In-Situ Phase Transition Control in the Supercooled State for Robust Active Glass Fiber.

Science.gov (United States)

Lv, Shichao; Cao, Maoqing; Li, Chaoyu; Li, Jiang; Qiu, Jianrong; Zhou, Shifeng

2017-06-21

The construction of a dopant-activated photonic composite is of great technological importance for various applications, including smart lighting, optical amplification, laser, and optical detection. The bonding arrangement around the introduced dopants largely determines the properties, yet it remains a daunting challenge to manipulate the local state of the matrix (i.e., phase) inside the transparent composite in a controllable manner. Here we demonstrate that the relaxation of the supercooled state enables in-situ phase transition control in glass. Benefiting from the unique local atom arrangement manner, the strategy offers the possibility for simultaneously tuning the chemical environment of the incorporated dopant and engineering the dopant-host interaction. This allows us to effectively activate the dopant with high efficiency (calculated as ∼100%) and profoundly enhance the dopant-host energy-exchange interaction. Our results highlight that the in-situ phase transition control in glass may provide new opportunities for fabrication of unusual photonic materials with intense broadband emission at ∼1100 nm and development of the robust optical detection unit with high compactness and broadband photon-harvesting capability (from X-ray to ultraviolet light).

Detection of structural heterogeneity of glass melts

DEFF Research Database (Denmark)

Yue, Yuanzheng

2004-01-01

The structural heterogeneity of both supercooled liquid and molten states of silicate has been studied using calorimetric method. The objects of this study are basaltic glasses and liquids. Two experimental approaches are taken to detect the structural heterogeneity of the liquids. One is the hyp......The structural heterogeneity of both supercooled liquid and molten states of silicate has been studied using calorimetric method. The objects of this study are basaltic glasses and liquids. Two experimental approaches are taken to detect the structural heterogeneity of the liquids. One...... is the hyperquench-anneal-calorimetric scan approach, by which the structural information of a basaltic supercooled liquid and three binary silicate liquids is acquired. Another is the calorimetrically repeated up- and downscanning approach, by which the structural heterogeneity, the intermediate range order...... is discussed. The ordered structure of glass melts above the liquidus temperature is indirectly characterized by use of X-ray diffraction method. The new approaches are of importance for monitoring the glass melting and forming process and for improving the physical properties of glasses and glass fibers....

The descent into glass formation in polymer fluids.

Science.gov (United States)

Freed, Karl F

2011-03-15

Glassy materials have been fundamental to technology since the dawn of civilization and remain so to this day: novel glassy systems are currently being developed for applications in energy storage, electronics, food, drugs, and more. Glass-forming fluids exhibit a universal set of transitions beginning at temperatures often in excess of twice the glass transition temperature T(g) and extending down to T(g), below which relaxation becomes so slow that systems no longer equilibrate on experimental time scales. Despite the technological importance of glasses, no prior theory explains this universal behavior nor describes the huge variations in the properties of glass-forming fluids that result from differences in molecular structure. Not surprisingly, the glass transition is currently regarded by many as the deepest unsolved problem in solid state theory. In this Account, we describe our recently developed theory of glass formation in polymer fluids. Our theory explains the origin of four universal characteristic temperatures of glass formation and their dependence on monomer-monomer van der Waals energies, conformational energies, and pressure and, perhaps most importantly, on molecular details, such as monomer structure, molecular weight, size of side groups, and so forth. The theory also provides a molecular explanation for fragility, a parameter that quantifies the rate of change with temperature of the viscosity and other dynamic mechanical properties at T(g). The fragility reflects the fluid's thermal sensitivity and determines the manner in which glass-formers can be processed, such as by extrusion, casting, or inkjet spotting. Specifically, the theory describes the change in thermodynamic properties and fragility of polymer glasses with variations in the monomer structure, the rigidity of the backbone and side groups, the cohesive energy, and so forth. The dependence of the structural relaxation time at lower temperatures emerges from the theory as the Vogel

Mechanical annealing in the flow of supercooled metallic liquid

International Nuclear Information System (INIS)

Zhang, Meng; Dai, Lan Hong; Liu, Lin

2014-01-01

Flow induced structural evolution in a supercooled metallic liquid Vit106a (Zr 58.5 Cu 15.6 Al 10.3 Ni 12.8 Nb 2.8 , at. %) was investigated via uni-axial compression combined with differential scanning calorimeter (DSC). Compression tests at strain rates covering the transition from Newtonian flow to non-Newtonian flow and at the same strain rate 2 × 10 −1 s −1 to different strains were performed at the end of glass transition (T g-end  = 703 K). The relaxation enthalpies measured by DSC indicate that the samples underwent non-Newtonian flow contain more free volume than the thermally annealed sample (703 K, 4 min), while the samples underwent Newtonian flow contain less, namely, the free volume of supercooled metallic liquids increases in non-Newtonian flow, while decreases in Newtonian flow. The oscillated variation of the relaxation enthalpies of the samples deformed at the same strain rate 2 × 10 −1 s −1 to different strains confirms that the decrease of free volume was caused by flow stress, i.e., “mechanical annealing.” Micro-hardness tests were also performed to show a similar structural evolution tendency. Based on the obtained results, the stress-temperature scaling in the glass transition of metallic glasses are supported experimentally, as stress plays a role similar to temperature in the creation and annihilation of free volume. In addition, a widening perspective angle on the glass transition of metallic glasses by exploring the 3-dimensional stress-temperature-enthalpy phase diagram is presented. The implications of the observed mechanical annealing effect on the amorphous structure and the work-hardening mechanism of metallic glasses are elucidated based on atomic level stress model

Pressure effect on crystallization of metallic glass Fe72P11C6Al5B4Ga2 alloy with wide supercooled liquid region

DEFF Research Database (Denmark)

Jiang, Jianzhong; Olsen, J. S.; Gerward, Leif

2000-01-01

The effect of pressure on the crystallization behavior of metallic glass Fe72P11C6Al5B4Ga2 alloy with a wide supercooled liquid region has been investigated by in situ high-pressure and high-temperature x-ray diffraction measurements using synchrotron radiation. In the pressure range from 0 to 2...... mobility and changes of the Gibbs free energy of various phases with pressure. ©2000 American Institute of Physics....

Improvement of bio-corrosion resistance for Ti42Zr40Si15Ta3 metallic glasses in simulated body fluid by annealing within supercooled liquid region.

Science.gov (United States)

Huang, C H; Lai, J J; Wei, T Y; Chen, Y H; Wang, X; Kuan, S Y; Huang, J C

2015-01-01

The effects of the nanocrystalline phases on the bio-corrosion behavior of highly bio-friendly Ti42Zr40Si15Ta3 metallic glasses in simulated body fluid were investigated, and the findings are compared with our previous observations from the Zr53Cu30Ni9Al8 metallic glasses. The Ti42Zr40Si15Ta3 metallic glasses were annealed at temperatures above the glass transition temperature, Tg, with different time periods to result in different degrees of α-Ti nano-phases in the amorphous matrix. The nanocrystallized Ti42Zr40Si15Ta3 metallic glasses containing corrosion resistant α-Ti phases exhibited more promising bio-corrosion resistance, due to the superior pitting resistance. This is distinctly different from the previous case of the Zr53Cu30Ni9Al8 metallic glasses with the reactive Zr2Cu phases inducing serious galvanic corrosion and lower bio-corrosion resistance. Thus, whether the fully amorphous or partially crystallized metallic glass would exhibit better bio-corrosion resistance, the answer would depend on the crystallized phase nature. Copyright © 2015 Elsevier B.V. All rights reserved.

A glance on the glass-transition phenomenon from the viewpoint of devitrification

International Nuclear Information System (INIS)

Louzguine-Luzgin, Dmitri V.; Inoue, Akihisa

2007-01-01

The formation of a supercooled liquid region and devitrification behaviour of metallic glasses on heating are discussed in relation with the glass-transition phenomenon observed using differential scanning and isothermal calorimetries as well as X-ray diffraction and transmission electron microscopy (TEM). One of the most clear sequences of the glassy ↔ supercooled liquid phase transition is the change of the devitrification behaviour and the kinetics of the devitrification reaction in Al-based and some other alloys after the transition from the glassy to the supercooled liquid state. The significant variation in the devitrification behaviour and thermodynamic parameters indicate the difference between the glassy and the supercooled liquid phases

Pressure effect of glass transition temperature in Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk metallic glass

DEFF Research Database (Denmark)

Jiang, Jianzhong; Roseker, W.; Sikorski, M.

2004-01-01

Pressure effects on glass transition temperature and supercooled liquid region of a Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk glass have been investigated by performing in situ high-temperature and high-pressure x-ray powder diffraction measurements using synchrotron radiation. The glass transition was det...... range of 0-2.2 GPa. This method opens a possibility to study the pressure effect of glass transition process in glassy systems under high pressures (>1 GPa). (C) 2004 American Institute of Physics.......Pressure effects on glass transition temperature and supercooled liquid region of a Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk glass have been investigated by performing in situ high-temperature and high-pressure x-ray powder diffraction measurements using synchrotron radiation. The glass transition...... was detected from the change of the slope of peak position as a function of temperature. It is found that the glass transition temperature increases with pressure by 4.4 K/GPa for the Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk glass, and the supercooled liquid range decreases with pressure by 2.9 K/GPa in a pressure...

Analogy between spin glasses and Yang--Mills fluids

International Nuclear Information System (INIS)

Holm, D.D.; Kupershmidt, B.A.

1988-01-01

A dictionary of correspondence is established between the dynamical variables for spin-glass fluid and Yang-Mills plasma. The Lie-algebraic interpretation of these variables is presented for the two theories. The noncanonical Poisson bracket for the Hamiltonian dynamics of an ideal spin glass is shown to be identical to that for the dynamics of a Yang--Mills fluid plasma, although the Hamiltonians differ for the two theories. This Poisson bracket is associated to the dual space of an infinite-dimensional Lie algebra of semidirect-product type

Communication: Towards first principles theory of relaxation in supercooled liquids formulated in terms of cooperative motion

Energy Technology Data Exchange (ETDEWEB)

Freed, Karl F., E-mail: freed@uchicago.edu [James Franck Institute and Department of Chemistry, University of Chicago, 929 East 57 Street, Chicago, Illinois 60637 (United States)

2014-10-14

A general theory of the long time, low temperature dynamics of glass-forming fluids remains elusive despite the almost 20 years since the famous pronouncement by the Nobel Laureate P. W. Anderson, “The deepest and most interesting unsolved problem in solid state theory is probably the theory of the nature of glass and the glass transition” [Science 267, 1615 (1995)]. While recent work indicates that Adam-Gibbs theory (AGT) provides a framework for computing the structural relaxation time of supercooled fluids and for analyzing the properties of the cooperatively rearranging dynamical strings observed in low temperature molecular dynamics simulations, the heuristic nature of AGT has impeded general acceptance due to the lack of a first principles derivation [G. Adam and J. H. Gibbs, J. Chem. Phys. 43, 139 (1965)]. This deficiency is rectified here by a statistical mechanical derivation of AGT that uses transition state theory and the assumption that the transition state is composed of elementary excitations of a string-like form. The strings are assumed to form in equilibrium with the mobile particles in the fluid. Hence, transition state theory requires the strings to be in mutual equilibrium and thus to have the size distribution of a self-assembling system, in accord with the simulations and analyses of Douglas and co-workers. The average relaxation rate is computed as a grand canonical ensemble average over all string sizes, and use of the previously determined relation between configurational entropy and the average cluster size in several model equilibrium self-associating systems produces the AGT expression in a manner enabling further extensions and more fundamental tests of the assumptions.

Communication: Towards first principles theory of relaxation in supercooled liquids formulated in terms of cooperative motion.

Science.gov (United States)

Freed, Karl F

2014-10-14

A general theory of the long time, low temperature dynamics of glass-forming fluids remains elusive despite the almost 20 years since the famous pronouncement by the Nobel Laureate P. W. Anderson, "The deepest and most interesting unsolved problem in solid state theory is probably the theory of the nature of glass and the glass transition" [Science 267, 1615 (1995)]. While recent work indicates that Adam-Gibbs theory (AGT) provides a framework for computing the structural relaxation time of supercooled fluids and for analyzing the properties of the cooperatively rearranging dynamical strings observed in low temperature molecular dynamics simulations, the heuristic nature of AGT has impeded general acceptance due to the lack of a first principles derivation [G. Adam and J. H. Gibbs, J. Chem. Phys. 43, 139 (1965)]. This deficiency is rectified here by a statistical mechanical derivation of AGT that uses transition state theory and the assumption that the transition state is composed of elementary excitations of a string-like form. The strings are assumed to form in equilibrium with the mobile particles in the fluid. Hence, transition state theory requires the strings to be in mutual equilibrium and thus to have the size distribution of a self-assembling system, in accord with the simulations and analyses of Douglas and co-workers. The average relaxation rate is computed as a grand canonical ensemble average over all string sizes, and use of the previously determined relation between configurational entropy and the average cluster size in several model equilibrium self-associating systems produces the AGT expression in a manner enabling further extensions and more fundamental tests of the assumptions.

Using thermoforming capacity of metallic glasses to produce multimaterials

International Nuclear Information System (INIS)

Ragani, J.; Volland, A.; Valque, S.; Liu, Y.; Gravier, S.; Blandin, J.J.; Suery, M.

2010-01-01

In addition to casting, thermoforming is a particularly interesting way to produce components in bulk metallic glasses since large strains can be achieved when the BMGs are deformed in their supercooled liquid region. The experimental window (temperature, time) in which high temperature forming can be carried out is directly related to the crystallization resistance of the glass. Such forming windows have been identified for zirconium based bulk metallic glasses thanks to thermal analysis and compression tests in the supercooled liquid region. Based on this identification, the thermoforming capacity of the studied glasses was used to produce multimaterials associating metallic glasses with conventional metallic alloys. Two processes have been preferentially investigated (co-extrusion and co-pressing) and the interface quality of the elaborated multi materials was studied.

Microscopic Theory for the Role of Attractive Forces in the Dynamics of Supercooled Liquids.

Science.gov (United States)

Dell, Zachary E; Schweizer, Kenneth S

2015-11-13

We formulate a microscopic, no adjustable parameter, theory of activated relaxation in supercooled liquids directly in terms of the repulsive and attractive forces within the framework of pair correlations. Under isochoric conditions, attractive forces can nonperturbatively modify slow dynamics, but at high enough density their influence vanishes. Under isobaric conditions, attractive forces play a minor role. High temperature apparent Arrhenius behavior and density-temperature scaling are predicted. Our results are consistent with recent isochoric simulations and isobaric experiments on a deeply supercooled molecular liquid. The approach can be generalized to treat colloidal gelation and glass melting, and other soft matter slow dynamics problems.

Composition Range and Glass Forming Ability of Ternary Ca-Mg-Cu Bulk Metallic Glasses (Preprint)

National Research Council Canada - National Science Library

Senkov, O. N; Scott, J. M; Miracle, D. B

2006-01-01

.... The maximum thickness at which an alloy remains fully amorphous, glass transition temperature, crystallization temperature, temperature interval of the super-cooled region, solidus and liquidus...

Strong-Superstrong Transition in Glass Transition of Metallic Glass

International Nuclear Information System (INIS)

Dan, Wang; Hong-Yan, Peng; Xiao-Yu, Xu; Bao-Ling, Chen; Chun-Lei, Wu; Min-Hua, Sun

2010-01-01

Dynamic fragility of bulk metallic glass (BMG) of Zr 64 Cu 16 Ni 10 Al 10 alloy is studied by three-point beam bending methods. The fragility parameter mfor Zr 64 Cu 16 Ni 10 Al 10 BMG is calculated to be 24.5 at high temperature, which means that the liquid is a 'strong' liquid, while to be 13.4 at low temperature which means that the liquid is a 'super-strong' liquid. The dynamical behavior of Zr 64 Cu 16 Ni 10 Al 10 BMG in the supercooled region undergoes a strong to super-strong transition. To our knowledge, it is the first time that a strong-to-superstrong transition is found in the metallic glass. Using small angle x-ray scattering experiments, we find that this transition is assumed to be related to a phase separation process in supercooled liquid. (condensed matter: structure, mechanical and thermal properties)

Glass transition and density fluctuations in the fragile glass former orthoterphenyl

International Nuclear Information System (INIS)

Monaco, G.; Fioretto, D.; Comez, L.; Ruocco, G.

2001-01-01

High-resolution Brillouin light scattering is used to measure the dynamic structure factor of the fragile glass former orthoterphenyl (OTP) in a wide temperature range around the glass transition region and up to the boiling point. The whole set of spectra is described in terms of a phenomenological generalized hydrodynamic model. In the supercooled phase, we show the contemporary existence of the structural process, whose main features come out to be consistent with the results obtained with other spectroscopies, and of a secondary, activated process, which occurs on the 10 -11 s time scale and has a low activation energy (E a f =0.28 kcal/mol). This latter process, which is also present in the glassy phase and seems to be insensitive to the glass transition, is attributed to the coupling between the density modes and intramolecular degrees of freedom. In the normal liquid phase, the two processes merge together, and the resulting characteristic time is no longer consistent with those derived with other spectroscopies. The analysis points to the conclusion that, for what concerns the long-wavelength density fluctuations in fragile glass formers such as OTP, the universal dynamical features related to the glass transition come out clearly only in the supercooled phase and at frequencies lower than ∼10 6 Hz

Scattering methods in complex fluids

CERN Document Server

Chen, Sow-Hsin

2015-01-01

Summarising recent research on the physics of complex liquids, this in-depth analysis examines the topic of complex liquids from a modern perspective, addressing experimental, computational and theoretical aspects of the field. Selecting only the most interesting contemporary developments in this rich field of research, the authors present multiple examples including aggregation, gel formation and glass transition, in systems undergoing percolation, at criticality, or in supercooled states. Connecting experiments and simulation with key theoretical principles, and covering numerous systems including micelles, micro-emulsions, biological systems, and cement pastes, this unique text is an invaluable resource for graduate students and researchers looking to explore and understand the expanding field of complex fluids.

