas hydrates all over the world due to the inevitable decline of oil and gas reserves. Many different countries are interested in this valuable resource. Unsurprisingly, developed countries with limited energy resources have taken the lead in worldwide gas hydrates research and exploration. The goal of this research project is to collect information in order to record and evaluate the relative strengths and goals of the different gas hydrates programs throughout the world. A thorough literature search about gas hydrates research activities has been conducted. The main participants in the research effort have been identified and summaries of their past and present activities reported. An evaluation section discussing present and future research activities has also been included.

Obsidian hydration dates glacial loading?

Science.gov (United States)

Friedman, I; Pierce, K L; Obradovich, J D; Long, W D

1973-05-18

Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming. The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow.

Effects of Nanosilica on Early Age Stages of Cement Hydration

Directory of Open Access Journals (Sweden)

Forood Torabian Isfahani

2017-01-01

Full Text Available Effects of nanosilica on cement hydration have been broadly investigated in the literature and early age cement hydration, as a whole, has been mainly considered, disregarding the substages of the hydration. The hydration of cement is characterized by different substages and nanosilica effect on the hydration could be a result of diverse, even contradictory, behavior of nanosilica in individual stages of the hydration. In this study, effects of nanosilica on different substages of cement hydration are investigated. Isothermal calorimetry results show that at early ages (initial 72 hours the effects of nanosilica depend on the phenomenon by which the hydration is governed: when the hydration is chemically controlled, that is, during initial reaction, dormant period, and acceleratory period, the hydration rate is accelerated by adding nanosilica; when the hydration is governed by diffusion process, that is, during postacceleratory period, the hydration rate is decelerated by adding nanosilica. The Thermal Gravimetric Analysis on the samples at the hardened state (after 28 days of curing reveals that, after adding nanosilica, the hydration degree slightly increased compared to the plain paste.

A unified approach for description of gas hydrate formation kinetics in the presence of kinetic promoters in gas hydrate converters

International Nuclear Information System (INIS)

ZareNezhad, Bahman; Varaminian, Farshad

2013-01-01

Highlights: • A unified kinetic model for description of promoted and non-promoted gas hydrate formation processes is presented. • Effects of impeller speed, promoter concentration and different kinetic promoters are investigated. • A unique region of gas hydrate formation is identified regarding gas hydrate formation processes. • The proposed model is useful for understanding the behavior of gas hydrate formation processes and design of GTH converters. - Abstract: The kinetic promoters have found wide applications in enhancing the rate of energy conversion and storage via gas hydrate formation processes. Effects of different kinetic promoters such as anionic surfactants sodium dodecyl sulfate (SDS), dodecylbenzene sulfonic acid (DBSA), and sodium dodecyl benzene sulfonate (SDBS); cationic surfactants, Cetyl trimethyl ammonium bromide (CTAB), dodecyl trimethyl ammonium bromide (DTAB) and non-ionic surfactants, alkylpolyglucoside (APG), dodecyl polysaccharide glycoside (DPG), TritonX-100 (TX100) on methane (CH 4 ), ethane (C 2 H 6 ) and propane (C 3 H 8 ) gas hydrate formation processes are investigated in this work. A macroscopic kinetic model based on the time variations of reaction chemical potential is also presented for global description of gas hydrate formation processes. Experimental gas hydrate formation data are employed to validate the proposed kinetic model. Effects of promoter’s concentrations and agitation intensities on the gas consumption profiles are also investigated. A universal correlation and a unified kinetic map have been proposed for macroscopic description of gas hydrate formation kinetics in the presence or absence of kinetic promoters. According to the presented unified kinetic map, a unique region of gas hydrate formation is identified for the first time. For negligible amounts of kinetic promoters, the presented region disappears and approaches to a unique path at high agitation intensities. The presented unified approach is

Protein Hydration Thermodynamics: The Influence of Flexibility and Salt on Hydrophobin II Hydration.

Science.gov (United States)

Remsing, Richard C; Xi, Erte; Patel, Amish J

2018-04-05

The solubility of proteins and other macromolecular solutes plays an important role in numerous biological, chemical, and medicinal processes. An important determinant of protein solubility is the solvation free energy of the protein, which quantifies the overall strength of the interactions between the protein and the aqueous solution that surrounds it. Here we present an all-atom explicit-solvent computational framework for the rapid estimation of protein solvation free energies. Using this framework, we estimate the hydration free energy of hydrophobin II, an amphiphilic fungal protein, in a computationally efficient manner. We further explore how the protein hydration free energy is influenced by enhancing flexibility and by the addition of sodium chloride, and find that it increases in both cases, making protein hydration less favorable.

Methane hydrate synthesis from ice: Influence of pressurization and ethanol on optimizing formation rates and hydrate yield

Science.gov (United States)

Chen, Po-Chun.; Huang, Wuu-Liang; Stern, Laura A.

2010-01-01

Polycrystalline methane gas hydrate (MGH) was synthesized using an ice-seeding method to investigate the influence of pressurization and ethanol on the hydrate formation rate and gas yield of the resulting samples. When the reactor is pressurized with CH4 gas without external heating, methane hydrate can be formed from ice grains with yields up to 25% under otherwise static conditions. The rapid temperature rise caused by pressurization partially melts the granular ice, which reacts with methane to form hydrate rinds around the ice grains. The heat generated by the exothermic reaction of methane hydrate formation buffers the sample temperature near the melting point of ice for enough time to allow for continuous hydrate growth at high rates. Surprisingly, faster rates and higher yields of methane hydrate were found in runs with lower initial temperatures, slower rates of pressurization, higher porosity of the granular ice samples, or mixtures with sediments. The addition of ethanol also dramatically enhanced the formation of polycrystalline MGH. This study demonstrates that polycrystalline MGH with varied physical properties suitable for different laboratory tests can be manufactured by controlling synthesis procedures or parameters. Subsequent dissociation experiments using a gas collection apparatus and flowmeter confirmed high methane saturation (CH 4·2O, with n = 5.82 ± 0.03) in the MGH. Dissociation rates of the various samples synthesized at diverse conditions may be fitted to different rate laws, including zero and first order.

Standardization and software infrastructure for gas hydrate data communications

Energy Technology Data Exchange (ETDEWEB)

Kroenlein, K.; Chirico, R.D.; Kazakov, A.; Frenkel, M. [National Inst. of Standards and Technology, Boulder, CO (United States). Physical and Chemical Properties Div.; Lowner, R. [GeoForschungsZentrum Potsdam (Germany); Wang, W. [Chinese Academy of Science, Beijing (China). Computer Network Information Center; Smith, T. [MIT Systems, Flushing, NY (United States); Sloan, E.D. [Colorado School of Mines, Golden, CO (United States). Centre for Hydrate Research

2008-07-01

The perceived value of gas hydrates as an energy resource for the future has led to extensive hydrate research studies and experiments. The hydrate deposits are widely dispersed throughout the world, and many countries are now investigating methods of extracting gas hydrate resources. This paper described a gas hydrates markup language (GHML) developed as an international standard for data transfer and storage within the gas hydrates community. The language is related to a hydrates database developed to facilitate a greater understanding of naturally occurring hydrate interactions with geophysical processes, and aid in the development of hydrate technologies for resource recovery and storage. Recent updates to the GHML included the addition of ThermoML, a communication standard for thermodynamic data into the GHML schema. The standard will be used to represent all gas hydrates thermodynamic data. A new element for the description of crystal structures has also been developed, as well as a guided data capture tool. The tool is available free of charge and is publicly licensed for use by gas hydrate data producers. A web service has also been provided to ensure that access to GHML files for gas hydrates and data files are available for users. It was concluded that the tool will help to ensure data quality assurance for the conversion of data and meta-data within the database. 28 refs., 9 figs.

Towards CO2 sequestration and applications of CO2 hydrates: the effects of tetrahydrofuran on the phase equilibria of CO2 hydrates

International Nuclear Information System (INIS)

Khalik, M.S.; Peters, C.J.