Generation of live offspring from vitrified embryos with synthetic polymers SuperCool X-1000 and SuperCool Z-1000.

Science.gov (United States)

Marco-Jimenez, F; Jimenez-Trigos, E; Lavara, R; Vicente, J S

2014-01-01

Ice growth and recrystallisation are considered important factors in determining vitrification outcomes. Synthetic polymers inhibit ice formation during cooling or warming of the vitrification process. The aim of this study was to assess the effect of adding commercially available synthetic polymers SuperCool X-1000 and SuperCool Z-1000 to vitrification media on in vivo development competence of rabbit embryos. Four hundred and thirty morphologically normal embryos recovered at 72 h of gestation were used. The vitrification media contained 20% dimethyl sulphoxide and 20% ethylene glycol, either alone or in combination with 1% of SuperCool X-1000 and 1% SuperCool. Our results show that embryos can be successfully vitrified using SuperCool X-1000 and SuperCool Z-1000 and when embryos are transferred, live offspring can be successfully produced. In conclusion, our results demonstrated that we succeeded for the first time in obtaining live offspring after vitrification of embryos using SuperCool X-1000 and SuperCool Z-1000 polymers.

Investigation of crystallization kinetics and deformation behavior in supercooled liquid region of CuZr-based bulk metallic glass

Energy Technology Data Exchange (ETDEWEB)

Yang, Ke; Fan, Xinhui; Li, Bing; Li, Yanhong; Wang, Xin; Xu, Xuanxuan [Xi' an Technological Univ. (China). School of Material and Chemical Engineering

2017-08-15

In this paper, a systematic study of crystallization kinetics and deformation behavior is presented for (Cu{sub 50}Zr{sub 50}){sub 94}Al{sub 6} bulk metallic glass in the supercooled liquid region. Crystallization results showed that the activation energy for (Cu{sub 50}Zr{sub 50}){sub 94}Al{sub 6} was calculated using the Arrhenius equation in isothermal mode and the Kissinger-Akahira-Sunose method in non-isothermal mode. The activation energy was quite high compared with other bulk metallic glasses. Based on isothermal transformation kinetics described by the Johson-Mehl-Avrami model, the average Avrami exponent of about 3.05 implies a mainly diffusion controlled three-dimensional growth with an increasing nucleation rate during the crystallization. For warm deformation, the results showed that deformation behavior, composed of homogeneous and inhomogeneous deformation, is strongly dependent on strain rate and temperature. The homogeneous deformation transformed from non-Newtonian flow to Newtonian flow with a decrease in strain rate and an increase in temperature. It was found that the crystallization during high temperature deformation is induced by heating. The appropriate working temperature/strain rate combination for the alloy forming, without in-situ crystallization, was deduced by constructing an empirical deformation map. The optimum process condition for (Cu{sub 50}Zr{sub 50}){sub 94}Al{sub 6} can be expressed as T∝733 K and ∝ ε 10{sup -3} s{sup -1}.

The role of the dynamic crossover temperature and the arrest in glass-forming fluids.

Science.gov (United States)

Mallamace, F; Corsaro, C; Stanley, H E; Chen, S-H

2011-09-01

We discuss the role of the dynamic glass-forming fragile-to-strong crossover (FSC) in supercooled liquids. In the FSC, significant dynamic changes such as the decoupling (the violation of the Stokes-Einstein relation) of homologous transport parameters, e.g., the density relaxation time τ and the viscosity η, occur at a characteristic temperature T(c). We study the FSC using a scaling law approach. In particular, we use both forms of the mode-coupling theory (MCT): the original (ideal) and the extended form, which explicitly describes energy hopping processes. We demonstrate that T(c) plays the most important physical role in understanding dynamic arrest processes.

Poor glass-forming ability of Fe-based alloys

DEFF Research Database (Denmark)

Zheng, H.J.; Hu, L.N.; Zhao, X.

2017-01-01

processes. By using the concept of fluid cluster and supercooled liquid fragility in metallic liquids, it has been found that this dynamic transition makes the Fe-based supercooled liquids become more unstable, which leads to the poor GFA of Fe-based alloys. Further, it has been found that the degree...

Phase diagram of supercooled water confined to hydrophilic nanopores

Science.gov (United States)

Limmer, David T.; Chandler, David

2012-07-01

We present a phase diagram for water confined to cylindrical silica nanopores in terms of pressure, temperature, and pore radius. The confining cylindrical wall is hydrophilic and disordered, which has a destabilizing effect on ordered water structure. The phase diagram for this class of systems is derived from general arguments, with parameters taken from experimental observations and computer simulations and with assumptions tested by computer simulation. Phase space divides into three regions: a single liquid, a crystal-like solid, and glass. For large pores, radii exceeding 1 nm, water exhibits liquid and crystal-like behaviors, with abrupt crossovers between these regimes. For small pore radii, crystal-like behavior is unstable and water remains amorphous for all non-zero temperatures. At low enough temperatures, these states are glasses. Several experimental results for supercooled water can be understood in terms of the phase diagram we present.

Applications and limitations of electron correlation microscopy to study relaxation dynamics in supercooled liquids

Energy Technology Data Exchange (ETDEWEB)

Zhang, Pei; He, Li [Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, WI 53706 (United States); Besser, Matthew F. [Materials Science and Engineering, Ames Laboratory, Iowa State University, Ames, IA 50011 (United States); Liu, Ze; Schroers, Jan [Department of Mechanical Engineering and Materials Science, Yale University, New Haven, CT 06511 (United States); Kramer, Matthew J. [Materials Science and Engineering, Ames Laboratory, Iowa State University, Ames, IA 50011 (United States); Voyles, Paul M., E-mail: paul.voyles@wisc.edu [Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, WI 53706 (United States)

2017-07-15

Electron correlation microscopy (ECM) is a way to measure structural relaxation times, τ, of liquids with nanometer-scale spatial resolution using coherent electron scattering equivalent of photon correlation spectroscopy. We have applied ECM with a 3.5 nm diameter probe to Pt{sub 57.5}Cu{sub 14.7}Ni{sub 5.3}P{sub 22.5} amorphous nanorods and Pd{sub 40}Ni{sub 40}P{sub 20} bulk metallic glass (BMG) heated inside the STEM into the supercooled liquid region. These data demonstrate that the ECM technique is limited by the characteristics of the time series, which must be at least 40τ to obtain a well-converged correlation function g{sub 2}(t), and the time per frame, which must be less than 0.1τ to obtain sufficient sampling. A high-speed direct electron camera enables fast acquisition and affords reliable g{sub 2}(t) data even with low signal per frame. - Highlights: • Electron Correlation Microscopy (ECM) technique was applied to measure structural relaxation times of supercooled liquids in metallic glass. • In Pt{sub 57.5}Cu{sub 14.7}Ni{sub 5.3}P{sub 22.5} nanowire, τ and β decreases over the measured supercooled liquid regime. • In Pd{sub 40}Ni{sub 40}P{sub 20} bulk alloy, τ decreases from T{sub g}+28 °C to T{sub g}+48 °C, then increases as the temperature approaches T{sub x}. • ECM experiment requires a length of time series at least 40 times the characteristic relaxation time and a time per diffraction pattern at most 0.1 times the relaxation time.

Fe-based bulk metallic glasses with a larger supercooled liquid region and high ductility

Energy Technology Data Exchange (ETDEWEB)

Qiu, K.Q. [School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110178 (China)], E-mail: kqqiu@yahoo.com.cn; Pang, J.; Ren, Y.L.; Zhang, H.B. [School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110178 (China); Ma, C.L.; Zhang, T. [School of Materials Science and Engineering, Beijing University of Aeronautics and Astronautics, Beijing 100083 (China)

2008-12-20

Bulk metallic glasses (BMGs) with compositions of Fe{sub 61.5-x}Co{sub 3}Mo{sub 14}C{sub 15}B{sub 6}Er{sub 0.5}M{sub x} (x = 2, 3; M = Ni, Nb) were fabricated by copper mold casting using raw industrial materials. The X-ray diffraction (XRD), differential scanning calorimetry (DSC), mechanical tester and scanning electron microscope (SEM) were employed to check the phase constituent, the thermal stability, the mechanical properties and the fracture surfaces of as-cast samples. The results indicate that the BMGs with diameters of 1.5-3 mm were fabricated for the alloys investigated. The largest supercooled liquid region (SLR) up to 76 K was found for Fe{sub 58.5}Co{sub 3}Mo{sub 14}C{sub 15}B{sub 6}Er{sub 0.5}Ni{sub 3} BMG. The BMGs with Ni addition exhibit not only high fracture strengths reaching 3770 MPa for x = 2 and 3980 MPa for x = 3 alloys, respectively, but also apparently plastic strains up to 0.67% and 0.93%, respectively. The fracture surfaces of the Fe{sub 61.5-x}Co{sub 3}Mo{sub 14}C{sub 15}B{sub 6}Er{sub 0.5}Ni{sub x} (x = 2, 3) alloys with plasticity show narrow ridges characteristic of venous patterns combining with tearing flow between the ridges. While the Nb containing alloys show not only a lower SLR below 60 K but also a lower stress below 2400 MPa, as well as almost no plastic strain before fracture.

Entropy Crisis, Defects and the Role of Competition in Monatomic Glass Formers

OpenAIRE

Gujrati, P. D.

2007-01-01

We establish the existence of an entropy crisis in monatomic glass formers. The work finally shows that the entropy crisis is ubiqutous in all supercooled liquids. We also study the roles of defects and energetic competition on the ideal glass.

Perspective: Highly stable vapor-deposited glasses

Science.gov (United States)

Ediger, M. D.

2017-12-01

This article describes recent progress in understanding highly stable glasses prepared by physical vapor deposition and provides perspective on further research directions for the field. For a given molecule, vapor-deposited glasses can have higher density and lower enthalpy than any glass that can be prepared by the more traditional route of cooling a liquid, and such glasses also exhibit greatly enhanced kinetic stability. Because vapor-deposited glasses can approach the bottom of the amorphous part of the potential energy landscape, they provide insights into the properties expected for the "ideal glass." Connections between vapor-deposited glasses, liquid-cooled glasses, and deeply supercooled liquids are explored. The generality of stable glass formation for organic molecules is discussed along with the prospects for stable glasses of other types of materials.

Evidence for compact cooperatively rearranging regions in a supercooled liquid

International Nuclear Information System (INIS)

Elenius, M; Dzugutov, M

2009-01-01

We examine structural relaxation in a supercooled glass-forming liquid simulated by constant-energy constant-volume (NVE) molecular dynamics. Time correlations of the total kinetic energy fluctuations are used as a comprehensive measure of the system's approach to the ergodic equilibrium. We find that, under cooling, the total structural relaxation becomes delayed as compared with the decay of the component of the intermediate scattering function corresponding to the main peak of the structure factor. This observation can be explained by collective movements of particles preserving many-body structural correlations within compact three-dimensional (3D) cooperatively rearranging regions.

Material Removal Rate for Magnetorheological Finishing (MRF) of Optical Glasses with Nanodiamond MR Fluid

Energy Technology Data Exchange (ETDEWEB)

DeGroote, J.E.; Marino, A.E.; Wilson, J.P.; Bishop, A.L.; Jacobs, S.D.

2007-07-13

We present a material removal rate model for MRF of optical glasses using nanodiamond MR fluid. The new model incorporates terms for drag force, polishing particle properties, chemical durability and glass composition into an existing model that contains only terms for the glass mechanical properties. Experimental results for six optical glasses are given that support this model.

Material Removal Rate for Magnetorheological Finishing (MRF) of Optical Glasses with Nanodiamond MR Fluid

International Nuclear Information System (INIS)

DeGroote, J.E.; Marino, A.E.; Wilson, J.P.; Bishop, A.L.; Jacobs, S.D.

2007-01-01

We present a material removal rate model for MRF of optical glasses using nanodiamond MR fluid. The new model incorporates terms for drag force, polishing particle properties, chemical durability and glass composition into an existing model that contains only terms for the glass mechanical properties. Experimental results for six optical glasses are given that support this model

Effects of PVA(Polyvinyl Alcohol) on Supercooling Phenomena of Water

Science.gov (United States)

Kumano, Hiroyuki; Saito, Akio; Okawa, Seiji; Takizawa, Hiroshi

In this paper, effects of polymer additive on supercooling of water were investigated experimentally. Poly-vinyl alcohol (PVA) were used as the polymer, and the samples were prepared by dissolving PVA in ultra pure water. Concentration, degree of polymerization and saponification of PVA were varied as the experimental parameters. The sample was cooled, and the temperature at the instant when ice appears was measured. Since freezing of supercooled water is statistical phenomenon, many experiments were carried out and average degrees of supercooling were obtained for each experimental condition. As the result, it was found that PVA affects nucleation of supercooling and the degree of supercooling increases by adding the PVA. Especially, it is found that the average degree of supercooling increases and the standard deviation of average degree of supercooling decreases with increase of degree of saponification of PVA. However, the average degree of supercooling are independent of the degree of polymerization of PVA in the range of this study.

Double stage crystallization of bulk Ge20Te80 glass

International Nuclear Information System (INIS)

Parthasarathy, G.; Bandyopadhyay, A.K.; Gopal, E.S.R.; Subbanna, G.N.

1984-01-01

The growing interest of the semiconducting glasses is partly because of their interesting electrical and optical properties. These properties are usually connected with their crystallization. In many glasses, the glass-supercooled liquid transition precedes crystallization. The glass transition temperature (Tsub(g)) is found to exhibit multistage processes for a few systems. In this communication, we report the observation of a double Tsub(g) effect in bulk Ge 20 Te 80 glass and also explain the structural changes taking place in the two stages. (author)

Supercooling of Water Controlled by Nanoparticles and Ultrasound

Science.gov (United States)

Cui, Wei; Jia, Lisi; Chen, Ying; Li, Yi'ang; Li, Jun; Mo, Songping

2018-05-01

Nanoparticles, including Al2O3 and SiO2, and ultrasound were adopted to improve the solidification properties of water. The effects of nanoparticle concentration, contact angle, and ultrasonic intensity on the supercooling degree of water were investigated, as well as the dispersion stability of nanoparticles in water during solidification. Experimental results show that the supercooling degree of water is reduced under the combined effect of ultrasound and nanoparticles. Consequently, the reduction of supercooling degree increases with the increase of ultrasonic intensity and nanoparticle concentration and decrease of contact angle of nanoparticles. Moreover, the reduction of supercooling degree caused by ultrasound and nanoparticles together do not exceed the sum of the supercooling degree reductions caused by ultrasound and nanoparticles separately; the reduction is even smaller than that caused by ultrasound individually under certain conditions of controlled nanoparticle concentration and contact angle and ultrasonic intensity. The dispersion stability of nanoparticles during solidification can be maintained only when the nanoparticles and ultrasound together show a superior effect on reducing the supercooling degree of water to the single operation of ultrasound. Otherwise, the aggregation of nanoparticles appears in water solidification, which results in failure. The relationships among the meaningful nanoparticle concentration, contact angle, and ultrasonic intensity, at which the requirements of low supercooling and high stability could be satisfied, were obtained. The control mechanisms for these phenomena were analyzed.

Effects of Nanodiamond Abrasive Friability in Experimental MR Fluids with Phosphate Laser Glass LHG-8 and Other Optical Glasses

Energy Technology Data Exchange (ETDEWEB)

DeGroote, J.E.; Marino, A.E.; Wilson, J.P.; Spencer, K.E.; Jacobs, S.D.

2005-09-22

Research is currently being conducted to better understand the role that nanodiamond abrasives play in the removal process of Magnetorheological Finishing (MRF). The following presents removal rate data for a set of six optical glasses that were spotted (not polished out) with four different MR fluids, as well as texturing/smoothing data for phosphate laser glass LHG-8.

Vapor Pressure Plus: An Experiment for Studying Phase Equilibria in Water, with Observation of Supercooling, Spontaneous Freezing, and the Triple Point

Science.gov (United States)

Tellinghuisen, Joel

2010-01-01

Liquid-vapor, solid-vapor, and solid-liquid-vapor equilibria are studied for the pure substance water, using modern equipment that includes specially fabricated glass cells. Samples are evaporatively frozen initially, during which they typically supercool to -5 to -10 [degrees]C before spontaneously freezing. Vacuum pumping lowers the temperature…

Quasi-Elastic Neutron Scattering Studies of the Slow Dynamics of Supercooled and Glassy Aspirin

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yang [ORNL; Tyagi, M. [NCNR and University of Maryland; Mamontov, Eugene [ORNL; Chen, Sow-hsin H [ORNL

2011-01-01

Aspirin, also known as acetylsalicylic acid (ASA), is not only a wonderful drug, but also a good glass former. Therefore, it serves as an important molecular system to study the near-arrest and arrested phenomena. In this paper, a high-resolution quasi-elastic neutron scattering (QENS) technique is used to investigate the slow dynamics of supercooled liquid and glassy aspirin from 410 K down to 350 K. The measured QENS spectra can be analyzed with a stretched exponential model. We find that (i) the stretched exponent (Q) is independent of the wave vector transfer Q in the measured Q-range, and (ii) the structural relaxation time (Q) follows a power law dependence on Q. Consequently, the Q-independent structural relaxation time 0 can be extracted for each temperature to characterize the slow dynamics of aspirin. The temperature dependence of 0 can be fitted with the mode coupling power law, the Vogel-Fulcher-Tammann equation and a universal equation for fragile glass forming liquids recently proposed by M. Tokuyama in the measured temperature range. The calculated dynamic response function T(Q,t) using the experimentally determined self-intermediate scattering function of the hydrogen atoms of aspirin shows a direct evidence of the enhanced dynamic fluctuations as the aspirin is increasingly supercooled, in agreement with the fixed-time mean squared displacement x2 and non-Gaussian parameter 2 extracted from the elastic scattering.

Super-cool Dark Matter arXiv

CERN Document Server

Hambye, Thomas; Teresi, Daniele

In dimension-less theories of dynamical generation of the weak scale, the Universe can undergo a period of low-scale inflation during which all particles are massless and super-cool. This leads to a new mechanism of generation of the cosmological Dark Matter (DM) relic density: super-cooling can easily suppress the amount of DM to the desired level. This is achieved for TeV-scale DM, if super-cooling ends when quark condensates form at the QCD phase transition. Along this scenario, the baryon asymmetry can be generated either at the phase transition or through leptogenesis. We show that the above mechanism takes place in old and new dimension-less models.

Structural fluctuations and orientational glass of levoglucosan--High stability against ordering and absence of structural glass.

Science.gov (United States)

Tombari, Elpidio; Johari, G P

2015-03-14

To investigate whether a non-exponential relaxation always indicates 2-4 nm-size regions of dynamic heterogeneity, we studied the kinetic freezing and unfreezing of structural fluctuations involving the rotational modes in orientationally disordered crystal (ODIC) of levoglucosan by calorimetry. The heat capacity, Cp, of levoglucosan measured over the 203 K-463 K range shows that its low-temperature, orientationally ordered crystal (ORC) transforms to ODIC phase on heating, which then melts to a low viscosity liquid. On cooling, the melt transforms to the ODIC which then does not transform to the ORC. Instead, the ODIC supercools. Fluctuations resulting from hindered (random) rotations of levoglucosan molecules confined to the lattice sites and from their conformational changes become progressively slower on cooling and an orientational glass (O-G) forms showing the sigmoid shape decrease in Cp characteristic of structural arrest like that of a glass. On heating the O-G state, rotational fluctuations begin to contribute to Cp at To-g of 247.8 K and there is an overshoot in Cp and thermal hysteresis (characteristic of physical ageing) in the temperature range of 230-260 K. The non-exponential relaxation parameter, β(cal), determined by fitting the Cp data to a non-exponential, nonlinear model for relaxation of a glass is 0.60, which is similar to β(cal) found for polymers, molecular liquids, and metal-alloy melts in which Brownian diffusion occurs. Such β(cal) glass formation, but its value of 0.60 for ODIC levoglucosan, in which Brownian diffusion does not occur, would not indicate such domains. Despite the lack of Brownian diffusion, we discuss these findings in the potential energy landscape paradigm. Levoglucosan melt, which is believed to vitrify and to stabilize a protein's disordered structure, did not supercool even at 200 K/min cooling rate. The findings have consequences for reports on the dielectric relaxation studies that indicated that levoglucosan

Thermal conductivity of supercooled water.

Science.gov (United States)

Biddle, John W; Holten, Vincent; Sengers, Jan V; Anisimov, Mikhail A

2013-04-01

The heat capacity of supercooled water, measured down to -37°C, shows an anomalous increase as temperature decreases. The thermal diffusivity, i.e., the ratio of the thermal conductivity and the heat capacity per unit volume, shows a decrease. These anomalies may be associated with a hypothesized liquid-liquid critical point in supercooled water below the line of homogeneous nucleation. However, while the thermal conductivity is known to diverge at the vapor-liquid critical point due to critical density fluctuations, the thermal conductivity of supercooled water, calculated as the product of thermal diffusivity and heat capacity, does not show any sign of such an anomaly. We have used mode-coupling theory to investigate the possible effect of critical fluctuations on the thermal conductivity of supercooled water and found that indeed any critical thermal-conductivity enhancement would be too small to be measurable at experimentally accessible temperatures. Moreover, the behavior of thermal conductivity can be explained by the observed anomalies of the thermodynamic properties. In particular, we show that thermal conductivity should go through a minimum when temperature is decreased, as Kumar and Stanley observed in the TIP5P model of water. We discuss physical reasons for the striking difference between the behavior of thermal conductivity in water near the vapor-liquid and liquid-liquid critical points.

Precision glass molding: Toward an optimal fabrication of optical lenses

Science.gov (United States)

Zhang, Liangchi; Liu, Weidong

2017-03-01

It is costly and time consuming to use machining processes, such as grinding, polishing and lapping, to produce optical glass lenses with complex features. Precision glass molding (PGM) has thus been developed to realize an efficient manufacture of such optical components in a single step. However, PGM faces various technical challenges. For example, a PGM process must be carried out within the super-cooled region of optical glass above its glass transition temperature, in which the material has an unstable non-equilibrium structure. Within a narrow window of allowable temperature variation, the glass viscosity can change from 105 to 1012 Pas due to the kinetic fragility of the super-cooled liquid. This makes a PGM process sensitive to its molding temperature. In addition, because of the structural relaxation in this temperature window, the atomic structure that governs the material properties is strongly dependent on time and thermal history. Such complexity often leads to residual stresses and shape distortion in a lens molded, causing unexpected changes in density and refractive index. This review will discuss some of the central issues in PGM processes and provide a method based on a manufacturing chain consideration from mold material selection, property and deformation characterization of optical glass to process optimization. The realization of such optimization is a necessary step for the Industry 4.0 of PGM.

A simulation study of homogeneous ice nucleation in supercooled salty water

Science.gov (United States)

Soria, Guiomar D.; Espinosa, Jorge R.; Ramirez, Jorge; Valeriani, Chantal; Vega, Carlos; Sanz, Eduardo

2018-06-01

We use computer simulations to investigate the effect of salt on homogeneous ice nucleation. The melting point of the employed solution model was obtained both by direct coexistence simulations and by thermodynamic integration from previous calculations of the water chemical potential. Using a seeding approach, in which we simulate ice seeds embedded in a supercooled aqueous solution, we compute the nucleation rate as a function of temperature for a 1.85 NaCl mol per water kilogram solution at 1 bar. To improve the accuracy and reliability of our calculations, we combine seeding with the direct computation of the ice-solution interfacial free energy at coexistence using the Mold Integration method. We compare the results with previous simulation work on pure water to understand the effect caused by the solute. The model captures the experimental trend that the nucleation rate at a given supercooling decreases when adding salt. Despite the fact that the thermodynamic driving force for ice nucleation is higher for salty water for a given supercooling, the nucleation rate slows down with salt due to a significant increase of the ice-fluid interfacial free energy. The salty water model predicts an ice nucleation rate that is in good agreement with experimental measurements, bringing confidence in the predictive ability of the model. We expect that the combination of state-of-the-art simulation methods here employed to study ice nucleation from solution will be of much use in forthcoming numerical investigations of crystallization in mixtures.

Experimental evidence for two distinct deeply supercooled liquid states of water – Response to “Comment on ‘Water's second glass transition”’, by G.P. Johari, Thermochim. Acta (2015)

Energy Technology Data Exchange (ETDEWEB)

Stern, J.; Seidl, M. [Institute of Physical Chemistry, University of Innsbruck, 6020 Innsbruck (Austria); Gainaru, C. [Fakultät Physik, Technische Universität Dortmund, 44221 Dortmund (Germany); Fuentes-Landete, V.; Amann-Winkel, K.; Handle, P.H. [Institute of Physical Chemistry, University of Innsbruck, 6020 Innsbruck (Austria); Köster, K.W.; Nelson, H. [Fakultät Physik, Technische Universität Dortmund, 44221 Dortmund (Germany); Böhmer, R., E-mail: roland.bohmer@tu-dortmund.de [Fakultät Physik, Technische Universität Dortmund, 44221 Dortmund (Germany); Loerting, T., E-mail: thomas.loerting@uibk.ac.at [Institute of Physical Chemistry, University of Innsbruck, 6020 Innsbruck (Austria)

2015-10-10

Highlights: • Two samples of amorphous ices quench-recovered from 140 K to 0.07 GPa are compared. • Calorimetry, X-ray diffraction, dielectric spectroscopy and volumetry are employed. • The two samples are distinct and cannot both be termed “pressure-densified glassy water”. • One route of preparation leads to high- (HDA), and the other to low-density amorphous ice (LDA). • Two distinct glass transitions are observed and interpreted to indicate two liquid H{sub 2}O phases. - Abstract: Recently, our earlier data which led us to conclude that deeply supercooled water displays a second glass transition (Amann-Winkel et al., 2013) was reinterpreted (Johari, 2015). In particular, the increase in heat capacity observed for high-density amorphous ice (HDA) samples at 116 K was reinterpreted to indicate sub-T{sub g} features of low-density amorphous ice's (LDA's) glass transition. We reply to the criticism in detail and report an experiment triggered by the comment on our work. This experiment unequivocally confirms our original interpretation of the observations and reinforces the case for water's second glass transition, its polyamorphism, and the observation of two distinct ultraviscous states of water differing by about 25% in density.

Amorphous ices explained in terms of nonequilibrium phase transitions in supercooled water

Science.gov (United States)

Limmer, David; Chandler, David

2013-03-01

We analyze the phase diagram of supercooled water out-of-equilibrium using concepts from space-time thermodynamics and the dynamic facilitation theory of the glass transition, together with molecular dynamics simulations. We find that when water is driven out-of-equilibrium, it can exist in multiple amorphous states. In contrast, we find that when water is at equilibrium, it can exist in only one liquid state. The amorphous non-equilibrium states are solids, distinguished from the liquid by their lack of mobility, and distinguished from each other by their different densities and local structure. This finding explains the experimentally observed polyamorphism of water as a class of nonequilibrium phenomena involving glasses of different densities. While the amorphous solids can be long lived, they are thermodynamically unstable. When allowed to relax to equilibrium, they crystallize with pathways that pass first through liquid state configurations and then to ordered ice.

Effects of poly-vinyl alcohol on supercooling phenomena of water

Energy Technology Data Exchange (ETDEWEB)

Kumano, Hiroyuki; Hirata, Tetsuo; Kudoh, Tomoya [Department of Mechanical Systems Engineering, Shinshu University, 4-17-1, Wakasato, Nagano City, 380-8553 (Japan)

2009-05-15

The effects of a polymer additive on the supercooling of water were investigated experimentally. Poly-vinyl alcohols (PVAs) were used as the additives, and samples were prepared by dissolving the PVA in water. Since the characteristics of PVA are decided by its degrees of polymerization and saponification, these were varied along with the concentration as the experimental parameters. Moreover, the effect of purity of the water was also considered. Each sample was cooled and the temperature at the instant when ice appeared was measured. Since the freezing of supercooled water is a statistical phenomenon, many experiments were carried out and the average degree of supercooling was obtained. It was found that PVA affects the nucleation of ice in supercooled water and the degree of supercooling increases with the addition of PVA even for water with low purity. The average degree of supercooling increases with an increase in the degree of saponification of PVA. (author)

Quasi-elastic neutron scattering studies of the slow dynamics of supercooled and glassy aspirin

International Nuclear Information System (INIS)

Zhang Yang; Mamontov, Eugene; Tyagi, Madhusudan; Chen, Sow-Hsin

2012-01-01

Aspirin, also known as acetylsalicylic acid (ASA), is not only a wonderful drug, but also a good glass former. Therefore, it serves as an important molecular system to study the near-arrest and arrested phenomena. In this paper, a high-resolution quasi-elastic neutron scattering (QENS) technique is used to investigate the slow dynamics of supercooled liquid and glassy aspirin from 410 down to 350 K. The measured QENS spectra can be analyzed with a stretched exponential model. We find that (i) the stretched exponent β(Q) is independent of the wavevector transfer Q in the measured Q range and (ii) the structural relaxation time τ(Q) follows a power-law dependence on Q. Consequently, the Q-independent structural relaxation time τ 0 can be extracted for each temperature to characterize the slow dynamics of aspirin. The temperature dependence of τ 0 can be fitted with the mode-coupling power law, the Vogel-Fulcher-Tammann equation and a universal equation for fragile glass forming liquids recently proposed by Tokuyama in the measured temperature range. The calculated dynamic response function χ T (Q, t) using the experimentally determined self-intermediate scattering function of the hydrogen atoms of aspirin shows direct evidence of the enhanced dynamic fluctuations as the aspirin is increasingly supercooled, in agreement with the fixed-time mean squared displacement (x 2 ) and the non-Gaussian parameter α 2 extracted from the elastic scattering.

Quasi-elastic neutron scattering studies of the slow dynamics of supercooled and glassy aspirin

Science.gov (United States)

Zhang, Yang; Tyagi, Madhusudan; Mamontov, Eugene; Chen, Sow-Hsin

2012-02-01

Aspirin, also known as acetylsalicylic acid (ASA), is not only a wonderful drug, but also a good glass former. Therefore, it serves as an important molecular system to study the near-arrest and arrested phenomena. In this paper, a high-resolution quasi-elastic neutron scattering (QENS) technique is used to investigate the slow dynamics of supercooled liquid and glassy aspirin from 410 down to 350 K. The measured QENS spectra can be analyzed with a stretched exponential model. We find that (i) the stretched exponent β(Q) is independent of the wavevector transfer Q in the measured Q range and (ii) the structural relaxation time τ(Q) follows a power-law dependence on Q. Consequently, the Q-independent structural relaxation time τ0 can be extracted for each temperature to characterize the slow dynamics of aspirin. The temperature dependence of τ0 can be fitted with the mode-coupling power law, the Vogel-Fulcher-Tammann equation and a universal equation for fragile glass forming liquids recently proposed by Tokuyama in the measured temperature range. The calculated dynamic response function χT(Q, t) using the experimentally determined self-intermediate scattering function of the hydrogen atoms of aspirin shows direct evidence of the enhanced dynamic fluctuations as the aspirin is increasingly supercooled, in agreement with the fixed-time mean squared displacement langx2rang and the non-Gaussian parameter α2 extracted from the elastic scattering.

Supercooled smectic nanoparticles

DEFF Research Database (Denmark)

Kuntsche, Judith; Westesen, K; Drechsler, M

2004-01-01

The possibility of preparing nanoparticles in the supercooled thermotropic liquid crystalline state from cholesterol esters with saturated acyl chains as well as the incorporation of model drugs into the dispersions was investigated using cholesteryl myristate (CM) as a model cholesterol ester....

Glass-forming ability and crystallization behavior of some binary and ternary Ni-based glassy alloys

International Nuclear Information System (INIS)

Louzguine-Luzgin, Dmitri V.; Louzguina-Luzgina, Larissa V.; Xie Guoqiang; Li Song; Zhang Wei; Inoue, Akihisa

2008-01-01

The purpose of the current paper is to study the influence of Ti, V, Nb, Al, Sn and Pd additions on the glass-forming ability, formation of a supercooled liquid region and a devitrification process of some Ni-Zr glassy alloys as well as to compare the results with those obtained for similar Cu-based alloys studied earlier. The Ni-based glassy alloys were investigated by using X-ray diffraction, differential scanning and isothermal calorimetries. Although the studied Ni-based alloys showed high values of the reduced glass-transition temperature of about 0.6, their glass-forming ability is quite low. This fact may be explained by low stability of the supercooled liquid against crystallization and formation of the equilibrium intermetallic compounds with a high growth rate compared to those observed in similar Cu-based alloys studied earlier. Relatively low thermal conductivity of Ni-based alloys is also found to be another factor limiting their glass-forming ability

Liquid -to-glass transition in bulk glass-forming Cu55-xZr45Agx alloys using molecular dynamic simulations

Directory of Open Access Journals (Sweden)

Celtek M.

2011-05-01

Full Text Available We report results from molecular dynamics (MD studies concerning the microscopic structure of the ternary, bulk metallic glass-forming Cu55-x Zr45Agx (x=0,10,20 alloys using tight-binding potentials. Understanding of the nature of Glass Forming Ability (GFA of studied alloys, GFA parameters, glass transition temperature (T-g, melting temperature (T-m, reduced glass transition temperature (T-g/T-m, the supercooled liquid region and other parameters were simulated and compared with experiments. The computed pair distribution functions reproduce well experimental x-ray data of Inoue and co-workers. Structure analysis of the Cu-Zr-Ag alloy based on MD simulation will be also presented

Supercooling of aqueous NaCl and KCl solutions under acoustic levitation.