2006-01-01

The increasing quantity of carbon dioxide (CO 2 ) in the atmosphere has caused widespread global concerns. Capturing CO 2 from its sources and stored it in the form of gas hydrates and application of CO 2 hydrates are among the proposed methods to overcome this problem. In order to make hydrate-based process more attractive, the use of cyclic ethers as promoters is suggested to reduce the required hydrate formation pressure and enhancing the corresponding kinetic rate. In the present work, tetrahydrofuran (THF) is chosen as a hydrate promoter, participating in forming hydrates and produces mixed hydrate together with CO 2 . The pressure and temperature ranges of hydrate stability region are carefully determined through phase equilibrium measurement of the ternary CO 2 , tetrahydrofuran (THF) and water systems. From the experimental results, it is confirmed that the presence of THF in CO 2 + water systems will extend the hydrate formation region to higher temperature at a constant pressure. The extension of the hydrate stability region is depended on the overall concentration of the ternary system. Moreover, four-phase equilibrium of H-Lw-Lv-V is observed in the system, which may be due to a liquid phase split. In the region where the four-phase equilibrium exists, the ternary system loses its concentration dependency of the hydrate equilibrium conditions. (Author)

LABORATORY STRATEGIES FOR HYDRATE FORMATION IN FINE-GRAINED SEDIMENTS

KAUST Repository

Lei, L.; Santamarina, Carlos

2018-01-01

Fine‐grained sediments limit hydrate nucleation, shift the phase boundary and hinder gas supply. Laboratory experiments in this study explore different strategies to overcome these challenges, including the use of a more soluble guest molecule rather than methane, grain‐scale gas‐storage within porous diatoms, ice‐to‐hydrate transformation to grow lenses at predefined locations, forced gas injection into water saturated sediments, and long‐term guest molecule transport. Tomographic images, thermal and pressure data provide rich information on hydrate formation and morphology. Results show that hydrate formation is inherently displacive in fine‐grained sediments; lenses are thicker and closer to each other in compressible, high specific surface area sediments subjected to low effective stress. Temperature and pressure trajectories follow a shifted phase boundary that is consistent with capillary effects. Exo‐pore growth results in freshly formed hydrate with a striped and porous structure; this open structure becomes an effective pathway for gas transport to the growing hydrate front. Ice‐to‐hydrate transformation goes through a liquid stage at pre‐melt temperatures; then, capillarity and cryogenic suction compete, and some water becomes imbibed into the sediment faster than hydrate reformation. The geometry of hydrate lenses and the internal hydrate structure continue evolving long after the exothermal response to hydrate formation has completely decayed. Multiple time‐dependent processes occur during hydrate formation, including gas, water and heat transport, sediment compressibility, reaction rate and the stochastic nucleation process. Hydrate formation strategies conceived for this study highlight the inherent difficulties in emulating hydrate formation in fine‐grained sediments within the relatively short time‐scale available for laboratory experiments.

LABORATORY STRATEGIES FOR HYDRATE FORMATION IN FINE-GRAINED SEDIMENTS

KAUST Repository

Lei, L.

2018-04-02

Fine‐grained sediments limit hydrate nucleation, shift the phase boundary and hinder gas supply. Laboratory experiments in this study explore different strategies to overcome these challenges, including the use of a more soluble guest molecule rather than methane, grain‐scale gas‐storage within porous diatoms, ice‐to‐hydrate transformation to grow lenses at predefined locations, forced gas injection into water saturated sediments, and long‐term guest molecule transport. Tomographic images, thermal and pressure data provide rich information on hydrate formation and morphology. Results show that hydrate formation is inherently displacive in fine‐grained sediments; lenses are thicker and closer to each other in compressible, high specific surface area sediments subjected to low effective stress. Temperature and pressure trajectories follow a shifted phase boundary that is consistent with capillary effects. Exo‐pore growth results in freshly formed hydrate with a striped and porous structure; this open structure becomes an effective pathway for gas transport to the growing hydrate front. Ice‐to‐hydrate transformation goes through a liquid stage at pre‐melt temperatures; then, capillarity and cryogenic suction compete, and some water becomes imbibed into the sediment faster than hydrate reformation. The geometry of hydrate lenses and the internal hydrate structure continue evolving long after the exothermal response to hydrate formation has completely decayed. Multiple time‐dependent processes occur during hydrate formation, including gas, water and heat transport, sediment compressibility, reaction rate and the stochastic nucleation process. Hydrate formation strategies conceived for this study highlight the inherent difficulties in emulating hydrate formation in fine‐grained sediments within the relatively short time‐scale available for laboratory experiments.

Extraction and characterisation of apatite- and tricalcium phosphate-based materials from cod fish bones

Energy Technology Data Exchange (ETDEWEB)

Piccirillo, C.; Silva, M.F. [CBQF/Escola Superior de Biotecnologia, Universidade Catolica Portuguesa, Porto (Portugal); Pullar, R.C. [Dept. Engenharia de Materiais e Ceramica/CICECO, Universidade de Aveiro, Aveiro (Portugal); Braga da Cruz, I. [CBQF/Escola Superior de Biotecnologia, Universidade Catolica Portuguesa, Porto (Portugal); WeDoTech, CiDEB/Escola Superior de Biotecnologia, Universidade Catolica Portuguesa, Porto (Portugal); Jorge, R. [WeDoTech, CiDEB/Escola Superior de Biotecnologia, Universidade Catolica Portuguesa, Porto (Portugal); Pintado, M.M.E. [CBQF/Escola Superior de Biotecnologia, Universidade Catolica Portuguesa, Porto (Portugal); Castro, P.M.L., E-mail: plcastro@porto.ucp.pt [CBQF/Escola Superior de Biotecnologia, Universidade Catolica Portuguesa, Porto (Portugal)

2013-01-01

Apatite- and tricalcium phosphate-based materials were produced from codfish bones, thus converting a waste by-product from the food industry into high added-valued compounds. The bones were annealed at temperatures between 900 and 1200 Degree-Sign C, giving a biphasic material of hydroxyapatite and tricalcium phosphate (Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2} and {beta}-Ca(PO{sub 4}){sub 3}) with a molar proportion of 75:25, a material widely used in biomedical implants. The treatment of the bones in solution prior to their annealing changed the composition of the material. Single phase hydroxyapatite, chlorapatite (Ca{sub 10}(PO{sub 4}){sub 6}Cl{sub 2}) and fluorapatite (Ca{sub 10}(PO{sub 4}){sub 6}F{sub 2}) were obtained using CaCl{sub 2} and NaF solutions, respectively. The samples were analysed by several techniques (X-ray diffraction, infrared spectroscopy, scanning electron microscopy and differential thermal/thermogravimetric analysis) and by elemental analyses, to have a more complete understanding of the conversion process. Such compositional modifications have never been performed before for these materials of natural origin to tailor the relative concentrations of elements. This paper shows the great potential for the conversion of this by-product into highly valuable compounds for biomedical applications, using a simple and effective valorisation process. - Highlights: Black-Right-Pointing-Pointer Apatite and calcium phosphate compounds extraction from cod fish bones Black-Right-Pointing-Pointer Bone calcination: biphasic material hydroxyapatite-calcium phosphate production Black-Right-Pointing-Pointer Bone pre-treatments in solution change the material composition. Black-Right-Pointing-Pointer Single phase materials (hydroxy-, chloro- or fluoroapatite) are obtained. Black-Right-Pointing-Pointer Concentration of other elements (Na, F, Cl) suitable for biomedical applications.

Structural transformations of sVI tert-butylamine hydrates to sII binary hydrates with methane.

Science.gov (United States)

Prasad, Pinnelli S R; Sugahara, Takeshi; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2009-10-22

Binary clathrate hydrates with methane (CH(4), 4.36 A) and tert-butylamine (t-BuNH(2), 6.72 A) as guest molecules were synthesized at different molar concentrations of t-BuNH(2) (1.00-9.31 mol %) with methane at 7.0 MPa and 250 K, and were characterized by powder X-ray diffraction (PXRD) and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed on pressurizing with methane. The PXRD showed sII signatures and the remnant sVI signatures were insignificant, implying the metastable nature of sVI binary hydrates. Raman spectroscopic data on these binary hydrates suggest that the methane molecules occupy the small cages and vacant large cages. The methane storage capacity in this system was nearly doubled to approximately 6.86 wt % for 5.56 mol % > t-BuNH(2) > 1.0 mol %.

The U.S. Geological Survey’s Gas Hydrates Project

Science.gov (United States)

Ruppel, Carolyn D.

2018-01-17

The Gas Hydrates Project at the U.S. Geological Survey (USGS) focuses on the study of methane hydrates in natural environments. The project is a collaboration between the USGS Energy Resources and the USGS Coastal and Marine Geology Programs and works closely with other U.S. Federal agencies, some State governments, outside research organizations, and international partners. The USGS studies the formation and distribution of gas hydrates in nature, the potential of hydrates as an energy resource, and the interaction between methane hydrates and the environment. The USGS Gas Hydrates Project carries out field programs and participates in drilling expeditions to study marine and terrestrial gas hydrates. USGS scientists also acquire new geophysical data and sample sediments, the water column, and the atmosphere in areas where gas hydrates occur. In addition, project personnel analyze datasets provided by partners and manage unique laboratories that supply state-of-the-art analytical capabilities to advance national and international priorities related to gas hydrates.