Science.gov (United States)

Lü, Y J; Wei, B

2006-10-14

The supercooling capability of aqueous NaCl and KCl solutions is investigated at containerless state by using acoustic levitation method. The supercooling of water is obviously enhanced by the alkali metal ions and increases linearly with the augmentation of concentrations. Furthermore, the supercooling depends on the nature of ions and is 2-3 K larger for NaCl solution than that for KCl solution in the present concentration range: Molecular dynamics simulations are performed to reveal the intrinsic correlation between supercoolability and microstructure. The translational and orientational order parameters are applied to quantitatively demonstrate the effect of ionic concentration on the hydrogen-bond network and ice melting point. The disrupted hydrogen-bond structure determines essentially the concentration dependence of supercooling. On the other hand, the introduced acoustic pressure suppresses the increase of supercooling by promoting the growth and coalescence of microbubbles, the effective nucleation catalysts, in water. However, the dissolved ions can weaken this effect, and moreover the degree varies with the ion type. This results in the different supercoolability for NaCl and KCl solutions under the acoustic levitation conditions.

Predicting How Nanoconfinement Changes the Relaxation Time of a Supercooled Liquid

DEFF Research Database (Denmark)

Ingebrigtsen, Trond; Errington, Jeff; Truskett, Tom

2013-01-01

The properties of nanoconfined fluids can be strikingly different from those of bulk liquids. A basic unanswered question is whether the equilibrium and dynamic consequences of confinement are related to each other in a simple way. We study this question by simulation of a liquid comprising...... asymmetric dumbbell-shaped molecules, which can be deeply supercooled without crystallizing. We find that the dimensionless structural relaxation times—spanning six decades as a function of temperature, density, and degree of confinement—collapse when plotted versus excess entropy. The data also collapse...

The effect of Al substitution on thermal and mechanical properties of Fe-based bulk metallic glass

International Nuclear Information System (INIS)

Ma, R.D.; Zhang, H.F.; Yu, H.S.; Hu, Z.Q.

2008-01-01

In this paper, a systematic investigation about the effect of Al substitution on properties of Fe-Cr-Mo-Er-C-B amorphous material, including glass-forming ability (GFA), thermal properties, and mechanical properties was presented. It was found out by X-ray diffraction (XRD) that the glass-forming ability decreased with the increase of Al, when Al reached 7 at%, fully amorphous specimen was not obtained. With regard to thermal parameters, such as glass transition temperature T g , crystallization temperature T x , supercooled liquid region ΔT x , and reduced glass temperature T rg were checked by differential scanning calorimeter. A rather wide supercooled liquid region more than 40 K was found. During compression test, results showed Al substitution slightly improved the fracture strength from 3.4 to 3.7 GPa. The fracture morphology was observed by scanning electron microscopy. Micrographs showed the same cleavage-like fracture in spite of different Al substitution

Ideal glass transitions by random pinning

Science.gov (United States)

Cammarota, Chiara; Biroli, Giulio

2012-01-01

We study the effect of freezing the positions of a fraction c of particles from an equilibrium configuration of a supercooled liquid at a temperature T. We show that within the random first-order transition theory pinning particles leads to an ideal glass transition for a critical fraction c = cK(T) even for moderate supercooling; e.g., close to the Mode-Coupling transition temperature. First we derive the phase diagram in the T - c plane by mean field approximations. Then, by applying a real-space renormalization group method, we obtain the critical properties for |c - cK(T)| → 0, in particular the divergence of length and time scales, which are dominated by two zero-temperature fixed points. We also show that for c = cK(T) the typical distance between frozen particles is related to the static point-to-set length scale of the unconstrained liquid. We discuss what are the main differences when particles are frozen in other geometries and not from an equilibrium configuration. Finally, we explain why the glass transition induced by freezing particles provides a new and very promising avenue of research to probe the glassy state and ascertain, or disprove, the validity of the theories of the glass transition. PMID:22623524

Formation of centimeter Fe-based bulk metallic glasses in low vacuum environment

Energy Technology Data Exchange (ETDEWEB)

Pan Jie; Chen Qi; Li Ning [State Key Lab of Materials Processing and Mould Technology, Department of Materials Science and Technology, Huazhong University of Science and Technology, 430074 Wuhan (China); Liu Lin [State Key Lab of Materials Processing and Mould Technology, Department of Materials Science and Technology, Huazhong University of Science and Technology, 430074 Wuhan (China)], E-mail: lliu2000@public.wh.hb.cn

2008-09-08

The formation of a Fe{sub 43.7}Co{sub 7.3}Cr{sub 14.7}Mo{sub 12.6}C{sub 15.5}B{sub 4.3}Y{sub 1.9} bulk metallic glass (BMG) was attempted in low vacuum environment and in air using commercial raw materials. The glass forming ability of the Fe-based alloys was studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and differential thermal analyzer (DTA). It was found that cylindric rods with diameters ranging from 10 mm to 5 mm could be successfully fabricated by copper-mold casting in the pressures from 1.5 Pa to 10{sup 5} Pa (10{sup 5} Pa = 1 atm). All BMGs exhibit a distinct glass transition and wide supercooled liquid region. The preparation condition seems not significantly affected by the thermodynamic parameters of BMG, such as supercooled liquid region, glass transition temperature and melting process. The oxygen content of the alloys prepared in different vacuum conditions was measured by a LECO oxygen analyzer, which revealed that the oxygen content was less than 100 ppm for all BMGs prepared, even in air. The good glass forming ability and excellent oxidation resistance for the present Fe-based alloy are discussed.

Supercooling suppression of microencapsulated phase change materials by optimizing shell composition and structure

International Nuclear Information System (INIS)

Cao, Fangyu; Yang, Bao

2014-01-01

Highlights: • A new method for supercooling suppression of microPCMs by optimizing the structure of the microcapsule shell. • Large effective latent heat (up to 213 J/g) of the microPCMs, much higher than those using additive as nucleating agents. • Change of shell composition and structure significantly affects the phase transition processes of the encapsulated PCMs. • The latent heat of the shell-induced phase transition is maximized, reaching 83.7% of the latent heat of bulk octadecane. • Hollow spheres with porous rather than solid resin shell are also formed when the SDS concentration is very high. - Abstract: A new method for supercooling suppression of microencapsulated phase change materials (PCMs) has been developed by optimizing the composition and structure of the microcapsule resin shell. The microcapsules comprising paraffin octadecane encapsulated in melamine–formaldehyde resin shell were synthesized with the use the oil-in-water emulsion technique. These PCM microcapsules are 5–15 μm in diameter. The supercooling of these octadecane microcapsules can be as large as 13.6 °C, when the homogeneous nucleation is dominant during the melt crystallization into the thermodynamically stable triclinic phase. It is discovered that the homogeneous nucleation can be mediated by shell-induced nucleation of the triclinic phase and the metastable rotator phase when the shell composition and structure are optimized, without need of any nucleating additives. The effects of synthesis parameters, such as ratio of melamine to formaldehyde, pH of pre-polymer, and pH of emulsion, on the phase transition properties of the octadecane microcapsules have been investigated systemically. The optimum synthesis conditions have been identified in terms of minimizing the supercooling while maintaining heat capacity. Potential applications of this type of phase changeable microcapsules include high heat capacity thermal fluids, thermal management in smart buildings

CFD Study of Fluid Flow in an All-glass Evacuated Tube Solar Water Heater

DEFF Research Database (Denmark)

Ai, Ning; Fan, Jianhua; Li, Yumin

2008-01-01

Abstract: The all-glass evacuated tube solar water heater is one of the most widely used solar thermal technologies. The aim of the paper is to investigate fluid flow in the solar water heater by means of computational fluid dynamics (CFD). The investigation was carried out with a focus on the co...... for future system optimization....

Supercooled dynamics of glass-forming liquids and polymers under hydrostatic pressure

Energy Technology Data Exchange (ETDEWEB)

Roland, C M [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States); Hensel-Bielowka, S [Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice (Poland); Paluch, M [Institute of Physics, Silesian University, ul. Uniwersytecka 4, 40-007 Katowice (Poland); Casalini, R [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States); Chemistry Department, George Mason University, Fairfax, VA 22030 (United States)

2005-06-01

An intriguing problem in condensed matter physics is understanding the glass transition, in particular the dynamics in the equilibrium liquid close to vitrification. Recent advances have been made by using hydrostatic pressure as an experimental variable. These results are reviewed, with an emphasis in the insight provided into the mechanisms underlying the relaxation properties of glass-forming liquids and polymers.

Density of states of colloidal glasses and supercooled liquids

NARCIS (Netherlands)

Ghosh, A.; Mari, R.; Chikkadi, V.; Schall, P.; Kurchan, J.; Bonn, D.

2010-01-01

The glass transition is perhaps the greatest unsolved problem in condensed matter physics: the main question is how to reconcile the liquid-like structure with solid-like mechanical properties. In solids, structure and mechanics are related directly through the vibrational density of states of the

Seasonal change in the capacity for supercooling by neonatal painted turtles.

Science.gov (United States)

Packard, G C; Packard, M J; McDaniel, L L

2001-05-01

Hatchlings of the North American painted turtle (Chrysemys picta) typically spend their first winter of life inside the shallow, subterranean nest where they completed incubation the preceding summer. This facet of their natural history commonly causes neonates in northerly populations to be exposed in mid-winter to ice and cold, which many animals survive by remaining unfrozen and supercooled. We measured the limit of supercooling in samples of turtles taken shortly after hatching and in other samples after 2 months of acclimation (or acclimatization) to a reduced temperature in the laboratory or field. Animals initially had only a limited capacity for supercooling, but they acquired an ability to undergo deeper supercooling during the course of acclimation. The gut of most turtles was packed with particles of soil and eggshell shortly after hatching, but not after acclimation. Thus, the relatively high limit of supercooling for turtles in the days immediately after hatching may have resulted from the ingestion of soil (and associated nucleating agents) by the animals as they were freeing themselves from their eggshell, whereas the relatively low limit of supercooling attained by acclimated turtles may have resulted from their purging their gut of its contents. Parallels may, therefore, exist between the natural-history strategy expressed by hatchling painted turtles and that expressed by numerous terrestrial arthropods that withstand the cold of winter by sustaining a state of supercooling.

Structural behavior of Pd40Cu30Ni10P20 bulk metallic glass below and above the glass transition

DEFF Research Database (Denmark)

Mattern, N.; Hermann, H.; Roth, S.

2003-01-01

The thermal behavior of the structure of Pd40Cu30Ni10P20 bulk metallic glass has been investigated in situ through the glass transition by means of high-temperature x-ray synchrotron diffraction. The dependence of the x-ray structure factor S(q) of the Pd40Cu30Ni10P20 glass on temperature follows...... the Debye theory up to the glass transition with a Debye temperature theta=296 K. Above the glass transition temperature T-g, the temperature dependence of S(q) is altered, pointing to a continuous development of structural changes in the liquid with temperature. The atomic pair correlation functions g......(r) indicate changes in short-range-order parameters of the first and the second neighborhood with temperature. The temperature dependence of structural parameters is different in glass and in supercooled liquid, with a continuous behavior through the glass transition. The nearest-neighbor distance decreases...

Fundamental research on supercooling phenomenon on heat transfer surface

International Nuclear Information System (INIS)

Saito, A.; Okawa, S.; Koganezawa, S.

1991-01-01

In relation to the problem of supercooling for ice storage devices, experiments on freezing a relatively large volume of supercooled water is carried out. In the experiment, an experimental method to determine a probability of freezing a large volume of supercooled water with a uniform temperature distribution is introduced. It is accomplished by dividing the water into many smaller droplets. In a statistical analysis, a method to improve an accuracy in a case of having a limited number of experiments is introduced, and the probability of freezing is calculated for each degree of supercooling. The average freezing temperature for the experiment is placed just at the extended region of the other researchers results worked on small droplets. By relating the value with the probability of freezing on various kinds of heat transfer surfaces, the probability of freezing which is independent of the surface is calculated. In this paper it is confirmed to be negligible compared with the one on the surface

Simulated body-fluid tests and electrochemical investigations on biocompatibility of metallic glasses

International Nuclear Information System (INIS)

Lin, C.H.; Huang, C.H.; Chuang, J.F.; Lee, H.C.; Liu, M.C.; Du, X.H.; Huang, J.C.; Jang, J.S.C.; Chen, C.H.

2012-01-01

This paper presents the in-vitro and electrochemical investigations of four metallic glasses (MGs) for finding potential MG-based bio-materials. The simulation body-fluid Hanks solution is utilized for testing the corrosion resistance of MGs, and microorganisms of Escherichia coli are used in testing the bio-toxicity. In addition, a simple cyclic voltammetry method is used for rapid verification of the potential electrochemical responses. It is found that the Zr-based MG can sustain in the body-fluid, exhibiting the best corrosion resistance and electrochemical stability. The microbiologic test shows that E. coli can grow on the surface of the Zr-based metallic glass, confirming the low cell toxicity of this Zr-based MG. Highlights: ► Vanadium is added in Cu–Zr–Al alloy to induce B2-CuZr formation. ► The more induced B2-CuZr phase can improve compressive plasticity. ► The plasticity improvement might be caused by B2 phase dynamic coarsening.

High-energy γ-irradiation effect on physical ageing in Ge-Se glasses

International Nuclear Information System (INIS)

Golovchak, R.; Kozdras, A.; Kozyukhin, S.; Shpotyuk, O.

2009-01-01

Effect of Co 60 γ-irradiation on physical ageing in binary Ge x Se 100-x glasses (5 ≤ x ≤ 27) is studied using conventional differential scanning calorimetry method. It is shown, that high-energy irradiation leads to additional increase in the glass transition temperature and endothermic peak area near the glass transition region over the one induced by isochronal storage of these glasses at normal conditions. This γ-induced physical ageing is shown to be well-pronounced in Se-rich glasses (x < 20), while only negligible changes are recorded for glasses of 20 ≤ x ≤ 27 compositions. The effect under consideration is supposed to be associated with γ-activated structural relaxation of the glass network towards thermodynamic equilibrium of supercooled liquid.

High-energy {gamma}-irradiation effect on physical ageing in Ge-Se glasses

Energy Technology Data Exchange (ETDEWEB)

Golovchak, R. [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202 Stryjska Str., Lviv, UA-79031 (Ukraine); Kozdras, A. [Department of Physics of Opole University of Technology, 75 Ozimska Str., Opole, PL-45370 (Poland); Department of Economy of Academy of Management and Administration in Opole, 18 Niedzialkowski Str., Opole, PL-45085 (Poland); Kozyukhin, S. [Institute of General and Inorganic Chemistry of RAS, Leninsky Pr. 31, Moscow 199991 (Russian Federation); Shpotyuk, O. [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202 Stryjska Str., Lviv, UA-79031 (Ukraine); Institute of Physics of Jan Dlugosz University, 13/15 al. Armii Krajowej, Czestochowa, PL-42201 (Poland)], E-mail: shpotyuk@novas.lviv.ua

2009-09-01

Effect of Co{sup 60} {gamma}-irradiation on physical ageing in binary Ge{sub x}Se{sub 100-x} glasses (5 {<=} x {<=} 27) is studied using conventional differential scanning calorimetry method. It is shown, that high-energy irradiation leads to additional increase in the glass transition temperature and endothermic peak area near the glass transition region over the one induced by isochronal storage of these glasses at normal conditions. This {gamma}-induced physical ageing is shown to be well-pronounced in Se-rich glasses (x < 20), while only negligible changes are recorded for glasses of 20 {<=} x {<=} 27 compositions. The effect under consideration is supposed to be associated with {gamma}-activated structural relaxation of the glass network towards thermodynamic equilibrium of supercooled liquid.

Xylem development in prunus flower buds and the relationship to deep supercooling.

Science.gov (United States)

Ashworth, E N

1984-04-01

Xylem development in eight Prunus species was examined and the relationship to deep supercooling assessed. Dormant buds of six species, P. armeniaca, P. avium, P. cerasus, P. persica, P. salicina, and P. sargentii deep supercooled. Xylem vessel elements were not observed within the dormant floral primordia of these species. Instead, discrete bundles containing procambial cells were observed. Vascular differentiation resumed and xylem continuity was established during the time that the capacity to deep supercool was lost. In P. serotina and P. virginiana, two species which do not supercool, xylem vessels ran the length of the inflorescence and presumably provided a conduit for the spread of ice into the bud. The results support the hypothesis that the lack of xylem continuity is an important feature of buds which deep supercool.

Predicting glass-to-glass and liquid-to-liquid phase transitions in supercooled water using classical nucleation theory

Science.gov (United States)

Tournier, Robert F.

2018-01-01

Glass-to-glass and liquid-to-liquid phase transitions are observed in bulk and confined water, with or without applied pressure. They result from the competition of two liquid phases separated by an enthalpy difference depending on temperature. The classical nucleation equation of these phases is completed by this quantity existing at all temperatures, a pressure contribution, and an enthalpy excess. This equation leads to two homogeneous nucleation temperatures in each liquid phase; the first one (Tn- below Tm) being the formation temperature of an "ordered" liquid phase and the second one corresponding to the overheating temperature (Tn+ above Tm). Thermodynamic properties, double glass transition temperatures, sharp enthalpy and volume changes are predicted in agreement with experimental results. The first-order transition line at TLL = 0.833 × Tm between fragile and strong liquids joins two critical points. Glass phase above Tg becomes "ordered" liquid phase disappearing at TLL at low pressure and at Tn+ = 1.302 × Tm at high pressure.

Breaking the glass ceiling: Configurational entropy measurements in extremely supercooled liquids

Science.gov (United States)

Berthier, Ludovic

Liquids relax extremely slowly on approaching the glass state. One explanation is that an entropy crisis, due to the rarefaction of available states, makes it increasingly arduous to reach equilibrium in that regime. Validating this scenario is challenging, because experiments offer limited resolution, while numerical studies lag more than eight orders of magnitude behind experimentally-relevant timescales. In this work we not only close the colossal gap between experiments and simulations but manage to create in-silico configurations that have no experimental analog yet. Deploying a range of computational tools, we obtain four independent estimates of their configurational entropy. These measurements consistently indicate that the steep entropy decrease observed in experiments is found in simulations even beyond the experimental glass transition. Our numerical results thus open a new observational window into the physics of glasses and reinforce the relevance of an entropy crisis for understanding their formation.

Predicting how nanoconfinement changes the relaxation time of a supercooled liquid.

Science.gov (United States)

Ingebrigtsen, Trond S; Errington, Jeffrey R; Truskett, Thomas M; Dyre, Jeppe C

2013-12-06

The properties of nanoconfined fluids can be strikingly different from those of bulk liquids. A basic unanswered question is whether the equilibrium and dynamic consequences of confinement are related to each other in a simple way. We study this question by simulation of a liquid comprising asymmetric dumbbell-shaped molecules, which can be deeply supercooled without crystallizing. We find that the dimensionless structural relaxation times-spanning six decades as a function of temperature, density, and degree of confinement-collapse when plotted versus excess entropy. The data also collapse when plotted versus excess isochoric heat capacity, a behavior consistent with the existence of isomorphs in the bulk and confined states.

Theory of glass

International Nuclear Information System (INIS)

Rivier, N.

1985-01-01

The physical properties of glass are direct consequences of its non-crystalline structure. The structure is described from a topological point of view, since topology is the only geometry surviving non-crystallinity, i.e. absence of metric and trivial space group. This fact has two main consequences: the overall homogeneity of glass is a gauge symmetry, and the only extended, structurally stable constituents are odd lines (or 2π-disclinations in the elastic continuum limit). A gauge theory of glass, based on odd lines as sources of frozen-in strain, can explain those properties of glasses which are both specific to, and universal in amorphous solids: low-temperature excitations, and relaxation at high temperatures. The methods of statistical mechanics can be applied to give a minimal description of amorphous structures in statistical equilibrium. Criteria for statistical equilibrium of the structure and detailed balance are given, together with structural equations of state, which turn out to be well-known empirically among botanists and metallurgists. This review is based on lectures given in 1984 in Niteroi. It contains five parts: I - Structure, from a topological viewpoint; II - gauge invariance; III - Tunneling modes; IV - Supercooled liquid and the glass transitions; V - Statistical crystallography. (Author) [pt

Preparation and studies on surface modifications of calcium-silico-phosphate ferrimagnetic glass-ceramics in simulated body fluid

International Nuclear Information System (INIS)

Sharma, K.; Dixit, A.; Singh, Sher; Jagannath,; Bhattacharya, S.; Prajapat, C.L.; Sharma, P.K.; Yusuf, S.M.; Tyagi, A.K.; Kothiyal, G.P.

2009-01-01

The structure and magnetic behaviour of 34SiO 2 -(45 - x) CaO-16P 2 O 5 -4.5 MgO-0.5 CaF 2 - x Fe 2 O 3 (where x = 5, 10, 15, 20 wt.%) glasses have been investigated. Ferrimagnetic glass-ceramics are prepared by melt quench followed by controlled crystallization. The surface modification and dissolution behaviour of these glass-ceramics in simulated body fluid (SBF) have also been studied. Phase formation and magnetic behaviour have been studied using XRD and SQUID magnetometer. The room temperature Moessbauer study has been done to monitor the local environment around Fe cations and valence state of Fe ions. X-ray photoelectron spectroscopy (XPS) was used to study the surface modification in glass-ceramics when immersed in simulated body fluid. Formation of bioactive layer in SBF has been ascertained using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The SBF solutions were analyzed using an absorption spectrophotometer. The magnetic measurements indicated that all these glasses possess paramagnetic character and the [Fe 2+ /Fe 3+ ] ions ratio depends on the composition of glass and varied with Fe 2 O 3 concentration in glass matrix. In glass-ceramics saturation magnetization increases with increase in amount of Fe 2 O 3 . The nanostructure of hematite and magnetite is formed in the glass-ceramics with 15 and 20 wt.% Fe 2 O 3 , which is responsible for the magnetic property of these glass-ceramics. Introduction of Fe 2 O 3 induces several modifications at the glass-ceramics surface when immersed in SBF solution and thereby affecting the surface dissolution and the formation of the bioactive layer.

Thermochemical modeling of nuclear waste glass

International Nuclear Information System (INIS)

Spear, K.E.; Besmann, T.M.; Beahm, E.C.

1998-06-01

The development of assessed and consistent phase equilibria and thermodynamic data for major glass constituents used to incorporate high-level nuclear waste is discussed in this paper. The initial research has included the binary Na 2 O-SiO 2 , Na 2 O-Al 2 O 3 , and SiO 2 -Al 2 O 3 systems. The nuclear waste glass is assumed to be a supercooled liquid containing the constituents in the glass at temperatures of interest for nuclear waste storage. Thermodynamic data for the liquid solutions were derived from mathematical comparisons of phase diagram information and the thermodynamic data available for crystalline solid phases. An associate model is used to describe the liquid solution phases. Utilizing phase diagram information provides very stringent limits on the relative thermodynamic stabilities of all phases which exist in a given system

Size-dependent penetrant diffusion in polymer glasses.

Science.gov (United States)

Meng, Dong; Zhang, Kai; Kumar, Sanat K

2018-05-18

Molecular Dynamics simulations are used to understand the underpinning basis of the transport of gas-like solutes in deeply quenched polymeric glasses. As found in previous work, small solutes, with sizes smaller than 0.15 times the chain monomer size, move as might be expected in a medium with large pores. In contrast, the motion of larger solutes is activated and is strongly facilitated by matrix motion. In particular, solute motion is coupled to the local elastic fluctuations of the matrix as characterized by the Debye-Waller factor. While similar ideas have been previously proposed for the viscosity of supercooled liquids above their glass transition, to our knowledge, this is the first illustration of this concept in the context of solute mass transport in deeply quenched polymer glasses.

Internal friction behaviours in Zr57Al10Ni12.4Cu15.6Nb5 bulk metallic glass

International Nuclear Information System (INIS)

Zhang Bo; Zu Fangqiu; Zhen Kang; Shui Jiapeng; Wen Ping

2002-01-01

The internal friction patterns of Zr 57 Al 10 Ni 12.4 Cu 15.6 Nb 5 bulk metallic glass (BMG) were investigated with different frequencies and heating rates. An internal friction peak with extremely large magnitude is observed in the internal friction curves as a function of temperature (Q -1 -T curves). The internal friction peak was fitted by an equation Q -1 =AX(T)/η, where A is a constant, X(T) is the fraction of the glass/supercooled liquid and the viscosity η obeys the Vogel-Fulcher-Tammann relation. We confirm that the internal friction peak originates from both of the glass transition and crystallization. The anomalous behaviours of the peak suggest that Zr 57 Al 10 Ni 12.4 Cu 15.6 Nb 5 BMG has a wide supercooled liquid region and the magnitude of the peak can be used to judge the glass forming ability (GFA) of the glass forming alloys. In addition, the internal friction technique proved to be a new powerful tool for studying structural relaxation and phase transition as well as the GFA of BMG. (author)

Thermal expansion accompanying the glass-liquid transition and crystallization

Directory of Open Access Journals (Sweden)

M. Q. Jiang

2015-12-01

Full Text Available We report the linear thermal expansion behaviors of a Zr-based (Vitreloy 1 bulk metallic glass in its as-cast, annealed and crystallized states. Accompanying the glass-liquid transition, the as-cast Vitreloy 1 shows a continuous decrease in the thermal expansivity, whereas the annealed glass shows a sudden increase. The crystallized Vitreloy 1 exhibits an almost unchanged thermal expansivity prior to its melting. Furthermore, it is demonstrated that the nucleation of crystalline phases can induce a significant thermal shrinkage of the supercooled liquid, but with the growth of these nuclei, the thermal expansion again dominates. These results are explained in the framework of the potential energy landscape, advocating that the configurational and vibrational contributions to the thermal expansion of the glass depend on both, structure and temperature.

Comparison of the Supercooled Spin Liquid States in the Pyrochlore Magnets Dy2Ti2O7 and Ho2Ti2O7

Science.gov (United States)

Eyal, Anna; Eyvazov, Azar B.; Dusad, Ritika; Munsie, Timothy J. S.; Luke, Graeme M.; Davis, J. C. Séamus

Despite a well-ordered crystal structure and strong magnetic interactions between the Dy or Ho ions, no long-range magnetic order has been detected in the pyrochlore titanates Ho2Ti2O7 and Dy2Ti2O7. The low temperature state in these materials is governed by spin-ice rules. These constrain the Ising like spins in the materials, yet does not result in a global broken symmetry state. To explore the actual magnetic phases, we simultaneously measure the time- and frequency-dependent magnetization dynamics of Dy2Ti2O7 and Ho2Ti2O7 using toroidal, boundary-free magnetization transport techniques. We demonstrate a distinctive behavior of the magnetic susceptibility of both compounds, that is indistinguishable in form from the permittivity of supercooled dipolar liquids. Moreover, we show that the microscopic magnetic relaxation times for both materials increase along a super-Arrhenius trajectory also characteristic of supercooled glass-forming liquids. Both materials therefore exhibit characteristics of a supercooled spin liquid. Strongly-correlated dynamics of loops of spins is suggested as a possible mechanism which could account for these findings. Potential connections to many-body spin localization will also be discussed.

New Scenario of Dynamical Heterogeneity in Supercooled Liquid and Glassy States of 2D Monatomic System.

Science.gov (United States)

Van Hoang, Vo; Teboul, Victor; Odagaki, Takashi

2015-12-24

Via analysis of spatiotemporal arrangements of atoms based on their dynamics in supercooled liquid and glassy states of a 2D monatomic system with a double-well Lennard-Jones-Gauss (LJG) interaction potential, we find a new scenario of dynamical heterogeneity. Atoms with the same or very close mobility have a tendency to aggregate into clusters. The number of atoms with high mobility (and size of their clusters) increases with decreasing temperature passing over a maximum before decreasing down to zero. Position of the peak moves toward a lower temperature if mobility of atoms in clusters is lower together with an enhancement of height of the peak. In contrast, the number of atoms with very low mobility or solidlike atoms (and size of their clusters) has a tendency to increase with decreasing temperature and then it suddenly increases in the vicinity of the glass transition temperature leading to the formation of a glassy state. A sudden increase in the number of strongly correlated solidlike atoms in the vicinity of a glass transition temperature (Tg) may be an origin of a drastical increase in viscosity of the glass-forming systems approaching the glass transition. In fact, we find that the diffusion coefficient decays exponentially with a fraction of solidlike atoms exhibiting a sudden decrease in the vicinity of the glass transition region.

COOPERATIVITY, CAGE EFFECT AND HOPPING DIFFUSION IN SUPERCOOLED LIQUIDS AND GLASSES

Directory of Open Access Journals (Sweden)

A.S.Bakai

2003-01-01

Full Text Available Molecular dynamic simulations of structure, thermodynamic and kinetic properties of model metallic Ag-Cu alloy are performed to elucidate its behavior at glass transition. In spite of small variations of inherent structure of the alloy the relaxation kinetics undergo dramatic changes at the glass transition. The time dependences of the mean square displacements and the non-Gaussianity parameter show the signs of anomalous diffusion in an intermediate time region. The analysis of time evolution of van Hove correlation function indicates the existence of both jump displacements and short-range cooperative atomic rearrangements. Below Tg these cooperative rearrangements do not contribute to a long-range diffusion but they still dominate the relaxation at short time.

Crystallization in Pd40Ni40P20 glass

DEFF Research Database (Denmark)

Jiang, Jianzhong; Saksl, K.; Nishiyama, N.

2002-01-01

Phase segregation and the effect of pressure on crystallization of bulk and ribbon Pd40Ni40P20 glasses have been studied by means of differential scanning calorimetry (DSC) and x-ray diffraction. The DSC measurements show only one glass transition event in the samples annealed at different...... temperatures in the supercooled liquid region. Phase analyses reveal at least five crystalline phases crystallized from the glass: monoclinic; body-centered tetragonal; orthorhombic; Ni2Pd2P and fcc-(Ni,Pd) solid solution phases. In the pressure range from 0 to 4.2 GPa, the crystallization temperature...... increases with pressure having a slope of 11 K/GPa. The eutectic crystallization reaction mode and crystalline phases formed are unchanged in the pressure range used. The enhancement of the crystallization temperature with increasing pressure in the glass can be explained by the suppression of atomic...

Long term thermal energy storage with stable supercooled sodium acetate trihydrate

DEFF Research Database (Denmark)

Dannemand, Mark; Schultz, Jørgen M.; Johansen, Jakob Berg

2015-01-01

Utilizing stable supercooling of sodium acetate trihydrate makes it possible to store thermal energy partly loss free. This principle makes seasonal heat storage in compact systems possible. To keep high and stable energy content and cycling stability phase separation of the storage material must...... it expands and will cause a pressure built up in a closed chamber which might compromise stability of the supercooling. This can be avoided by having an air volume above the phase change material connected to an external pressure less expansion tank. Supercooled sodium acetate trihydrate at 20 °C stores up...

Configurational entropy measurements in extremely supercooled liquids that break the glass ceiling

Science.gov (United States)

Berthier, Ludovic; Charbonneau, Patrick; Coslovich, Daniele; Ninarello, Andrea; Ozawa, Misaki; Yaida, Sho

2017-10-01

Liquids relax extremely slowly on approaching the glass state. One explanation is that an entropy crisis, because of the rarefaction of available states, makes it increasingly arduous to reach equilibrium in that regime. Validating this scenario is challenging, because experiments offer limited resolution, while numerical studies lag more than eight orders of magnitude behind experimentally relevant timescales. In this work, we not only close the colossal gap between experiments and simulations but manage to create in silico configurations that have no experimental analog yet. Deploying a range of computational tools, we obtain four estimates of their configurational entropy. These measurements consistently confirm that the steep entropy decrease observed in experiments is also found in simulations, even beyond the experimental glass transition. Our numerical results thus extend the observational window into the physics of glasses and reinforce the relevance of an entropy crisis for understanding their formation.

Anomalous structural evolution and liquid fragility signatures in Cu–Zr and Cu–Hf liquids and glasses

International Nuclear Information System (INIS)

Mauro, N.A.; Vogt, Adam J.; Johnson, Mark L.; Bendert, James C.; Soklaski, Ryan; Yang, Li; Kelton, K.F.

2013-01-01

The results of high energy X-ray scattering studies of equilibrium and supercooled Cu 100−x Zr x (x = 46 and 54) and Cu x Hf 100−x (x = 55 and 60.8) liquids and the corresponding glasses are presented. The liquid data were obtained in a containerless environment using the beamline electrostatic levitation (BESL) technique. The total structure factor and total pair correlation functions were measured as a function of temperature for the liquids, and for the glasses at room temperature. A developing asymmetry in the peak of the first coordination shell in the total pair correlation function suggests chemical ordering in the liquids with cooling. This asymmetry takes the form of two prominent peaks, suggesting two prominent ordering length scales. When the magnitudes of these peaks are extrapolated to the glass transition temperature a discontinuity is observed, indicating that an abrupt increase in the magnitude is required to match the observed peak heights in the glass. This suggests that the structure of the supercooled liquid orders more rapidly near the glass transition temperature, a conclusion that is supported by molecular dynamics simulations. This observed structural evolution of the liquid indicates that the concept of fragility, typically defined from the behavior of viscosity with temperature, has a measurable structural signature as well, which can be observed in X-ray diffraction studies

Supercooling release of micro-size water droplets on microporous surfaces with cooling

Energy Technology Data Exchange (ETDEWEB)

Park, Chun Wan; Kang, Chae Dong [Chonbuk National University, Jeonju (Korea, Republic of)

2012-06-15

The gas diffusion layer (GDL) of polymer electrolyte membrane fuel cells plays a key role in controlling moisture in these cells. When the GDL is exposed to a cold environment, the water droplets or water nets in the GDL freeze. This work observed the supercooling and freezing behaviors of water droplets under low temperature. A GDL made of carbon fiber was coated with a waterproof material with 0%, 40%, and 60% PTFE (polytetrafluoroethylene) contents. The cooling process was investigated according to temperature, and the water droplets on the GDL were supercooled and frozen. Delay in the supercooling release was correlated with the size of water droplets on the GDL and the coating rate of the layer. Moreover, the supercooling degree of the droplets decreased as the number of freeze thaw cycles in the GDL increased.

Analysis of supercooling activity of tannin-related polyphenols.