Cryogenic-SEM investigation of CO{sub 2} hydrate morphologies

Energy Technology Data Exchange (ETDEWEB)

Camps, A.P.; Milodowski, A.; Rochelle, C.; Williams, J.F.; Jackson, P. D. [British Geological Survey, Keyworth, Nottinghamshire (United Kingdom); Camps, A.P; Lovell, M.; Williams, J.F. [Leicester Univ., Leicester (United Kingdom). Dept. of Geology

2008-07-01

Gas hydrates occur naturally around the world in the shallow-marine geosphere, and are seen as a drilling hazard in the petroleum industry due to their role in the carbon cycle, and their possible contribution in past and present climate change. Hydrates are ice-like structures composed of cages of water molecules containing one or more guest molecules, such as methane and carbon dioxide (CO{sub 2}). CO{sub 2} hydrates also occur naturally on earth and are being investigated for their potential to store large volumes of CO{sub 2} to reduce atmospheric emissions of greenhouse gases as a climate change mitigation strategy. However, the mineralogy and formation processes of hydrates are relatively poorly understood. Different imaging techniques have been utilized to study gas hydrates, such as nuclear magnetic resonance, magnetic resonance imaging, and x-ray computed tomography. Scanning Electron Microscopy (SEM) at cryogenic temperatures is another technique to study hydrates, and has been used successfully for investigation of methane and CO{sub 2} hydrates. This paper presented a study that investigated CO{sub 2} hydrates formed in laboratories, using a cryogenic-SEM. The paper presented the study methods and observations, including euhedral crystalline carbon dioxide hydrate; acicular carbon dioxide hydrate; granoblastic carbon dioxide hydrate; and gas rich carbon dioxide hydrate. It was concluded that the investigation produced various different hydrate morphologies resulting from different formation conditions. Morphologies ranged from well-defined euhedral crystals to acicular needles, and more complex, intricate forms. 22 refs., 6 figs., 1 appendix.

Gas Hydrates | Alaska Division of Geological & Geophysical Surveys

Science.gov (United States)

Preliminary Report - Cascadia Margin Gas Hydrates, Volume 204 Initial Report Mallik 2002 GSC Bulletin 585 : Scientific results from the Mallik 2002 gas hydrate production well program Offshore gas hydrate sample

Structure and properties of polymer-silicate nanocomposites based on polytetrafluoroethylene

Energy Technology Data Exchange (ETDEWEB)

Sleptsova, Sardana A.; Okhlopkova, Aitalina A. [North-Eastern Federal University, Yakutsk (Russian Federation)

2011-07-01

The results of physicomechanical, tribological , and structural investigation of polytetrafluoroethylene based polymers and natural layered silicates are reported. It is shown that the tribological behaviour of the composites can be significantly improved by introducing a small amount of activated silicates. The results of structural examination of the composite friction surfaces by scanning-probe microscopy and IR spectroscopy are discussed. Key words: polytetrafluoroethylene, layered silicates, wear resistance, friction coefficient, structure, IR-spectrum.

Hydration of tricalcium aluminate in the presence of gypsum

Directory of Open Access Journals (Sweden)

Triviño Vázquez, F.

1974-06-01

Full Text Available Not availabePara el estudio del comportamiento del cemento Portland tiene una importancia fundamental el conocimiento de la hidratación del aluminato tricálcico, por ser uno de sus componentes que primero se hidrata y porque se le achacan la mayoría de los defectos que sufre la pasta de cemento; tales son: retracciones, contracciones, fenómenos exotérmicos y sensibilidad a agentes exteriores de tipo químico. En lo que sigue se estudia por métodos fisicoquímicos la hidratación del aluminato tricálcico junto con el yeso, ya que éste se emplea como regulador del fraguado en los cementos Portland.

Effect of the crystal chemistry on the hydration mechanism of swelling micas

Science.gov (United States)

Pavón, Esperanza; Alba, María D.; Castro, Miguel A.; Cota, A.; Osuna, Francisco J.; Pazos, M. Carolina

2017-11-01

Swelling and dehydration under minor changes in temperature and water vapor pressure is an important property that clays and clay minerals exhibit. In particular, their interlayer space, the solid-water interface and the layers' collapse and re-expansion have received much attention because it affects to the dynamical properties of interlayer cations and thus the transfer and fate of water and pollutants. In this contribution, the dehydration and rehydration mechanism of a swelling high-charge mica family is examined by in situ X-ray Diffraction. The effect of the aluminosilicate layer charge and the physicochemical properties of the interlayer cations on these processes are analyzed. The results showed that the dehydration temperature and the number of steps involved in this process are related to the layer charge of the silicate and the physicochemical properties of the interlayer cations. Moreover, the ability to adsorb water molecules in a confined space with high electric field by the interlayer cations does not only depend on their hydration enthalpy but also on the electrostatic parameters of these cations.

Silicon K-edge XANES spectra of silicate minerals

Science.gov (United States)

Li, Dien; Bancroft, G. M.; Fleet, M. E.; Feng, X. H.

1995-03-01

Silicon K-edge x-ray absorption near-edge structure (XANES) spectra of a selection of silicate and aluminosilicate minerals have been measured using synchrotron radiation (SR). The spectra are qualitatively interpreted based on MO calculation of the tetrahedral SiO{4/4-}cluster. The Si K-edge generally shifts to higher energy with increased polymerization of silicates by about 1.3 eV, but with considerable overlap for silicates of different polymerization types. The substitution of Al for Si shifts the Si K-edge to lower energy. The chemical shift of Si K-edge is also sensitive to cations in more distant atom shells; for example, the Si K-edge shifts to lower energy with the substitution of Al for Mg in octahedral sites. The shifts of the Si K-edge show weak correlation with average Si-O bond distance (dSi-O), Si-O bond valence (sSi-O) and distortion of SiO4 tetrahedra, due to the crystal structure complexity of silicate minerals and multiple factors effecting the x-ray absorption processes.

Preparation of β-belite using liquid alkali silicates

International Nuclear Information System (INIS)

Koutník, P.

2017-01-01

The aim of this study is the preparation of β-belite by a solid-state reaction using powdered limestone, amorphous silica and liquid alkali silicates. The raw materials were blended, the mixtures were agglomerated and then burnt. The resulting samples were characterized by X-ray diffraction analysis and scanning electron microscopy. Free lime content in the β-belite samples was also determined. The effects of CaO/SiO2 ratio (1.6–2.1), burning temperature (800–1400 °C), utilization of different raw materials (silica fume, synthetic silica, potassium silicate, sodium silicate, potassium hydroxide) and burning time (0.5–16 h) on free lime content and mineralogical composition were investigated. The purest ?-belite samples were prepared from a mixture of powdered limestone, silica fume and liquid potassium silicate with a ratio CaO/SiO2 = 2 by burning at temperatures between 1100 and 1300 °C for more than 2 h. Decreasing of the CaO/SiO2 ratio led to rankinite formation and lower a burning temperature led to the formation of wollastonite. [es

Comparative Assessment of Advanced Gay Hydrate Production Methods

Energy Technology Data Exchange (ETDEWEB)

M. D. White; B. P. McGrail; S. K. Wurstner

2009-06-30

Displacing natural gas and petroleum with carbon dioxide is a proven technology for producing conventional geologic hydrocarbon reservoirs, and producing additional yields from abandoned or partially produced petroleum reservoirs. Extending this concept to natural gas hydrate production offers the potential to enhance gas hydrate recovery with concomitant permanent geologic sequestration. Numerical simulation was used to assess a suite of carbon dioxide injection techniques for producing gas hydrates from a variety of geologic deposit types. Secondary hydrate formation was found to inhibit contact of the injected CO{sub 2} regardless of injectate phase state, thus diminishing the exchange rate due to pore clogging and hydrate zone bypass of the injected fluids. Additional work is needed to develop methods of artificially introducing high-permeability pathways in gas hydrate zones if injection of CO{sub 2} in either gas, liquid, or micro-emulsion form is to be more effective in enhancing gas hydrate production rates.

Terahertz Time Domain Spectroscopy for Structure-II Gas Hydrates

DEFF Research Database (Denmark)

Takeya, Kei; Zhang, Caihong; Kawayama, Iwao

2009-01-01

For the nondestructive inspection of gas hydrates, terahertz (THz) time-domain spectroscopy (TDS) was applied to tetrahydrofuran (THF) hydrate and propane hydrate. The absorption of propane hydrate monotonically increases with frequency, similar to the case of ice, while THF hydrate has...... a characteristic broad absorption peak at 0.5 THz corresponding to the dipole moment of THF molecules. The refractive indices of THF and propane hydrates are 1.725 and 1.775 at 1 THz, respectively, and show a slight but clear difference from the refractive index of ice (1.79). THz-TDS is a potentially useful...... technique for the ondestructive inspection of gas hydrates. # 2009 The Japan Society of Applied Physics...