Science.gov (United States)

Kuwabara, Chikako; Wang, Donghui; Endoh, Keita; Fukushi, Yukiharu; Arakawa, Keita; Fujikawa, Seizo

2013-08-01

Based on the discovery of novel supercooling-promoting hydrolyzable gallotannins from deep supercooling xylem parenchyma cells (XPCs) in Katsura tree (see Wang et al. (2012) [38]), supercooling capability of a wide variety of tannin-related polyphenols (TRPs) was examined in order to find more effective supercooling-promoting substances for their applications. The TRPs examined were single compounds including six kinds of hydrolyzable tannins, 11 kinds of catechin derivatives, two kinds of structural analogs of catechin and six kinds of phenolcarboxylic acid derivatives, 11 kinds of polyphenol mixtures and five kinds of crude plant tannin extracts. The effects of these TRPs on freezing were examined by droplet freezing assays using various solutions containing different kinds of identified ice nucleators such as the ice nucleation bacterium (INB) Erwinia ananas, the INB Xanthomonas campestris, silver iodide and phloroglucinol as well as a solution containing only unintentionally included unidentified airborne ice nucleators. Among the 41 kinds of TRPs examined, all of the hydrolyzable tannins, catechin derivatives, polyphenol mixtures and crude plant tannin extracts as well as a few structural analogs of catechin and phenolcarboxylic acid derivatives exhibited supercooling-promoting activity (SCA) with significant differences (p>0.05) from at least one of the solutions containing different kinds of ice nucleators. It should be noted that there were no TRPs exhibiting ice nucleation-enhancing activity (INA) in all solutions containing identified ice nucleators, whereas there were many TRPs exhibiting INA with significant differences in solutions containing unidentified ice nucleators alone. An emulsion freezing assay confirmed that these TRPs did not essentially affect homogeneous ice nucleation temperatures. It is thought that not only SCA but also INA in the TRPs are produced by interactions with heterogeneous ice nucleators, not by direct interaction with water

Glass Transition Temperature of Saccharide Aqueous Solutions Estimated with the Free Volume/Percolation Model.

Science.gov (United States)

Constantin, Julian Gelman; Schneider, Matthias; Corti, Horacio R

2016-06-09

The glass transition temperature of trehalose, sucrose, glucose, and fructose aqueous solutions has been predicted as a function of the water content by using the free volume/percolation model (FVPM). This model only requires the molar volume of water in the liquid and supercooled regimes, the molar volumes of the hypothetical pure liquid sugars at temperatures below their pure glass transition temperatures, and the molar volumes of the mixtures at the glass transition temperature. The model is simplified by assuming that the excess thermal expansion coefficient is negligible for saccharide-water mixtures, and this ideal FVPM becomes identical to the Gordon-Taylor model. It was found that the behavior of the water molar volume in trehalose-water mixtures at low temperatures can be obtained by assuming that the FVPM holds for this mixture. The temperature dependence of the water molar volume in the supercooled region of interest seems to be compatible with the recent hypothesis on the existence of two structure of liquid water, being the high density liquid water the state of water in the sugar solutions. The idealized FVPM describes the measured glass transition temperature of sucrose, glucose, and fructose aqueous solutions, with much better accuracy than both the Gordon-Taylor model based on an empirical kGT constant dependent on the saccharide glass transition temperature and the Couchman-Karasz model using experimental heat capacity changes of the components at the glass transition temperature. Thus, FVPM seems to be an excellent tool to predict the glass transition temperature of other aqueous saccharides and polyols solutions by resorting to volumetric information easily available.

Step-wise kinetics of natural physical ageing in arsenic selenide glasses

International Nuclear Information System (INIS)

Golovchak, R; Kozdras, A; Balitska, V; Shpotyuk, O

2012-01-01

The long-term kinetics of physical ageing at ambient temperature is studied in Se-rich As-Se glasses using the conventional differential scanning calorimetry technique. It is analysed through the changes in the structural relaxation parameters occurring during the glass-to-supercooled liquid transition in the heating mode. Along with the time dependences of the glass transition temperature (T g ) and partial area (A) under the endothermic relaxation peak, the enthalpy losses (ΔH) and calculated fictive temperature (T F ) are analysed as key parameters, characterizing the kinetics of physical ageing. The latter is shown to have step-wise character, revealing some kinds of subsequent plateaus and steep regions. A phenomenological description of physical ageing in the investigated glasses is proposed on the basis of an alignment-shrinkage mechanism and first-order kinetic equations.

Nanostructure analysis of friction welded Pd-Ni-P/Pd-Cu-Ni-P metallic glass interface

International Nuclear Information System (INIS)

Ohkubo, T.; Shoji, S.; Kawamura, Y.; Hono, K.

2005-01-01

Friction welded Pd 40 Ni 40 P 20 /Pd 40 Cu 30 Ni 10 P 20 metallic glass interface has been characterized by energy filtering transmission electron microscopy. The interface is fully amorphous with a gradual compositional change of Cu and Ni in the range of 30 nm. By annealing above T g , the interdiffusion of Cu and Ni progressed in the supercooled liquid region, and the crystallization occurred from the Pd 40 Ni 40 P 20 glass

Effects of Nb addition on icosahedral quasicrystalline phase formation and glass-forming ability of Zr--Ni--Cu--Al metallic glasses

International Nuclear Information System (INIS)

Fan, Cang; Li, Chunfei; Inoue, Akihisa; Haas, Volker

2001-01-01

This work shows that the crystallization process of Zr--Ni--Cu--Al metallic glass is greatly influenced by adding Nb as an alloying element. Based on the results of the differential scanning calorimetry experiments for metallic glasses Zr 69-x Nb x Ni 10 Cu 12 Al 9 (x=0--15at.%), the crystallization process takes place through two individual stages. For Zr 69 Ni 10 Cu 12 Al 9 (x=0), metastable hexagonal ω-Zr and a small fraction of tetragonal Zr 2 Cu are precipitated upon completion of the first exothermic reaction. Contrary to this alloy, the precipitation of a nanoquasicrystalline phase is detected when 5--10 at.% Nb is added. Furthermore, the crystallization temperature T x , supercooled liquid region ΔT x and reduced temperature T g /T L (T g is the glass transition temperature, T L the liquidus temperature) increase with increasing Nb content. These results indicate that adding Nb content to Zr--Ni--Cu--Al metallic glasses not only induces quasicrystalline phase formation, but also enhances glass-forming ability. Copyright 2001 American Institute of Physics

Ageing effects in As10Se90 chalcogenide glasses induced by gamma-irradiation

International Nuclear Information System (INIS)

Golovchak, R.; Shpotyuk, O.; Shpotyuk, M.; Gorecki, Cz.; Kozdras, A.

2005-01-01

The peculiarities of gamma-induced (Co 60 source, 1.85 MGy absorbed dose) ageing phenomena in As 10 Se 90 chalcogenide glasses are investigated for the first time. The analogy between the observed radiation-induced ageing and the thermally induced one in vitreous selenium is emphasized. Like to thermal treatment, gamma-irradiation leads to an increase in the glass transition temperature and the relaxation rate towards a thermodynamic equilibrium of supercooled liquid, the value of this increase being greater in the case of radiation influence

Thermal properties and surface reactivity in simulated body fluid of new strontium ion-containing phosphate glasses.

Science.gov (United States)

Massera, J; Petit, L; Cardinal, T; Videau, J J; Hupa, M; Hupa, L

2013-06-01

In this paper, we investigate the effect of SrO substitution for CaO in 50P₂O₅-10Na₂-(40-x)CaO-xSrO glass system (x from 0 to 40) on the thermal and structural properties and also on the glass reactivity in simulated body fluid (SBF) in order to find new glass candidates for biomedical glass fibers. The addition of SrO at the expense of CaO seems to restrain the leaching of phosphate ions in the solution limiting the reduction of the solution pH. We observed the formation of an apatite layer at the surface of the glasses when in contact with SBF. SrO and MgO were found in the apatite layer of the strontium ion-containing glasses, the concentration of which increases with an increase of SrO content. We think that it is the presence of MgO and SrO in the layer which limits the leaching of phosphate in the solution and thus the glass dissolution in SBF.

Infrared spectroscopy study of structural changes in glass-forming salol.

Science.gov (United States)

Baran, J; Davydova, N A

2010-03-01

We report the investigation of glass-forming salol upon different courses of the temperature changes from liquid to glass state and back using FT-IR spectroscopy measurements in the wide spectral and temperature ranges. The formation of the ordered clusters in supercooled liquid salol has been observed at 250 K. When the temperature is decreased further to 11 K these ordered clusters become an element of the glass structure. With increasing temperature to 270 K through the glass transition noticeable evolutions of the IR spectrum occurs up till the ordered clusters are developed into crystal. So produced crystal melts in the temperature range 300-310 K, that corresponds to the melting temperature of the metastable phase (Tmelt=302 K) . Thus, the crystalline structure of the ordered clusters corresponds to the structure of metastable phase and is monoclinic.

Mechanism of Supercooled Water Droplet Breakup near the Leading Edge of an Airfoil

Science.gov (United States)

Veras-Alba, Belen; Palacios, Jose; Vargas, Mario; Ruggeri, Charles; Bartkus, Tadas P.

2017-01-01

This work presents the results of an experimental study on supercooled droplet deformation and breakup near the leading edge of an airfoil. The results are compared to prior room temperature droplet deformation results to explore the effects of droplet supercooling. The experiments were conducted in the Adverse Environment Rotor Test Stand (AERTS) at The Pennsylvania State University. An airfoil model placed at the end of the rotor blades mounted onto the hub in the AERTS chamber was moved at speeds ranging between 50 and 80 m/sec. The temperature of the chamber was set at -20°C. A monotonic droplet generator was used to produce droplets that fell from above, perpendicular to the path of the airfoil. The supercooled state of the droplets was determined by measurement of the temperature of the drops at various locations below the droplet generator exit. A temperature prediction code was also used to estimate the temperature of the droplets based on vertical velocity and the distance traveled by droplets from the droplet generator to the airfoil stagnation line. High speed imaging was employed to observe the interaction between the droplets and the airfoil. The high speed imaging provided droplet deformation information as the droplet approached the airfoil near the stagnation line. A tracking software program was used to measure the horizontal and vertical displacement of the droplet against time. It was demonstrated that to compare the effects of water supercooling on droplet deformation, the ratio of the slip velocity and the initial droplet velocity must be equal. A case with equal slip velocity to initial velocity ratios was selected for room temperature and supercooled droplet conditions. The airfoil velocity was 60 m/s and the slip velocity for both sets of data was 40 m/s. In these cases, the deformation of the weakly supercooled and warm droplets did not present different trends. The similar behavior for both environmental conditions indicates that water

Structural crossover in a supercooled metallic liquid and the link to a liquid-to-liquid phase transition

Energy Technology Data Exchange (ETDEWEB)

Lan, S.; Ma, J. L.; Fan, J. [Department of Physics and Material Science, City University of Hong Kong 83 Tat Chee Ave., Kowloon (Hong Kong); Blodgett, M.; Kelton, K. F. [Department of Physics and Institute of Materials Science and Engineering, Washington University One Brookings Drive, St. Louis, Missouri 63130-4899 (United States); Wang, X.-L., E-mail: xlwang@cityu.edu.hk [Department of Physics and Material Science, City University of Hong Kong 83 Tat Chee Ave., Kowloon (Hong Kong); City University of Hong Kong Shenzhen Research Institute, Shenzhen 518057 (China)

2016-05-23

Time-resolved synchrotron measurements were carried out to capture the structure evolution of an electrostatically levitated metallic-glass-forming liquid during free cooling. The experimental data shows a crossover in the liquid structure at ∼1000 K, about 115 K below the melting temperature and 150 K above the crystallization temperature. The structure change is characterized by a dramatic growth in the extended-range order below the crossover temperature. Molecular dynamics simulations have identified that the growth of the extended-range order was due to an increased correlation between solute atoms. These results provide structural evidence for a liquid-to-liquid-phase-transition in the supercooled metallic liquid.

Time scales of supercooled water and implications for reversible polyamorphism

Science.gov (United States)

Limmer, David T.; Chandler, David

2015-09-01

Deeply supercooled water exhibits complex dynamics with large density fluctuations, ice coarsening and characteristic time scales extending from picoseconds to milliseconds. Here, we discuss implications of these time scales as they pertain to two-phase coexistence and to molecular simulations of supercooled water. Specifically, we argue that it is possible to discount liquid-liquid criticality because the time scales imply that correlation lengths for such behaviour would be bounded by no more than a few nanometres. Similarly, it is possible to discount two-liquid coexistence because the time scales imply a bounded interfacial free energy that cannot grow in proportion to a macroscopic surface area. From time scales alone, therefore, we see that coexisting domains of differing density in supercooled water can be no more than nanoscale transient fluctuations.

Down- and up-conversion luminescent carbon dot fluid: inkjet printing and gel glass fabrication

Science.gov (United States)

Wang, Fu; Xie, Zheng; Zhang, Bing; Liu, Yun; Yang, Wendong; Liu, Chun-Yan

2014-03-01

Room temperature liquid-like nanoparticles have emerged as an exciting new research and development area, because their properties could be tailored over a broad range by manipulating geometric and chemical characteristics of the inorganic core and organic canopy. However, related applications are rarely reported due to the multi-step synthesis process and potential toxicity of cadmium based nanomaterials. In this study, we prepared inexpensive and eco-friendly carbon dot fluid by the direct thermal decomposition method. The carbon dot fluid can be excited from UV to near infrared light, and can be prepared as highly concentrated luminescent ink or incorporated into sol-gel derived organically modified silicate glass, suggesting that it has great application potential in the field of printable electronics, solid state lighting and so on.Room temperature liquid-like nanoparticles have emerged as an exciting new research and development area, because their properties could be tailored over a broad range by manipulating geometric and chemical characteristics of the inorganic core and organic canopy. However, related applications are rarely reported due to the multi-step synthesis process and potential toxicity of cadmium based nanomaterials. In this study, we prepared inexpensive and eco-friendly carbon dot fluid by the direct thermal decomposition method. The carbon dot fluid can be excited from UV to near infrared light, and can be prepared as highly concentrated luminescent ink or incorporated into sol-gel derived organically modified silicate glass, suggesting that it has great application potential in the field of printable electronics, solid state lighting and so on. Electronic supplementary information (ESI) available: Details of FTIR, XRD and DLS of CDF, optical properties of CDF, TEM images of other obtained products, luminescent spectra of CDF at different temperatures, and the optical photographs of CDF inks and silica glasses with different concentrations

Evidence for the existence of supercooled ethane droplets under conditions prevalent in Titan's atmosphere.

Science.gov (United States)

Sigurbjörnsson, Omar F; Signorell, Ruth

2008-11-07

Recent evidence for ethane clouds and condensation in Titan's atmosphere raise the question whether liquid ethane condensation nuclei and supercooled liquid ethane droplets exist under the prevalent conditions. We present laboratory studies on the phase behaviour of pure ethane aerosols and ethane aerosols formed in the presence of other ice nuclei under conditions relevant to Titan's atmosphere. Combining bath gas cooling with infrared spectroscopy, we find evidence for the existence of supercooled liquid ethane aerosol droplets. The observed homogeneous freezing rates imply that supercooled ethane could be a long-lived species in ethane-rich regions of Titan's atmosphere similar to supercooled water in the Earth's atmosphere.

Green glass vitrophyre 78526 - An impact of very low-Ti mare basalt composition

Science.gov (United States)

Warner, R. D.; Taylor, G. J.; Kiel, K.; Planner, H. H.; Nehru, C. E.; Ma, M.-S.; Schmitt, R. A.

1978-01-01

Rake sample 78526 is an 8.77 g rock consisting primarily of vitrophyric pale green glass with subordinate mineral and lithic relics. Petrographic and compositional evidence leads to the following conclusions: (1) the bulk composition represents that of a mixture formed by impact melting of at least two different textural and compositional varieties of VLT mare basalt that are now present in the rock as lithic relics and a poorly defined low-Ti mare basalt component observed in thin section only in the form of isolated mineral relics; (2) the admixed VLT mare basalts had REE abundances lower than those found in other mare basalts (but probably higher than emerald green glass) and REE patterns showing significant enrichment of the heavy relative to light REE's, suggesting that they were derived by comparatively high degrees of partial melting of a clinopyroxene-rich source region; and (3) the impact melt supercooled to produce the vitrophyre, with rather sharply contrasting textural domains present in the vitrophyre resulting from differences in nucleation kinetics and degrees of supercooling in various portions of the sample.

Liquid structure and temperature invariance of sound velocity in supercooled Bi melt

International Nuclear Information System (INIS)

Emuna, M.; Mayo, M.; Makov, G.; Greenberg, Y.; Caspi, E. N.; Yahel, E.; Beuneu, B.

2014-01-01

Structural rearrangement of liquid Bi in the vicinity of the melting point has been proposed due to the unique temperature invariant sound velocity observed above the melting temperature, the low symmetry of Bi in the solid phase and the necessity of overheating to achieve supercooling. The existence of this structural rearrangement is examined by measurements on supercooled Bi. The sound velocity of liquid Bi was measured into the supercooled region to high accuracy and it was found to be invariant over a temperature range of ∼60°, from 35° above the melting point to ∼25° into the supercooled region. The structural origin of this phenomenon was explored by neutron diffraction structural measurements in the supercooled temperature range. These measurements indicate a continuous modification of the short range order in the melt. The structure of the liquid is analyzed within a quasi-crystalline model and is found to evolve continuously, similar to other known liquid pnictide systems. The results are discussed in the context of two competing hypotheses proposed to explain properties of liquid Bi near the melting: (i) liquid bismuth undergoes a structural rearrangement slightly above melting and (ii) liquid Bi exhibits a broad maximum in the sound velocity located incidentally at the melting temperature

Influence of Nanoparticles and Graphite Foam on the Supercooling of Acetamide

International Nuclear Information System (INIS)

Yu, J.; Chen, X.; Ma, X.; Song, Q.; Zhao, Y.; Cao, J.

2014-01-01

Acetamide is a promising phase change materials (PCMs) for thermal storage,but the large supercooling during the freezing process has limited its application. In this study, we prepared acetamide-SiO 2 composites by adding nano-SiO 2 into acetamide. This modified PCM was then impregnated into the porous graphite foam forming acetamide-SiO 2 -graphite foam form-stable composites. These composites were subjected to melting-solidification cycles 50 times; the time-temperature curves were tracked and recorded during these cycles. The time-temperature curves showed that, for the acetamide containing 2 wt. % SiO 2 , the supercooling phenomenon was eliminated and the material’s performance was stable for 50 cycles. The solidification temperature of the acetamide-SiO 2 -graphite foam samples was 65°C and the melting temperature was lowered to 65°C. The samples exhibited almost no supercooling and the presence of SiO 2 had no significant effect on the melting-solidification temperature. The microscopic supercooling of the acetamide-SiO 2 composite was measured using differential scanning calorimetry (DSC). The results indicated that when the content of SiO 2 was 1 wt. to 2 wt. %, the supercooling could be reduced to less than 10°C and heat was sufficiently released during solidification. Finally, a set of algorithms was derived using MATLAB software for simulating the crystallization of samples based on the classical nucleation theory. The results of the simulation agreed with the experiment results.

Glass transition in the spin-density wave phase of (TMTSF)2PF6

DEFF Research Database (Denmark)

Lasjaunias, J.C.; Biljakovic, K.; Nad, F.

1994-01-01

We present the results of low frequency dielectric measurements and a detailed kinetic investigation of the specific heat anomaly in the spin-density wave phase of (TMTSF)(2)PF6 in the temperature range between 2 and 4 K. The dielectric relaxation shows a critical slowing down towards a ''static'......'' glass transition around 2 K. The jump in the specific heat in different controlled kinetic conditions shows all the characteristics of freezing in supercooled liquids. Both effects give direct evidence of a glass transition in the spin-density wave ground state....

The protective effect of rapid cold-hardening develops more quickly in frozen versus supercooled larvae of the Antarctic midge, Belgica antarctica.

Science.gov (United States)

Kawarasaki, Yuta; Teets, Nicholas M; Denlinger, David L; Lee, Richard E

2013-10-15

During the austral summer, larvae of the terrestrial midge Belgica antarctica (Diptera: Chironomidae) experience highly variable and often unpredictable thermal conditions. In addition to remaining freeze tolerant year-round, larvae are capable of swiftly increasing their cold tolerance through the rapid cold-hardening (RCH) response. The present study compared the induction of RCH in frozen versus supercooled larvae. At the same induction temperature, RCH occurred more rapidly and conferred a greater level of cryoprotection in frozen versus supercooled larvae. Furthermore, RCH in frozen larvae could be induced at temperatures as low as -12°C, which is the lowest temperature reported to induce RCH. Remarkably, as little as 15 min at -5°C significantly enhanced larval cold tolerance. Not only is protection from RCH acquired swiftly, but it is also quickly lost after thawing for 2 h at 2°C. Because the primary difference between frozen and supercooled larvae is cellular dehydration caused by freeze concentration of body fluids, we also compared the effects of acclimation in dehydrated versus frozen larvae. Because slow dehydration without chilling significantly increased larval survival to a subsequent cold exposure, we hypothesize that cellular dehydration caused by freeze concentration promotes the rapid acquisition of cold tolerance in frozen larvae.

Optimum Combination of Thermoplastic Formability and Electrical Conductivity in Al-Ni-Y Metallic Glass

Science.gov (United States)

Na, Min Young; Park, Sung Hyun; Kim, Kang Cheol; Kim, Won Tae; Kim, Do Hyang

2018-05-01

Both thermoplastic formability and electrical conductivity of Al-Ni-Y metallic glass with 12 different compositions have been investigated in the present study with an aim to apply as a functional material, i.e. as a binder of Ag powders in Ag paste for silicon solar cell. The thermoplastic formability is basically influenced by thermal stability and fragility of supercooled liquid which can be reflected by the temperature range for the supercooled liquid region (ΔT x ) and the difference in specific heat between the frozen glass state and the supercooled liquid state (ΔC p ). The measured ΔT x and ΔC p values show a strong composition dependence. However, the composition showing the highest ΔT x and ΔC p does not correspond to the composition with the highest amount of Ni and Y. It is considered that higher ΔT x and ΔC p may be related to enhancement of icosahedral SRO near T g during cooling. On the other hand, electrical resistivity varies with the change of Al contents as well as with the change of the volume fraction of each phase after crystallization. The composition range with the optimum combination of thermoplastic formability and electrical conductivity in Al-Ni-Y system located inside the composition triangle whose vertices compositions are Al87Ni3Y10, Al85Ni5Y10, and Al86Ni5Y9.

The effect of fluid flow due to the crystal-melt density change on the growth of a parabolic isothermal dendrite

Science.gov (United States)

Mcfadden, G. B.; Coriell, S. R.

1986-01-01

The Ivantsov (1947) analysis of an isolated isothermal dendrite (with zero surface tension) growing into a supercooled liquid is extended to include the effects of the fluid flow due to volume contraction or expansion upon solidification. For an axisymmetric paraboloidal dendrite, an analytic solution to the Navier-Stokes equations is obtained. The magnitude of the flow is proportional to the relative density change epsilon, and the flow becomes negligible far from the surface of the dendrite. The temperature field consistent with this flow can also be found explicitly. The well-known expression that relates the dimensionless supercooling to the Peclet number in the absence of fluid flow is modified for nonzero epsilon, but the effect is of order epsilon and hence is seen to be minor for most values of epsilon and dimensionless supercooling that occur in practice.

Supercooling and cold energy storage characteristics of nano-media in ball-packed porous structures

Directory of Open Access Journals (Sweden)

Zhao Qunzhi

2015-04-01

Full Text Available The presented experiments aimed to study the supercooling and cold-energy storage characteristics of nanofluids and water-based nano-media in ball-packed porous structures (BPS. Titanium dioxide nanoparticles (TiO2 NPs measuring 20nm and 80nm were used as additives and sodium dodecyl benzene sulphonate (SDBS was used as anionic surfactant. The experiments used different concentrations of nanofluid, distilled with BPS of different spherical diameter and different concentrations of nano-media, and were conducted 20 times. Experimental results of supercooling were analysed by statistical methods. Results show that the average and peak supercooling degrees of nanofluids and nano-media in BPS are lower than those of distilled water. For the distilled water in BPS, the supercooling degree decreases on the whole with the decrease of the ball diameter. With the same spherical diameter (8mm of BPS, the supercooling degree of TiO2 NPs measuring 20nm is lower than the supercooling degree of distilled water in BPS. Step-cooling experiments of different concentrations of nanofluids and nano-media in BPS were also conducted. Results showed that phase transition time is reduced because of the presence of TiO2 NPs. The BPS substrate and the NPs enhance the heat transfer. Distilled water with a porous solid base and nanoparticles means the amount of cold-energy storage increases and the supercooling degree and the total time are greatly reduced. The phase transition time of distilled water is about 3.5 times that of nano-media in BPS.

Supercooling of natural water, heavy water and of the blends H2O-D2O

International Nuclear Information System (INIS)

Lafargue, C.; Babin, L.; Clausse, D.; Lere-Porte, M.; Broto, F.

1975-01-01

It is shown that the coherency of the results of various measurements on water freezing temperatures proves that freezing temperatures must be dependent on the structure of the supercooled liquid. Recent experiments that confirm this interpretation are described: study of the stability of supercooled water as a function of time at fixed temperature, study of the influence of various thermal treatments on the behavior of supercooled water, study of the supercooling of heavy water and of D 2 O-H 2 O blends [fr

Linking structure to fragility in bulk metallic glass-forming liquids

International Nuclear Information System (INIS)

Wei, Shuai; Stolpe, Moritz; Gross, Oliver; Gallino, Isabella; Hembree, William; Busch, Ralf; Evenson, Zach; Bednarcik, Jozef; Kruzic, Jamie J.

2015-01-01

Using in-situ synchrotron X-ray scattering, we show that the structural evolution of various bulk metallic glass-forming liquids can be quantitatively connected to their viscosity behavior in the supercooled liquid near T g . The structural signature of fragility is identified as the temperature dependence of local dilatation on distinct key atomic length scales. A more fragile behavior results from a more pronounced thermally induced dilatation of the structure on a length scale of about 3 to 4 atomic diameters, coupled with shallower temperature dependence of structural changes in the nearest neighbor environment. These findings shed light on the structural origin of viscous slowdown during undercooling of bulk metallic glass-forming liquids and demonstrate the promise of predicting the properties of bulk metallic glasses from the atomic scale structure

Linking structure to fragility in bulk metallic glass-forming liquids

Energy Technology Data Exchange (ETDEWEB)

Wei, Shuai, E-mail: shuai.wei@asu.edu, E-mail: m.stolpe@mx.uni-saarland.de [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287 (United States); Stolpe, Moritz, E-mail: shuai.wei@asu.edu, E-mail: m.stolpe@mx.uni-saarland.de; Gross, Oliver; Gallino, Isabella; Hembree, William; Busch, Ralf [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Evenson, Zach [Department of Materials Science and Engineering, Saarland University, Campus C63, 66123 Saarbrücken (Germany); Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und Raumfahrt (DLR), 51170 Köln (Germany); Bednarcik, Jozef [Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, D-22603 Hamburg (Germany); Kruzic, Jamie J. [Material Science, School of Mechanical, Industrial, and Manufacturing Engineering, Oregon State University, Corvallis, Oregon 97331 (United States)

2015-05-04

Using in-situ synchrotron X-ray scattering, we show that the structural evolution of various bulk metallic glass-forming liquids can be quantitatively connected to their viscosity behavior in the supercooled liquid near T{sub g}. The structural signature of fragility is identified as the temperature dependence of local dilatation on distinct key atomic length scales. A more fragile behavior results from a more pronounced thermally induced dilatation of the structure on a length scale of about 3 to 4 atomic diameters, coupled with shallower temperature dependence of structural changes in the nearest neighbor environment. These findings shed light on the structural origin of viscous slowdown during undercooling of bulk metallic glass-forming liquids and demonstrate the promise of predicting the properties of bulk metallic glasses from the atomic scale structure.

Fragile to strong crossover at the Widom line in supercooled aqueous solutions of NaCl

Energy Technology Data Exchange (ETDEWEB)

Gallo, P. [Dipartimento di Matematica e Fisica, Università Roma Tre, Via della Vasca Navale 84, I-00146 Rome, Italy and INFN, Sezione di Roma Tre, Via della Vasca Navale 84, I-00146 Rome (Italy); Corradini, D.; Rovere, M., E-mail: rovere@fis.uniroma3.it [Dipartimento di Matematica e Fisica, Università Roma Tre, Via della Vasca Navale 84, I-00146 Rome (Italy)

2013-11-28

We study by molecular dynamics simulations the dynamical properties of an aqueous solution of NaCl at a concentration of 0.67 mol/kg upon supercooling. In a previous study of the same ionic solution, we have located the liquid-liquid critical point (LLCP) and determined the Widom line connected to the liquid-liquid transition. We present here the results obtained from the study of the self-intermediate scattering function in a large range of temperatures and densities approaching the LLCP. The structural relaxation is in agreement with the mode coupling theory (MCT) in the region of mild supercooling. In the deeper supercooled region the α-relaxation time as function of temperature deviates from the MCT power law prediction showing a crossover from a fragile to a strong behavior. This crossover is found upon crossing the Widom line. The same trend was found in bulk water upon supercooling and it appears almost unchanged by the interaction with ions apart from a shift in the thermodynamic plane toward lower pressures and higher temperatures. These results show that the phenomenology of supercooled water transfers from bulk to solution where the study of the supercooled region is experimentally less difficult.

Dynamical, structural and chemical heterogeneities in a binary metallic glass-forming liquid

Science.gov (United States)

Puosi, F.; Jakse, N.; Pasturel, A.

2018-04-01

As it approaches the glass transition, particle motion in liquids becomes highly heterogeneous and regions with virtually no mobility coexist with liquid-like domains. This complex dynamic is believed to be responsible for different phenomena including non-exponential relaxation and the breakdown of the Stokes-Einstein relation. Understanding the relationships between dynamical heterogeneities and local structure in metallic liquids and glasses is a major scientific challenge. Here we use classical molecular dynamics simulations to study the atomic dynamics and microscopic structure of Cu50Zr50 alloy in the supercooling regime. Dynamical heterogeneities are identified via an isoconfigurational analysis. We demonstrate the transition from isolated to clustering low mobility with decreasing temperature. These slow clusters, whose sizes grow upon cooling, are also associated with concentration fluctuations, characterized by a Zr-enriched phase, with a composition CuZr2 . In addition, a structural analysis of slow clusters based on Voronoi tessellation evidences an increase with respect of the bulk system of the fraction of Cu atoms having a local icosahedral order. These results are in agreement with the consolidated scenario of the relevant role played by icosahedral order in the dynamic slowing-down in supercooled metal alloys.

Influence of Nanoparticles and Graphite Foam on the Supercooling of Acetamide

Directory of Open Access Journals (Sweden)

Jia Yu

2014-01-01

Full Text Available Acetamide is a promising phase change materials (PCMs for thermal storage,but the large supercooling during the freezing process has limited its application. In this study, we prepared acetamide-SiO2 composites by adding nano-SiO2 into acetamide. This modified PCM was then impregnated into the porous graphite foam forming acetamide-SiO2-graphite foam form-stable composites. These composites were subjected to melting-solidification cycles 50 times; the time-temperature curves were tracked and recorded during these cycles. The time-temperature curves showed that, for the acetamide containing 2 wt. % SiO2, the supercooling phenomenon was eliminated and the material’s performance was stable for 50 cycles. The solidification temperature of the acetamide-SiO2-graphite foam samples was 65°C and the melting temperature was lowered to 65°C. The samples exhibited almost no supercooling and the presence of SiO2 had no significant effect on the melting-solidification temperature. The microscopic supercooling of the acetamide-SiO2 composite was measured using differential scanning calorimetry (DSC. The results indicated that when the content of SiO2 was 1 wt. to 2 wt. %, the supercooling could be reduced to less than 10°C and heat was sufficiently released during solidification. Finally, a set of algorithms was derived using MATLAB software for simulating the crystallization of samples based on the classical nucleation theory. The results of the simulation agreed with the experiment results.

Experimental evidence for stochastic switching of supercooled phases in NdNiO3 nanostructures

Science.gov (United States)

Kumar, Devendra; Rajeev, K. P.; Alonso, J. A.

2018-03-01

A first-order phase transition is a dynamic phenomenon. In a multi-domain system, the presence of multiple domains of coexisting phases averages out the dynamical effects, making it nearly impossible to predict the exact nature of phase transition dynamics. Here, we report the metal-insulator transition in samples of sub-micrometer size NdNiO3 where the effect of averaging is minimized by restricting the number of domains under study. We observe the presence of supercooled metallic phases with supercooling of 40 K or more. The transformation from the supercooled metallic to the insulating state is a stochastic process that happens at different temperatures and times in different experimental runs. The experimental results are understood without incorporating material specific properties, suggesting that the behavior is of universal nature. The size of the sample needed to observe individual switching of supercooled domains, the degree of supercooling, and the time-temperature window of switching are expected to depend on the parameters such as quenched disorder, strain, and magnetic field.

The Widom line of supercooled water

International Nuclear Information System (INIS)

Franzese, Giancarlo; Stanley, H Eugene

2007-01-01

Water can be supercooled to temperatures as low as -92 deg. C, the experimental crystal homogeneous nucleation temperature T H at 2 kbar. Within the supercooled liquid phase its response functions show an anomalous increase consistent with the presence of a liquid-liquid critical point located in a region inaccessible to experiments on bulk water. Recent experiments on the dynamics of confined water show that a possible way to understand the properties of water is to investigate the supercooled phase diagram in the vicinity of the Widom line (locus of maximum correlation length) that emanates from the hypothesized liquid-liquid critical point. Here we explore the Widom line for a Hamiltonian model of water using an analytic approach, and discuss the plausibility of the hypothesized liquid-liquid critical point, as well as its possible consequences, on the basis of the assumptions of the model. The present analysis allows us (i) to find an analytic expression for the spinodal line of the high-density liquid phase, with respect to the low-density liquid phase, showing that this line becomes flat in the P-T phase diagram in the physical limit of a large number of available orientations for the hydrogen bonds, as recently seen in simulations and experiments (Xu et al 2005 Proc. Natl Acad. Sci. 102 16558); (ii) to find an estimate of the values for the hypothesized liquid-liquid critical point coordinates that compare very well with Monte Carlo results; and (iii) to show how the Widom line can be located by studying the derivative of the probability of forming hydrogen bonds with local tetrahedral orientation which can be calculated analytically within this approach

The atomic-scale nucleation mechanism of NiTi metallic glasses upon isothermal annealing studied via molecular dynamics simulations.

Science.gov (United States)

Li, Yang; Li, JiaHao; Liu, BaiXin

2015-10-28

Nucleation is one of the most essential transformation paths in phase transition and exerts a significant influence on the crystallization process. Molecular dynamics simulations were performed to investigate the atomic-scale nucleation mechanisms of NiTi metallic glasses upon devitrification at various temperatures (700 K, 750 K, 800 K, and 850 K). Our simulations reveal that at 700 K and 750 K, nucleation is polynuclear with high nucleation density, while at 800 K it is mononuclear. The underlying nucleation mechanisms have been clarified, manifesting that nucleation can be induced either by the initial ordered clusters (IOCs) or by the other precursors of nuclei evolved directly from the supercooled liquid. IOCs and other precursors stem from the thermal fluctuations of bond orientational order in supercooled liquids during the quenching process and during the annealing process, respectively. The simulation results not only elucidate the underlying nucleation mechanisms varied with temperature, but also unveil the origin of nucleation. These discoveries offer new insights into the devitrification mechanism of metallic glasses.