Lead-silicate glass optical microbubble resonator

Energy Technology Data Exchange (ETDEWEB)

Wang, Pengfei, E-mail: pengfei.wang@dit.ie [Photonics Research Centre, Dublin Institute of Technology, Kevin Street, Dublin 8 (Ireland); Optoelectronics Research Centre, University of Southampton, Southampton SO17 1BJ (United Kingdom); Ward, Jonathan; Yang, Yong; Chormaic, Síle Nic [Light-Matter Interactions Unit, OIST Graduate University, 1919-1 Tancha, Onna-son, Okinawa 904-0495 (Japan); Feng, Xian; Brambilla, Gilberto [Optoelectronics Research Centre, University of Southampton, Southampton SO17 1BJ (United Kingdom); Farrell, Gerald [Photonics Research Centre, Dublin Institute of Technology, Kevin Street, Dublin 8 (Ireland)

2015-02-09

Microbubble whispering gallery resonators have the potential to become key components in a variety of active and passive photonic circuit devices by offering a range of significant functionalities. Here, we report on the fabrication, optical characterization, and theoretical analysis of lead-silicate glass and optical microbubble resonators. Evanescent field coupling to the microbubbles was achieved using a 1 μm diameter, silica microfiber at a wavelength of circa 775 nm. High Q-factor modes were efficiently excited in both single-stem and two-stem, lead-silicate glass, and microbubble resonators, with bubble diameters of 38 μm (single-stem) and 48 μm (two-stem). Whispering gallery mode resonances with Q-factors as high as 2.3 × 10{sup 5} (single-stem) and 7 × 10{sup 6} (two-stem) were observed. By exploiting the high-nonlinearity of the lead-silicate glass, this work will act as a catalyst for studying a range of nonlinear optical effects in microbubbles, such as Raman scattering and four-wave mixing, at low optical powers.

Hydrate Control for Gas Storage Operations

Energy Technology Data Exchange (ETDEWEB)

Jeffrey Savidge

2008-10-31

The overall objective of this project was to identify low cost hydrate control options to help mitigate and solve hydrate problems that occur in moderate and high pressure natural gas storage field operations. The study includes data on a number of flow configurations, fluids and control options that are common in natural gas storage field flow lines. The final phase of this work brings together data and experience from the hydrate flow test facility and multiple field and operator sources. It includes a compilation of basic information on operating conditions as well as candidate field separation options. Lastly the work is integrated with the work with the initial work to provide a comprehensive view of gas storage field hydrate control for field operations and storage field personnel.

Development of hydrate risk quantification in oil and gas production

Science.gov (United States)

Chaudhari, Piyush N.

Subsea flowlines that transport hydrocarbons from wellhead to the processing facility face issues from solid deposits such as hydrates, waxes, asphaltenes, etc. The solid deposits not only affect the production but also pose a safety concern; thus, flow assurance is significantly important in designing and operating subsea oil and gas production. In most subsea oil and gas operations, gas hydrates form at high pressure and low temperature conditions, causing the risk of plugging flowlines, with a undesirable impact on production. Over the years, the oil and gas industry has shifted their perspective from hydrate avoidance to hydrate management given several parameters such as production facility, production chemistry, economic and environmental concerns. Thus, understanding the level of hydrate risk associated with subsea flowlines is an important in developing efficient hydrate management techniques. In the past, hydrate formation models were developed for various flow-systems (e.g., oil dominated, water dominated, and gas dominated) present in the oil and gas production. The objective of this research is to extend the application of the present hydrate prediction models for assessing the hydrate risk associated with subsea flowlines that are prone to hydrate formation. It involves a novel approach for developing quantitative hydrate risk models based on the conceptual models built from the qualitative knowledge obtained from experimental studies. A comprehensive hydrate risk model, that ranks the hydrate risk associated with the subsea production system as a function of time, hydrates, and several other parameters, which account for inertial, viscous, interfacial forces acting on the flow-system, is developed for oil dominated and condensate systems. The hydrate plugging risk for water dominated systems is successfully modeled using The Colorado School of Mines Hydrate Flow Assurance Tool (CSMHyFAST). It is found that CSMHyFAST can be used as a screening tool in

Advanced Gas Hydrate Reservoir Modeling Using Rock Physics

Energy Technology Data Exchange (ETDEWEB)

McConnell, Daniel

2017-12-30

Prospecting for high saturation gas hydrate deposits can be greatly aided with improved approaches to seismic interpretation and especially if sets of seismic attributes can be shown as diagnostic or direct hydrocarbon indicators for high saturation gas hydrates in sands that would be of most interest for gas hydrate production.

A large 3D seismic data set in the deep water Eastern Gulf of Mexico was screened for gas hydrates using a set of techniques and seismic signatures that were developed and proven in the Central deepwater Gulf of Mexico in the DOE Gulf of Mexico Joint Industry Project JIP Leg II in 2009 and recently confirmed with coring in 2017.

A large gas hydrate deposit is interpreted in the data where gas has migrated from one of the few deep seated faults plumbing the Jurassic hydrocarbon source into the gas hydrate stability zone. The gas hydrate deposit lies within a flat-lying within Pliocene Mississippi Fan channel that was deposited outboard in a deep abyssal environment. The uniform architecture of the channel aided the evaluation of a set of seismic attributes that relate to attenuation and thin-bed energy that could be diagnostic of gas hydrates. Frequency attributes derived from spectral decomposition also proved to be direct hydrocarbon indicators by pseudo-thickness that could be only be reconciled by substituting gas hydrate in the pore space. The study emphasizes that gas hydrate exploration and reservoir characterization benefits from a seismic thin bed approach.

Experimental Setup to Characterize Bentonite Hydration Processes

International Nuclear Information System (INIS)

Bru, A.; Casero, D.; Pastor, J. M.

2001-01-01

We present an experimental setup to follow-up the hydration process of a bentonite. Clay samples, of 2 cm x 12 cm x 12 cm, were made and introduced in a Hele-Shaw cell with two PMM windows and two steel frames. In hydration experiments, a fluid enters by an orifice in the frame, located both at the top and the bottom of the cell, to perform hydration in both senses. To get a uniform hydration we place a diffuser near the orifice. Volume influxes in hydration cells are registered in time. The evolution of the developed interface was recorded on a videotape. The video cameras was fixed to a holder so that the vertical direction in the monitor was the same as the direction of the larger extension of the cell. (Author) 6 refs

Marine Gas Hydrates - An Untapped Non-conventional Energy ...

Indian Academy of Sciences (India)

Table of contents. Marine Gas Hydrates - An Untapped Non-conventional Energy Resource · Slide 2 · Slide 3 · Slide 4 · Gas Hydrate Stability Zone · Slide 6 · Slide 7 · Exploration of gas hydrates (seismic) · Characteristics of BSR · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Distribution of Gas Hydrates in KG ...

The structure of hydrate bearing fine grained marine sediments

Energy Technology Data Exchange (ETDEWEB)

Priest, J.; Kingston, E.; Clayton, C. [Southampton Univ., Highfield (United Kingdom). School of Civil Engineering and the Environment; Schultheiss, P.; Druce, M. [Geotek Ltd., Daventry (United Kingdom)

2008-07-01

This paper discussed the structure of naturally occurring methane gas hydrates in fine-grained sediments from core samples recovered using in situ pressures from the eastern margin of the Indian Ocean. High resolution X-ray computed tomography (CT) images were taken of gas hydrate cores. The hydrate structure was examined and comparisons were made between low resolution X-ray images obtained on the cores prior to sub-sectioning and depressurization procedures. The X-ray images showed the presence of high-angle, sub-parallel veins within the recovered sediments. The scans indicated that the hydrates occurred as fracture filing veins throughout the core. Fracture orientation was predominantly sub-vertical. Thick millimetric hydrate veins were composed of sub-millimetric veins with variations in fracture angle. The analysis indicated that hydrate formation was episodic in nature and subject to changes in the stress regime. Results of the study showed that depressurization and subsequent freezing alter the structure of the sediment even when the gas hydrate has not been altered. A large proportion of the hydrate survived when outside of its stability region. The self-preserving behaviour of the hydrate was attributed to the endothermic nature of gas hydrate dissociation. It was concluded that the accurate physical characterization of gas hydrates can only be conducted when the core section remains under in situ stress conditions. 13 refs., 9 figs.

I-Xe dating of silicate and troilite from IAB iron meteorites

International Nuclear Information System (INIS)

Niemeyer, S.

1979-01-01

Silicate and troilite (FeS) from IAB irons were analyzed by the I-Xe technique. Four IAB silicate samples gave well-defined I-Xe ages [in millions of years relative to Bjurbole: - 3.7 +- 0.3 for Woodbine, -0.7 +- 0.6 for Mundrabilla, + 1.4 +- 0.7 for Copiapo, and +2.6 +- 0.6 for Landes. The ( 129 Xe/ 132 Xe)sub(trapped) ratios are consistent with previous values for chondrites, with the exception of Landes which has an extraordinary trapped ratio of 3.5 +- 0.2. Both analyses of silicate from Pitts gave anomalous I-Xe patterns. Troilite samples were also analyzed: Pitts troilite gave a complex I-Xe pattern, which suggests an age of +17 Myr; Mundrabilla troilite defined a good I-Xe correlation, which after correction for neutron capture on 128 Te gave an age of -10.8 +- 0.7 Myr. Thus, low-melting troilite predates high-melting silicate in Mundrabilla. Abundances of Ga, Ge, and Ni in metal from these meteorites are correlated with I-Xe ages of the silicate; meteorites with older silicates have greater Ni contents. No model easily accounts for this result as well as other properties of IAB irons; nevertheless, these results, taken at face value, favour a nebular formation model. The great age of troilite from Mundrabilla suggests that this troilite formed in a different nebular region from the silicate and metal, and was later mechanically mixed with these other phases. The correlation between the trace elements in the metal and the I-Xe ages of the silicate provides one of the first known instances in which another well-defined meteoritic property correlates with I-Xe ages. In addition, almost all the 129 Xe in Mundrabilla silicate (etched in acid) was correlated with 128 Xe. These two results further support the validity of the I-Xe dating method. (author)

Design and Fabrication of Biodegradable Porous Chitosan/Gelatin/Tricalcium Phosphate Hybrid Scaffolds for Tissue Engineering

Directory of Open Access Journals (Sweden)

Y. Mohammadi

2007-08-01

Full Text Available In this study, based on a biomimetic approach, novel 3D biodegradable porous hybrid scaffolds consisting of chitosan, gelatin, and tricalcium phosphate were developed for bone and cartilage tissue engineering. Macroporous chitosan/ gelatin/β-TCP scaffolds were prepared through the process of freeze-gelation/solid-liquid phase separation. The results showed that the prepared scaffolds are highly porous, with porosities larger than 80%, and have interconnected pores. Biocompatibility studies were successfully performed by in vitro and in vivo assays. Moreover, the attachment, migration, and proliferation of chondrocytes on these unique temporary scaffolds were examined to determine their potentials in tissue engineering applications.

On the Relation of Silicates and SiO Maser in Evolved Stars

Energy Technology Data Exchange (ETDEWEB)

Liu, Jiaming; Jiang, Biwei, E-mail: bjiang@bnu.edu.cn [Department of Astronomy, Beijing Normal University, Beijing 100875 (China)

2017-04-01

The SiO molecule is one of the candidates for the seed of silicate dust in the circumstellar envelope of evolved stars, but this opinion is challenged. In this work we investigate the relation of the SiO maser emission power and the silicate dust emission power. With both our own observation by using the PMO/Delingha 13.7 m telescope and archive data, a sample is assembled of 21 SiO v  = 1, J  = 2 − 1 sources and 28 SiO v  = 1, J  = 1 − 0 sources that exhibit silicate emission features in the ISO /SWS spectrum as well. The analysis of their SiO maser and silicate emission power indicates a clear correlation, which is not against the hypothesis that the SiO molecules are the seed nuclei of silicate dust. On the other hand, no correlation is found between SiO maser and silicate crystallinity, which may imply that silicate crystallinity does not correlate with mass-loss rate.

Supramolecular Organization of Nonstoichiometric Drug Hydrates: Dapsone

Directory of Open Access Journals (Sweden)

Doris E. Braun

2018-02-01

Full Text Available The observed moisture- and temperature dependent transformations of the dapsone (4,4′-diaminodiphenyl sulfone, DDS 0. 33-hydrate were correlated to its structure and the number and strength of the water-DDS intermolecular interactions. A combination of characterization techniques was used, including thermal analysis (hot-stage microscopy, differential scanning calorimetry and thermogravimetric analysis, gravimetric moisture sorption/desorption studies and variable humidity powder X-ray diffraction, along with computational modeling (crystal structure prediction and pair-wise intermolecular energy calculations. Depending on the relative humidity the hydrate contains between 0 and 0.33 molecules of water per molecule DDS. The crystal structure is retained upon dehydration indicating that DDS hydrate shows a non-stoichiometric (dehydration behavior. Unexpectedly, the water molecules are not located in structural channels but at isolated-sites of the host framework, which is counterintuitively for a hydrate with non-stoichiometric behavior. The water-DDS interactions were estimated to be weaker than water-host interactions that are commonly observed in stoichiometric hydrates and the lattice energies of the isomorphic dehydration product (hydrate structure without water molecules and (form III differ only by ~1 kJ mol−1. The computational generation of hypothetical monohydrates confirms that the hydrate with the unusual DDS:water ratio of 3:1 is more stable than a feasible monohydrate structure. Overall, this study highlights that a deeper understanding of the formation of hydrates with non-stoichiometric behavior requires a multidisciplinary approach including suitable experimental and computational methods providing a firm basis for the development and manufacturing of high quality drug products.

TOUGH+Hydrate v1.0 User's Manual: A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media

Energy Technology Data Exchange (ETDEWEB)

Moridis, George; Moridis, George J.; Kowalsky, Michael B.; Pruess, Karsten

2008-03-01

TOUGH+HYDRATE v1.0 is a new code for the simulation of the behavior of hydrate-bearing geologic systems. By solving the coupled equations of mass and heat balance, TOUGH+HYDRATE can model the non-isothermal gas release, phase behavior and flow of fluids and heat under conditions typical of common natural CH{sub 4}-hydrate deposits (i.e., in the permafrost and in deep ocean sediments) in complex geological media at any scale (from laboratory to reservoir) at which Darcy's law is valid. TOUGH+HYDRATE v1.0 includes both an equilibrium and a kinetic model of hydrate formation and dissociation. The model accounts for heat and up to four mass components, i.e., water, CH{sub 4}, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dissociation or formation, phase changes and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects and inhibitor-induced effects. TOUGH+HYDRATE is the first member of TOUGH+, the successor to the TOUGH2 [Pruess et al., 1991] family of codes for multi-component, multiphase fluid and heat flow developed at the Lawrence Berkeley National Laboratory. It is written in standard FORTRAN 95, and can be run on any computational platform (workstation, PC, Macintosh) for which such compilers are available.

Effect of zinc-containing β-tricalcium phosphate nano particles injection on jawbone mineral density and mechanical strength of osteoporosis model rats

International Nuclear Information System (INIS)

Tokudome, Yoshihiro; Otsuka, Makoto; Ito, Atsuo

2011-01-01

Zinc-containing β-tricalcium phosphate (ZnTCP) nano particles were injected into zinc-deficient rats to promote osteogenesis. Sprague-Dawley (SD) rats (4 weeks old, average weight of 70 g) were divided into four groups: Normal rats (not ovariectomized (OVX)), Control rats (OVX), and OVX rats injected with a suspension of ZnTCP nano particles or ZnSO 4 . The ZnTCP contained 6.17% zinc. The suspensions (0.6 mg as a zinc volume/0.2 ml) were injected around the jaw bone once a week for 12 weeks. Local effects on the bone mineral content (BMC) of jawbone, and systemic effects on body weight, the BMC of both femurs determined by X-ray computed tomography, and bone mechanical strength (BMS) measured by the three-point bending method, were examined. The BMC of jaw bone was significantly higher in the ZnTCP-treated group than un-treated or ZnSO 4 -treated group. Body weight, the BMC of femurs, and BMS were also significantly higher in the ZnTCP treated-group. The zinc-containing β-tricalcium phosphate nano particles were effective at preventing bone loss induced by ovariectomy in rats and have potential uses for treating periodontitis. (author)

Surgical Treatment of Periodontal Intrabony Defects with Calcium Sulphate in Combination with Beta-Tricalcium Phosphate: Clinical Observations Two Years Post-Surgery

Directory of Open Access Journals (Sweden)

Sujith Sukumar

2011-01-01

Full Text Available The study was designed to evaluate the clinical outcome of a composite material, beta-tricalcium phosphate in combination with calcium sulphate, in the treatment of periodontal intrabony defects. The combination of these materials is believed to aid in guided tissue regeneration owing to their properties. A total of 47 teeth with intrabony defects in 26 periodontitis patients were treated with Fortoss® Vital (Biocomposites, Staffordshire, UK. Clinical parameters were evaluated which included changes in probing depth, clinical attachment level/loss and gingival recession at the baseline and 2 years postoperatively. The mean differences in measurements between the baseline and 2 years postoperatively were a reduction of 2.07±1.14 mm (p=0.000 in case of probing depth and a gain of 1.93±1.36 mm (p=0.000 in clinical attachment level; but an increase of 0.14±0.73 mm (p=0.571 in gingival recession. The study results show that the treatment with a combination of beta tricalcium phosphate and calcium sulphate led to a significantly favorable clinical improvement in periodontal intrabony defects 2 years after the surgery.

EFFECT OF SILICATE ON GRAM STAINING AND VIABILITY OF PNEUMOCOCCI AND OTHER BACTERIA

Science.gov (United States)

MacLeod, Colin M.; Roe, Amy S.

1956-01-01

Application of silicate solutions to living or heat-killed pneumococci and to certain "viridans" streptococci causes their conversion from a Gram-positive to a Gram-negative state. The original staining properties can be restored by suspending the silicate-treated bacteria in alkaline solutions of various salts but not by simple washing in water. Living pneumococci and the strains of streptococci whose staining properties are similarly affected are killed when suspended in silicate solutions. In other Gram-positive species silicate causes conversion to Gram negativity but restoration to positivity occurs upon washing in water. In a third group of Gram-positive organisms silicate has no effect on the Gram reaction. The viability of organisms in these two groups is unaffected by silicate under the conditions employed. No effect on staining or viability of Gram-negative bacteria has been observed. The effects of silicate on staining and viability are inhibited by nutrient broth or whole serum but not by purified serum albumin. Lecithin, choline, and other substituted ammonium compounds also inhibit the effects of silicate on pneumococci. PMID:13306854

Odontogenic differentiation of human dental pulp cells by calcium silicate materials stimulating via FGFR/ERK signaling pathway

International Nuclear Information System (INIS)

Liu, Chao-Hsin; Hung, Chi-Jr; Huang, Tsui-Hsien; Lin, Chi-Chang; Kao, Chia-Tze; Shie, Ming-You

2014-01-01

Bone healing needs a complex interaction of growth factors that establishes an environment for efficient bone formation. We examine how calcium silicate (CS) and tricalcium phosphate (β-TCP) cements influence the behavior of human dental pulp cells (hDPCs) through fibroblast growth factor receptor (FGFR) and active MAPK pathways, in particular ERK. The hDPCs are cultured with β-TCP and CS, after which the cells' viability and odontogenic differentiation markers are determined by using PrestoBlue® assay and western blot, respectively. The effect of small interfering RNA (siRNA) transfection targeting FGFR was also evaluated. The results showed that CS promoted cell proliferation and enhances FGFR expression. It was also found that CS increases ERK and p38 activity in hDPCs, and furthermore, raises the expression and secretion of DSP, and DMP-1. Additionally, statistically significant differences (p < 0.05) have been found in the calcium deposition in si-FGFR transfection and ERK inhibitor between CS and β-TCP; these variations indicated that ERK/MAPK signaling is involved in the silicon-induced odontogenic differentiation of hDPCs. The current study shows that CS substrates play a key role in odontoblastic differentiation of hDPCs through FGFR and modulate ERK/MAPK activation. - Highlights: • CS influences the behavior of hDPCs through fibroblast growth factor receptor. • CS increases ERK and p38 activity in hDPCs. • ERK/MAPK signaling is involved in the Si-induced odontogenic differentiation of hDPCs. • Ca staining shows that FGFR regulates hDPC differentiation on CS, but not on β-TCP

Gas composition and isotopic geochemistry of cuttings, core, and gas hydrate from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well

Science.gov (United States)

Lorenson, T.D.

1999-01-01

Molecular and isotopic composition of gases from the JAPEX/JNOC/GSC Mallik 2L-38 gas hydrate research well demonstrate that the in situ gases can be divided into three zones composed of mixtures of microbial and thermogenic gases. Sediments penetrated by the well are thermally immature; thus the sediments are probably not a source of thermogenic gas. Thermogenic gas likely migrated from depths below 5000 m. Higher concentrations of gas within and beneath the gas hydrate zone suggest that gas hydrate is a partial barrier to gas migration. Gas hydrate accumulations occur wholly within zone 3, below the base of permafrost. The gas in gas hydrate resembles, in part, the thermogenic gas in surrounding sediments and gas desorbed from lignite. Gas hydrate composition implies that the primary gas hydrate form is Structure I. However, Structure II stabilizing gases are more concentrated and isotopically partitioned in gas hydrate relative to the sediment hosting the gas hydrate, implying that Structure II gas hydrate may be present in small quantities.

Carbonation of metal silicates for long-term CO2 sequestration

Science.gov (United States)

Blencoe, James G; Palmer, Donald A; Anovitz, Lawrence M; Beard, James S

2014-03-18

In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

Hydration shells exchange charge with their protein

DEFF Research Database (Denmark)

Abitan, Haim; Lindgård, Per-Anker; Nielsen, Bjørn Gilbert

2010-01-01

. In our experiments, the amplitude of an ultrasonic pressure wave is gradually increased (0–20 atm) while we simultaneously measure the Raman spectra from the hydrated protein (β-lactoglobulin and lysozyme). We detected two types of spectral changes: first, up to 70% increase in the intensity......Investigation of the interaction between a protein and its hydration shells is an experimental and theoretical challenge. Here, we used ultrasonic pressure waves in aqueous solutions of a protein to explore the conformational states of the protein and its interaction with its hydration shells...... the presence of an ultrasonic pressure, a protein and its hydration shells are in thermodynamic and charge equilibrium, i.e. a protein and its hydration shells exchange charges. The ultrasonic wave disrupts these equilibria which are regained within 30–45 min after the ultrasonic pressure is shut off....

Oceanic hydrates: more questions than answers

International Nuclear Information System (INIS)

Laherrere, Jean

2000-01-01

Methane hydrates create problems by blocking pipelines and casing; they are also accused of contributing to environmental problems (e.g. global warming). Methane hydrates are also found in permafrost areas and in oceanic sediments where the necessary temperature and pressure for stability occur. Claims for the widespread occurrence in thick oceanic deposits are unfounded: apparently indirect evidence from seismic reflectors, seismic hydrocarbon indicators, logs and free samples is unreliable. At one time, hydrate was seen as a static, biogenic, continuous, huge resource but that view is changing to one of a dynamic, overpressurised, discontinuous and unreliable resource. Only Japan and India are currently showing any serious interest in hydrates. Academic research has raised more questions than answers. It is suggested that more hard exploratory evidence rather than theoretical study is required

Viscosity of Heterogeneous Silicate Melts: A Non-Newtonian Model

Science.gov (United States)

Liu, Zhuangzhuang; Blanpain, Bart; Guo, Muxing

2017-12-01

The recently published viscosity data of heterogeneous silicate melts with well-documented structure and experimental conditions are critically re-analyzed and tabulated. By using these data, a non-Newtonian viscosity model incorporating solid fraction, solid shape, and shear rate is proposed on the basis of the power-law equation. This model allows calculating the viscosity of the heterogeneous silicate melts with solid fraction up to 34 vol pct. The error between the calculated and measured data is evaluated to be 32 pct, which is acceptable considering the large error in viscosity measurement of the completely liquid silicate melt.

Chloral Hydrate

Science.gov (United States)

... if you are allergic to chloral hydrate, aspirin, tartrazine (a yellow dye in some processed foods and ... in, tightly closed, and out of reach of children. Store it at room temperature, away from excess ...

Phase behavior of methane hydrate in silica sand

International Nuclear Information System (INIS)

Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang; Liu, Yu-Feng

2014-01-01

Highlights: • Hydrate p-T trace in coarse-grained sediment is consistent with that in bulk water. • Fine-grained sediment affects hydrate equilibrium for the depressed water activity. • Hydrate equilibrium in sediment is related to the pore size distribution. • The application of hydrate equilibrium in sediment depends on the actual condition. -- Abstract: Two kinds of silica sand powder with different particle size were used to investigate the phase behavior of methane hydrate bearing sediment. In coarse-grained silica sand, the measured temperature and pressure range was (281.1 to 284.2) K and (5.9 to 7.8) MPa, respectively. In fine-grained silica sand, the measured temperature and pressure range was (281.5 to 289.5) K and (7.3 to 16.0) MPa, respectively. The results show that the effect of coarse-grained silica sand on methane hydrate phase equilibrium can be ignored; however, the effect of fine-grained silica sand on methane hydrate phase equilibrium is significant, which is attributed to the depression of water activity caused by the hydrophilicity and negatively charged characteristic of silica particle as well as the pore capillary pressure. Besides, the analysis of experimental results using the Gibbs–Thomson equation shows that methane hydrate phase equilibrium is related to the pore size distribution of silica sand. Consequently, for the correct application of phase equilibrium data of hydrate bearing sediment, the geological condition and engineering requirement should be taken into consideration in gas production, resource evaluation, etc

Carbon dioxide hydrate formation in a fixed-bed reactor

Energy Technology Data Exchange (ETDEWEB)

Fan, S.; Lang, X. [South China Univ. of Technology, Guangzhou (China). Key Laboratory of Enhanced Heat Transfer and Energy Conservation; Wang, Y.; Liang, D. [Chinese Academy of Sciences, Guangzhou (China). Guangzhou Inst. of Energy Conversion and Guangzhou Center of Natural Gas Hydrate; Sun, X.; Jurcik, B. [Air Liquide Laboratories, Tsukuba (Japan)

2008-07-01

Gas hydrates are thermodynamically stable at high pressures and near the freezing temperature of pure water. Methane hydrates occur naturally in sediments in the deep oceans and permafrost regions and constitute an extensive hydrocarbon reservoir. Carbon dioxide (CO{sub 2}) hydrates are of interest as a medium for marine sequestration of anthropogenic carbon dioxide. Sequestering CO{sub 2} as hydrate has potential advantages over most methods proposed for marine CO{sub 2} sequestration. Because this technique requires a shallower depth of injection when compared with other ocean sequestration methods, the costs of CO{sub 2} hydrate sequestration may be lower. Many studies have successfully used different continuous reactor designs to produce CO{sub 2} hydrates in both laboratory and field settings. This paper discussed a study that involved the design and construction of a fixed-bed reactor for simulation of hydrate formation system. Water, river sands and carbon dioxide were used to simulate the seep kind of hydrate formation. Carbon dioxide gas was distributed as small bubbles to enter from the bottom of the fixed-bed reactor. The paper discussed the experimental data and presented a diagram of the gas hydrate reactor system. The morphology as well as the reaction characters of CO{sub 2} hydrate was presented in detail. The results were discussed in terms of experimental phenomena and hydrate formation rate. A mathematical model was proposed for describing the process. 17 refs., 7 figs.

Ab initio modelling of methane hydrate thermophysical properties.

Science.gov (United States)

Jendi, Z M; Servio, P; Rey, A D

2016-04-21

The key thermophysical properties of methane hydrate were determined using ab initio modelling. Using density functional theory, the second-order elastic constants, heat capacity, compressibility, and thermal expansion coefficient were calculated. A wide and relevant range of pressure-temperature conditions were considered, and the structures were assessed for stability using the mean square displacement and radial distribution functions. Methane hydrate was found to be elastically isotropic with a linear dependence of the bulk modulus on pressure. Equally significant, multi-body interactions were found to be important in hydrates, and water-water interactions appear to strongly influence compressibility like in ice Ih. While the heat capacity of hydrate was found to be higher than that of ice, the thermal expansion coefficient was significantly lower, most likely due to the lower rigidity of hydrates. The mean square displacement gave important insight into stability, heat capacity, and elastic moduli, and the radial distribution functions further confirmed stability. The presented results provide a much needed atomistic thermoelastic characterization of methane hydrates and are essential input for the large-scale applications of hydrate detection and production.

Decomposition of pre calcined aluminium silicate ores of Afghanistan by hydrochloric acid

International Nuclear Information System (INIS)

Khomidi, A.K.; Mamatov, E.D.

2015-01-01

Present article is devoted to decomposition of pre calcined aluminium silicate ores of Afghanistan by hydrochloric acid. The physicochemical properties of initial aluminium silicate ores were studied by means of X-ray phase, differential thermal and silicate analysis. The chemical composition of aluminium containing ores was determined. The optimal conditions of interaction of initial and pre calcined siallites with hydrochloric acid were defined. The kinetics of acid decomposition of aluminium silicate ores was studied as well.

Long term mechanical properties of alkali activated slag

Science.gov (United States)

Zhu, J.; Zheng, W. Z.; Xu, Z. Z.; Leng, Y. F.; Qin, C. Z.

2018-01-01

This article reports a study on the microstructural and long-term mechanical properties of the alkali activated slag up to 180 days, and cement paste is studied as the comparison. The mechanical properties including compressive strength, flexural strength, axis tensile strength and splitting tensile strength are analyzed. The results showed that the alkali activated slag had higher compressive and tensile strength, Slag is activated by potassium silicate (K2SiO3) and sodium hydroxide (NaOH) solutions for attaining silicate modulus of 1 using 12 potassium silicate and 5.35% sodium hydroxide. The volume dosage of water is 35% and 42%. The results indicate that alkali activated slag is a kind of rapid hardening and early strength cementitious material with excellent long-term mechanical properties. Single row of holes block compressive strength, single-hole block compressive strength and standard solid brick compressive strength basically meet engineering requirements. The microstructures of alkali activated slag are studied by X-ray diffraction (XRD). The hydration products of alkali-activated slag are assured as hydrated calcium silicate and hydrated calcium aluminate.

Dehydration kinetics of a natural montmorillonite

International Nuclear Information System (INIS)

Andreotti, G.; Loria, A.; Mazzega, E.; Valeri, S.

1978-01-01

The dehydration mass loss of samples of montmorillonite (a layered hydrated silicate) was measured in an environment at constant temperature and at constant undersatured water vapour content. The hydration curves were analyzed by assuming the model of thermally activated, monoenergetic and first-order process compatible with the experimental results. Two dehydration kinetics with activation energies (0.21+-0.02) eV and (0.34+-0.02) eV were found that can be related to the existence of two kinds of water (structured and nonstructured) in the hydrated silicate interlayers. The possibility of an icelike structure of a fraction of the adsorbed molecules is briefly discussed. The experimental results show, furthermore, that in the investigated hydration range (up to about 10% in mass) the fraction of structured water has a maximum when the hydration is about 6%. (author)

CO2 injection into submarine, CH4-hydrate bearing sediments: Parameter studies towards the development of a hydrate conversion technology

Science.gov (United States)

Deusner, Christian; Bigalke, Nikolaus; Kossel, Elke; Haeckel, Matthias

2013-04-01

In the recent past, international research efforts towards exploitation of submarine and permafrost hydrate reservoirs have increased substantially. Until now, findings indicate that a combination of different technical means such as depressurization, thermal stimulation and chemical activation is the most promising approach for producing gas from natural hydrates. Moreover, emission neutral exploitation of CH4-hydrates could potentially be achieved in a combined process with CO2 injection and storage as CO2-hydrate. In the German gas hydrate initiative SUGAR, a combination of experimental and numerical studies is used to elucidate the process mechanisms and technical parameters on different scales. Experiments were carried out in the novel high-pressure flow-through system NESSI (Natural Environment Simulator for sub-Seafloor Interactions). Recent findings suggest that the injection of heated, supercritical CO2 is beneficial for both CH4 production and CO2 retention. Among the parameters tested so far are the CO2 injection regime (alternating vs. continuous injection) and the reservoir pressure / temperature conditions. Currently, the influence of CO2 injection temperature is investigated. It was shown that CH4 production is optimal at intermediate reservoir temperatures (8 ° C) compared to lower (2 ° C) and higher temperatures (10 ° C). The reservoir pressure, however, was of minor importance for the production efficiency. At 8 ° C, where CH4- and CO2-hydrates are thermodynamically stable, CO2-hydrate formation appears to be slow. Eventual clogging of fluid conduits due to CO2-rich hydrate formation force open new conduits, thereby tapping different regions inside the CH4-hydrate sample volume for CH4gas. In contrast, at 2 ° C immediate formation of CO2-hydrate results in rapid and irreversible obstruction of the entire pore space. At 10 ° C pure CO2-hydrates can no longer be formed. Consequently the injected CO2 flows through quickly and interaction with

Investigating the Metastability of Clathrate Hydrates for Energy Storage

Energy Technology Data Exchange (ETDEWEB)

Koh, Carolyn Ann [Colorado School of Mines, Golden, CO (United States)

2014-11-18

Important breakthrough discoveries have been achieved from the DOE award on the key processes controlling the synthesis and structure-property relations of clathrate hydrates, which are critical to the development of clathrate hydrates as energy storage materials. Key achievements include: (i) the discovery of key clathrate hydrate building blocks (stable and metastable) leading to clathrate hydrate nucleation and growth; (ii) development of a rapid clathrate hydrate synthesis route via a seeding mechanism; (iii) synthesis-structure relations of H2 + CH4/CO2 binary hydrates to control thermodynamic requirements for energy storage and sequestration applications; (iv) discovery of a new metastable phase present during clathrate hydrate structural transitions. The success of our research to-date is demonstrated by the significant papers we have published in high impact journals, including Science, Angewandte Chemie, J. Am. Chem. Soc. Intellectual Merits of Project Accomplishments: The intellectual merits of the project accomplishments are significant and transformative, in which the fundamental coupled computational and experimental program has provided new and critical understanding on the key processes controlling the nucleation, growth, and thermodynamics of clathrate hydrates containing hydrogen, methane, carbon dioxide, and other guest molecules for energy storage. Key examples of the intellectual merits of the accomplishments include: the first discovery of the nucleation pathways and dominant stable and metastable structures leading to clathrate hydrate formation; the discovery and experimental confirmation of new metastable clathrate hydrate structures; the development of new synthesis methods for controlling clathrate hydrate formation and enclathration of molecular hydrogen. Broader Impacts of Project Accomplishments: The molecular investigations performed in this project on the synthesis (nucleation & growth)-structure-stability relations of clathrate

The impact of permafrost-associated microorganisms on hydrate formation kinetics

Science.gov (United States)

Luzi-Helbing, Manja; Liebner, Susanne; Spangenberg, Erik; Wagner, Dirk; Schicks, Judith M.

2016-04-01

The relationship between gas hydrates, microorganisms and the surrounding sediment is extremely complex: On the one hand, microorganisms producing methane provide the prerequisite for gas hydrate formation. As it is known most of the gas incorporated into natural gas hydrates originates from biogenic sources. On the other hand, as a result of microbial activity gas hydrates are surrounded by a great variety of organic compounds which are not incorporated into the hydrate structure but may influence the formation or degradation process. For gas hydrate samples from marine environments such as the Gulf of Mexico a direct association between microbes and gas hydrates was shown by Lanoil et al. 2001. It is further assumed that microorganisms living within the gas hydrate stability zone produce biosurfactants which were found to enhance the hydrate formation process significantly and act as nucleation centres (Roger et al. 2007). Another source of organic compounds is sediment organic matter (SOM) originating from plant material or animal remains which may also enhance hydrate growth. So far, the studies regarding this relationship were focused on a marine environment. The scope of this work is to extend the investigations to microbes originating from permafrost areas. To understand the influence of microbial activity in a permafrost environment on the methane hydrate formation process and the stability conditions of the resulting hydrate phase we will perform laboratory studies. Thereby, we mimic gas hydrate formation in the presence and absence of methanogenic archaea (e.g. Methanosarcina soligelidi) and other psychrophilic bacteria isolated from permafrost environments of the Arctic and Antarctic to investigate their impact on hydrate induction time and formation rates. Our results may contribute to understand and predict the occurrences and behaviour of potential gas hydrates within or adjacent to the permafrost. Lanoil BD, Sassen R, La Duc MT, Sweet ST, Nealson KH

Sodium Silicate Behavior in Porous Media Applied for In-Depth Profile Modifications

Directory of Open Access Journals (Sweden)

Hossein A. Akhlaghi Amiri

2014-03-01

Full Text Available This paper addresses alkaline sodium silicate (Na-silicate behavior in porous media. One of the advantages of the Na-silicate system is its water-like injectivity during the placement stage. Mixing Na-silicate with saline water results in metal silicate precipitation as well as immediate gelation. This work demonstrated that low salinity water (LSW, sea water diluted 25 times could be used as a pre-flush in flooding operations. A water override phenomenon was observed during gel formation which is caused by gravity segregation. Dynamic adsorption tests in the sand-packed tubes showed inconsiderable adsorbed silicon density (about 8.5 × 10−10 kg/cm3 for a solution with 33 mg/L silicon content, which is less than the estimated mono-layer adsorption density of 1.4 × 10−8 kg/cm3. Na-silicate enhanced water sweep efficiency after application in a dual-permeability sand-pack system, without leak off into the oil-bearing low permeability (LP zone. Field-scale numerical sensitivity studies in a layered reservoir demonstrated that higher permeability and viscosity contrasts and lower vertical/horizontal permeability ratio result in lower Na-silicate leakoff into the matrix. The length of the mixing zone between reservoir water and the injected Na-silicate solution, which is formed by low salinity pre-flush, acts as a buffer zone.

Nuclear Well Log Properties of Natural Gas Hydrate Reservoirs

Science.gov (United States)

Burchwell, A.; Cook, A.

2015-12-01

Characterizing gas hydrate in a reservoir typically involves a full suite of geophysical well logs. The most common method involves using resistivity measurements to quantify the decrease in electrically conductive water when replaced with gas hydrate. Compressional velocity measurements are also used because the gas hydrate significantly strengthens the moduli of the sediment. At many gas hydrate sites, nuclear well logs, which include the photoelectric effect, formation sigma, carbon/oxygen ratio and neutron porosity, are also collected but often not used. In fact, the nuclear response of a gas hydrate reservoir is not known. In this research we will focus on the nuclear log response in gas hydrate reservoirs at the Mallik Field at the Mackenzie Delta, Northwest Territories, Canada, and the Gas Hydrate Joint Industry Project Leg 2 sites in the northern Gulf of Mexico. Nuclear logs may add increased robustness to the investigation into the properties of gas hydrates and some types of logs may offer an opportunity to distinguish between gas hydrate and permafrost. For example, a true formation sigma log measures the thermal neutron capture cross section of a formation and pore constituents; it is especially sensitive to hydrogen and chlorine in the pore space. Chlorine has a high absorption potential, and is used to determine the amount of saline water within pore spaces. Gas hydrate offers a difference in elemental composition compared to water-saturated intervals. Thus, in permafrost areas, the carbon/oxygen ratio may vary between gas hydrate and permafrost, due to the increase of carbon in gas hydrate accumulations. At the Mallik site, we observe a hydrate-bearing sand (1085-1107 m) above a water-bearing sand (1107-1140 m), which was confirmed through core samples and mud gas analysis. We observe a decrease in the photoelectric absorption of ~0.5 barnes/e-, as well as an increase in the formation sigma readings of ~5 capture units in the water-bearing sand as

Removal of sulphur dioxide from flue gases

International Nuclear Information System (INIS)

Ersoy-Mericboyu, A.

1999-01-01

Mixtures of Ca(OH) 2 and different siliceous materials such as fly ash, bentonite, silica fume, and diatomite were hydrated to produce reactive SO 2 sorbents. It was observed that these sorbents showed a better reactivity toward SO 2 than the Ca(OH) 2 itself. This behavior is closely related to the pozzolanic nature of the hydrated sorbents and to the greater surface area. The reactivity of the sorbents was strongly influenced by the source of siliceous material and the hydration conditions. The total sulphation capacities of the sorbents were determined at 338 K with a synthetic gaseous mixture containing 5,000 ppm SO 2 and 55% relative humidity. Depending on the chemical and physical properties of the sorbents, the SO 2 captures ranged from 1.20 to 5.58 mmol SO 2 /g sorbent. The amount of SO 2 capture increased with the increasing surface area of the sorbent. The utilization of Ca(OH) 2 with SO 2 improved significantly when Ca(OH) 2 was hydrated with siliceous materials first and later exposed to SO 2 . (author)

Manufacture of Methane Hydrate using Carbon Nano Tubes

International Nuclear Information System (INIS)

Park, Sung Seek

2010-02-01

Methane hydrate is formed by physical binding between water molecule and gas such as methane, ethane, propane, or carbon dioxide, etc., which is captured in the cavities of water molecule under the specific temperature and pressure. More than 99% of naturally produced methane hydrate consists of methane, and is widely dispersed in the continental slope and continental Shelf of the Pacific and the Atlantic, the Antarctica etc. The reserve of fossil fuel is 500 billion carbon ton and the reserve of methane is 360 million carbon ton. The reserve of gas hydrate is more than 1 trillion carbon ton, which is twice the fossil fuel. Therefore, natural gas hydrate as a kind of gas hydrate is expected to replace fossil fuel as new energy source of 21st century. Also 1 m 3 hydrate of pure methane can be decomposed to the maximum of 216 m 3 methane at standard condition. If these characteristics of hydrate are reversely utilized, natural gas is fixed into water in the form of hydrate solid. Therefore, the hydrate is considered to be a great way to transport and store natural gas in large quantity. Especially the transportation cost is known to be 18∼25% less than the liquefied transportation. However, when natural gas hydrate is artificially formed, its reaction time may be too long and the gas consumption in water becomes relatively low, because the reaction rate between water and gas is low. Therefore, for the practical purpose in the application, the present investigation focuses on the rapid production of hydrates and increases gas consumption by adding MWCNT and NaCl into pure water. The results show that the equilibrium pressure in seawater is more higher than that in pure water, and methane hydrate could be formed rapidly during pressurization if the subcooling is maintained at 9K or above in seawater and 8K or above in pure water, respectively. Also, amount of consumed gas volume in pure water is more higher that in seawater at the same experimental conditions

First-principles elasticity of monocarboaluminate hydrates

KAUST Repository

Moon, J.; Yoon, S.; Wentzcovitch, R. M.; Monteiro, P. J. M.

2014-01-01

The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

First-principles elasticity of monocarboaluminate hydrates

KAUST Repository

Moon, J.

2014-07-01

The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

SILICATE EVOLUTION IN BROWN DWARF DISKS

International Nuclear Information System (INIS)

Riaz, B.

2009-01-01

We present a compositional analysis of the 10 μm silicate spectra for brown dwarf disks in the Taurus and Upper Scorpius (UppSco) star-forming regions, using archival Spitzer/Infrared Spectrograph observations. A variety in the silicate features is observed, ranging from a narrow profile with a peak at 9.8 μm, to nearly flat, low-contrast features. For most objects, we find nearly equal fractions for the large-grain and crystalline mass fractions, indicating both processes to be active in these disks. The median crystalline mass fraction for the Taurus brown dwarfs is found to be 20%, a factor of ∼2 higher than the median reported for the higher mass stars in Taurus. The large-grain mass fractions are found to increase with an increasing strength in the X-ray emission, while the opposite trend is observed for the crystalline mass fractions. A small 5% of the Taurus brown dwarfs are still found to be dominated by pristine interstellar medium-like dust, with an amorphous submicron grain mass fraction of ∼87%. For 15% of the objects, we find a negligible large-grain mass fraction, but a >60% small amorphous silicate fraction. These may be the cases where substantial grain growth and dust sedimentation have occurred in the disks, resulting in a high fraction of amorphous submicron grains in the disk surface. Among the UppSco brown dwarfs, only usd161939 has a signal-to-noise ratio high enough to properly model its silicate spectrum. We find a 74% small amorphous grain and a ∼26% crystalline mass fraction for this object.

Water Dynamics in the Hydration Shells of Biomolecules