Formation of apatite layers on modified canasite glass-ceramics in simulated body fluid.

Science.gov (United States)

Miller, C A; Kokubo, T; Reaney, I M; Hatton, P V; James, P F

2002-03-05

Canasite glass-ceramics were modified by either increasing the concentration of calcium in the glass, or by the addition of P2O5. Samples of these novel materials were placed in simulated body fluid (SBF), along with a control material (commercial canasite), for periods ranging from 12 h to 28 days. After immersion, surface analysis was performed using thin film X-ray diffraction, Fourier transform infrared reflection spectroscopy, and scanning electron microscopy equipped with energy dispersive X-ray detectors. The concentrations of sodium, potassium, calcium, silicon, and phosphorus in the SBF solution were measured using inductively coupled plasma emission spectroscopy. No apatite was detected on the surface of commercial canasite, even after 28 days of immersion in SBF. A crystalline apatite layer was formed on the surface of a P2O5-containing canasite after 5 days, and after 3 days for calcium-enriched canasite. Ion release data suggested that the mechanism for apatite deposition was different for P2O5 and non-P2O5-containing glass-ceramics. Copyright 2001 John Wiley & Sons, Inc.

Temperature-induced structural changes in fluorozirconate glasses and liquids

International Nuclear Information System (INIS)

Sen, S.; Youngman, R.E.

2002-01-01

The atomic structure and its temperature dependence in fluorozirconate glasses and supercooled liquids have been studied with high-resolution and high-temperature 19 F and 23 Na nuclear-magnetic-resonance (NMR) spectroscopy. The 19 F NMR spectra in these glasses show the presence of multiple F environments. Temperature dependence of the 19 F magic-angle-spinning NMR spectra indicates a progressive change in the average F coordination environment in the glass structure, besides motional narrowing due to substantial mobility of F - ions. The observed change in the average 19 F NMR chemical shift is consistent with progressive breaking of the Zr-F-Zr linkages in the glass structure with increasing temperature. The onset of such a change in F speciation is observed at temperatures well below T g . This result is evidence of changes in the average equilibrium structure in an inorganic glass-forming liquid at T g , albeit on a local scale. The 23 Na NMR spectra indicate that the cations in these glasses become significantly mobile only at temperatures T≥T g , which allows for the onset of global structural relaxation and viscous flow

High density liquid structure enhancement in glass forming aqueous solution of LiCl

Science.gov (United States)

Camisasca, G.; De Marzio, M.; Rovere, M.; Gallo, P.

2018-06-01

We investigate using molecular dynamics simulations the dynamical and structural properties of LiCl:6H2O aqueous solution upon supercooling. This ionic solution is a glass forming liquid of relevant interest in connection with the study of the anomalies of supercooled water. The LiCl:6H2O solution is easily supercooled and the liquid state can be maintained over a large decreasing temperature range. We performed simulations from ambient to 200 K in order to investigate how the presence of the salt modifies the behavior of supercooled water. The study of the relaxation time of the self-density correlation function shows that the system follows the prediction of the mode coupling theory and behaves like a fragile liquid in all the range explored. The analysis of the changes in the water structure induced by the salt shows that while the salt preserves the water hydrogen bonds in the system, it strongly affects the tetrahedral hydrogen bond network. Following the interpretation of the anomalies of water in terms of a two-state model, the modifications of the oxygen radial distribution function and the angular distribution function of the hydrogen bonds in water indicate that LiCl has the role of enhancing the high density liquid component of water with respect to the low density component. This is in agreement with recent experiments on aqueous ionic solutions.

Optimization of experimental conditions for the monitoring of nucleation and growth of racemic Diprophylline from the supercooled melt

Science.gov (United States)

Lemercier, Aurélien; Viel, Quentin; Brandel, Clément; Cartigny, Yohann; Dargent, Eric; Petit, Samuel; Coquerel, Gérard

2017-08-01

Since more and more pharmaceutical substances are developed as amorphous forms, it is nowadays of major relevance to get insights into the nucleation and growth mechanisms from supercooled melts (SCM). A step-by-step approach of recrystallization from a SCM is presented here, designed to elucidate the impact of various experimental parameters. Using the bronchodilator agent Diprophylline (DPL) as a model compound, it is shown that optimal conditions for informative observations of the crystallization behaviour from supercooled racemic DPL require to place samples between two cover slides with a maximum sample thickness of 20 μm, and to monitor recrystallization during an annealing step of 30 min at 70 °C, i.e. about 33 °C above the temperature of glass transition. In these optimized conditions, it could be established that DPL crystallization proceeds in two steps: spontaneous nucleation and growth of large and well-faceted particles of a new crystal form (primary crystals: PC) and subsequent crystallization of a previously known form (RII) that develops from specific surfaces of PC. The formation of PC particles therefore constitutes the key-step of the crystallization events and is shown to be favoured by at least 2.33 wt% of the major chemical impurity, Theophylline.

Resolving glass transition in Te-based phase-change materials by modulated differential scanning calorimetry

Science.gov (United States)

Chen, Yimin; Mu, Sen; Wang, Guoxiang; Shen, Xiang; Wang, Junqiang; Dai, Shixun; Xu, Tiefeng; Nie, Qiuhua; Wang, Rongping

2017-10-01

Glass transitions of Te-based phase-change materials (PCMs) were studied by modulated differential scanning calorimetry. It was found that both Ge2Sb2Te5 and GeTe are marginal glass formers with ΔT (= T x - T g) less than 2.1 °C when the heating rate is below 3 °C min-1. The fragilities of Ge2Sb2Te5 and GeTe can be estimated as 46.0 and 39.7, respectively, around the glass transition temperature, implying that a fragile-to-strong transition would be presented in such Te-based PCMs. The above results provide direct experimental evidence to support the investigation of crystallization kinetics in supercooled liquid PCMs.

Computer simulations of supercooled polymer melts in the bulk and in confined geometry

International Nuclear Information System (INIS)

Baschnagel, J; Varnik, F

2005-01-01

We survey results of computer simulations for the structure and dynamics of supercooled polymer melts and films. Our survey is mainly concerned with features of a coarse grained polymer model-a bead-spring model-in the temperature regime above the critical glass temperature T c of the ideal mode-coupling theory (MCT). We divide our discussion into two parts: a part devoted to bulk properties and a part dealing with thin films. The discussion of the bulk properties focuses on two aspects: a comparison of the simulation results with MCT and an analysis of dynamic heterogeneities. We explain in detail how the analyses are performed and what results may be obtained, and we critically assess their strengths and weaknesses. In discussing the application of MCT we also present first results of a quantitative comparison which does not rely on fits, but exploits static input from the simulation to predict the relaxation dynamics. The second part of this review is devoted to extensions of the simulations from the bulk to thin films. We explore in detail the influence of the boundary condition, imposed by smooth or rough walls, on the structure and dynamics of the polymer melt. Geometric confinement is found to shift the glass transition temperature T g (or T c in our case) relative to the bulk. We compare our and other simulation results for the T g shift with experimental data, briefly survey some theoretical ideas for explaining these shifts and discuss related simulation work on the glass transition of confined liquids. Finally, we also present some technical details of how to perform fits to MCT and give a brief introduction to another approach to the glass transition based on the potential energy landscape of a liquid. (topical review)

Unusual glass-forming ability induced by changes in the local atomic structure in Ti-based bulk metallic glass

International Nuclear Information System (INIS)

Kim, Y C; Chang, H J; Kim, D H; Kim, W T; Cha, P R

2007-01-01

The effect of partial replacement of Cu by Be in Ti 50 Cu 32 Ni 15 Sn 3 alloy on the thermal properties, structure, and forming ability of an amorphous phase were investigated by differential scanning calorimetry (DSC), x-ray diffraction (XRD), extended x-ray absorption fine structure (EXAFS), and high-resolution transmission electron microscopy (HRTEM). Ti 50 Cu 25 Ni 15 Sn 3 Be 7 alloy shows enhanced glass-forming ability, enabling one to fabricate a fully amorphous bulk metallic glass sample 2 mm in diameter by injection casting. With the replacement, the supercooled liquid region ΔT x (= T x -T g , where T x is the crystallization temperature and T g is the glass transition temperature) decreased from 73 to 45 K and the reduced glass transition temperature T rg (= T g /T 1 , where T 1 is the liquidus temperature) increased from 0.53 to 0.57. The amorphous Ti 50 Cu 25 Ni 15 Sn 3 Be 7 phase showed a formation of short-range-ordered clusters 1-2 nm in size, which is attributed to the strong interaction between Ti and Be. The results show that ΔT x can be used as a thermal parameter reflecting the glass-forming ability of the alloy only when the phase formed during crystallization is the same as the phase competing with the glass transition during solidification

Singularity-free interpretation of the thermodynamics of supercooled water

International Nuclear Information System (INIS)

Sastry, S.; Debenedetti, P.G.; Sciortino, F.; Stanley, H.E.

1996-01-01

The pronounced increases in isothermal compressibility, isobaric heat capacity, and in the magnitude of the thermal expansion coefficient of liquid water upon supercooling have been interpreted either in terms of a continuous, retracing spinodal curve bounding the superheated, stretched, and supercooled states of liquid water, or in terms of a metastable, low-temperature critical point. Common to these two scenarios is the existence of singularities associated with diverging density fluctuations at low temperature. We show that the increase in compressibility upon lowering the temperature of a liquid that expands on cooling, like water, is not contingent on any singular behavior, but rather is a thermodynamic necessity. We perform a thermodynamic analysis for an anomalous liquid (i.e., one that expands when cooled) in the absence of a retracing spinodal and show that one may in general expect a locus of compressibility extrema in the anomalous regime. Our analysis suggests that the simplest interpretation of the behavior of supercooled water consistent with experimental observations is free of singularities. We then develop a waterlike lattice model that exhibits no singular behavior, while capturing qualitative aspects of the thermodynamics of water. copyright 1996 The American Physical Society

Physical limit of stability in supercooled D2O and D2O+H2O mixtures

Science.gov (United States)

Kiselev, S. B.; Ely, J. F.

2003-01-01

The fluctuation theory of homogeneous nucleation was applied for calculating the physical boundary of metastable states, the kinetic spinodal, in supercooled D2O and D2O+H2O mixtures. The kinetic spinodal in our approach is completely determined by the surface tension and equation of state of the supercooled liquid. We developed a crossover equation of state for supercooled D2O, which predicts a second critical point of low density water-high density water equilibrium, CP2, and represents all available experimental data in supercooled D2O within experimental accuracy. Using Turnbull's expression for the surface tension we calculated with the crossover equation of state for supercooled D2O the kinetic spinodal, TKS, which lies below the homogeneous nucleation temperature, TH. We show that CP2 always lies inside in the so-called "nonthermodynamic habitat" and physically does not exist. However, the concept of a second "virtual" critical point is physical and very useful. Using this concept we have extended this approach to supercooled D2O+H2O mixtures. As an example, we consider here an equimolar D2O+H2O mixture in normal and supercooled states at atmospheric pressure, P=0.1 MPa.

Mechanism of supercooled droplet freezing on surfaces.

Science.gov (United States)

Jung, Stefan; Tiwari, Manish K; Doan, N Vuong; Poulikakos, Dimos

2012-01-10

Understanding ice formation from supercooled water on surfaces is a problem of fundamental importance and general utility. Superhydrophobic surfaces promise to have remarkable 'icephobicity' and low ice adhesion. Here we show that their icephobicity can be rendered ineffective by simple changes in environmental conditions. Through experiments, nucleation theory and heat transfer physics, we establish that humidity and/or the flow of a surrounding gas can fundamentally switch the ice crystallization mechanism, drastically affecting surface icephobicity. Evaporative cooling of the supercooled liquid can engender ice crystallization by homogeneous nucleation at the droplet-free surface as opposed to the expected heterogeneous nucleation at the substrate. The related interplay between droplet roll-off and rapid crystallization is also studied. Overall, we bring a novel perspective to icing and icephobicity, unveiling the strong influence of environmental conditions in addition to the accepted effects of the surface conditions and hydrophobicity.

Gelation on heating of supercooled gelatin solutions.

Science.gov (United States)

Guigo, Nathanaël; Sbirrazzuoli, Nicolas; Vyazovkin, Sergey

2012-04-23

Diluted (1.0-1.5 wt%) aqueous gelatin solutions have been cooled to -10 °C at a cooling rate 20 °C min(-1) without freezing and detectable gelation. When heated at a constant heating rate (0.5 -2 °C min(-1)), the obtained supercooled solutions demonstrate an atypical process of gelation that has been characterized by regular and stochastically modulated differential scanning calorimetry (DSC) as well as by isoconversional kinetic analysis. The process is detectable as an exothermic peak in the total heat flow of regular DSC and in the nonreversing heat flow of stochastically modulated DSC. Isoconversional kinetic analysis applied to DSC data reveals that the effective activation energy of the process increases from approximately 75 to 200 kJ mol(-1) as a supercooled solution transforms to gel on continuous heating. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

TRIS buffer in simulated body fluid distorts the assessment of glass-ceramic scaffold bioactivity.

Science.gov (United States)

Rohanová, Dana; Boccaccini, Aldo Roberto; Yunos, Darmawati Mohamad; Horkavcová, Diana; Březovská, Iva; Helebrant, Aleš

2011-06-01

The paper deals with the characterisation of the bioactive phenomena of glass-ceramic scaffold derived from Bioglass® (containing 77 wt.% of crystalline phases Na(2)O·2CaO·3SiO(2) and CaO·SiO(2) and 23 wt.% of residual glass phase) using simulated body fluid (SBF) buffered with tris-(hydroxymethyl) aminomethane (TRIS). A significant effect of the TRIS buffer on glass-ceramic scaffold dissolution in SBF was detected. To better understand the influence of the buffer, the glass-ceramic scaffold was exposed to a series of in vitro tests using different media as follows: (i) a fresh liquid flow of SBF containing tris (hydroxymethyl) aminomethane; (ii) SBF solution without TRIS buffer; (iii) TRIS buffer alone; and (iv) demineralised water. The in vitro tests were provided under static and dynamic arrangements. SBF buffered with TRIS dissolved both the crystalline and residual glass phases of the scaffold and a crystalline form of hydroxyapatite (HAp) developed on the scaffold surface. In contrast, when TRIS buffer was not present in the solutions only the residual glassy phase dissolved and an amorphous calcium phosphate (Ca-P) phase formed on the scaffold surface. It was confirmed that the TRIS buffer primarily dissolved the crystalline phase of the glass-ceramic, doubled the dissolving rate of the scaffold and moreover supported the formation of crystalline HAp. This significant effect of the buffer TRIS on bioactive glass-ceramic scaffold degradation in SBF has not been demonstrated previously and should be considered when analysing the results of SBF immersion bioactivity tests of such systems. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Oxidation feature and diffusion mechanism of Zr-based metallic glasses near the glass transition point

Science.gov (United States)

Hu, Zheng; Lei, Xianqi; Wang, Yang; Zhang, Kun

2018-03-01

The oxidation behaviors of as-cast, pre-deformed, and crystallized Zr47.9Ti0.3Ni3.1Cu39.3Al9.4 metallic glasses (MGs) were studied near the glass transition point. The oxidation kinetics of the crystallized MGs followed a parabolic-rate law, and the as-cast and pre-deformed MGs exerted a typical two-stage behavior above the glass transition temperature (T g). Most interesting, pre-deformed treatment can significantly improve the oxidation rate of MGs, as the initial oxidation appeared earlier than for the as-cast MGs, and was accompanied by much thicker oxide scale. The EDS and XPS results showed that the metal Al acted as the preferred scavenger that absorbed intrinsic oxygen in the near-surface region of as-cast MGs. However, a homogeneous mixed layer without Al was observed in the pre-deformed MGs. We speculated the accelerated diffusion of other elements in the MGs was due to the local increase in the free volume and significant shear-induced dilation of the local structure. The results from this study demonstrate that MGs exhibit controllable atomic diffusion during the oxidation process, which can facilitate use in super-cooled liquid region applications.

Mixing effects in the crystallization of supercooled quantum binary liquids

International Nuclear Information System (INIS)

Kühnel, M.; Kalinin, A.; Fernández, J. M.; Tejeda, G.; Moreno, E.; Montero, S.; Tramonto, F.; Galli, D. E.; Nava, M.; Grisenti, R. E.

2015-01-01

By means of Raman spectroscopy of liquid microjets, we have investigated the crystallization process of supercooled quantum liquid mixtures composed of parahydrogen (pH 2 ) or orthodeuterium (oD 2 ) diluted with small amounts of neon. We show that the introduction of the Ne impurities affects the crystallization kinetics in terms of a significant reduction of the measured pH 2 and oD 2 crystal growth rates, similarly to what found in our previous work on supercooled pH 2 -oD 2 liquid mixtures [Kühnel et al., Phys. Rev. B 89, 180201(R) (2014)]. Our experimental results, in combination with path-integral simulations of the supercooled liquid mixtures, suggest in particular a correlation between the measured growth rates and the ratio of the effective particle sizes originating from quantum delocalization effects. We further show that the crystalline structure of the mixtures is also affected to a large extent by the presence of the Ne impurities, which likely initiate the freezing process through the formation of Ne-rich crystallites

Mixing effects in the crystallization of supercooled quantum binary liquids

Energy Technology Data Exchange (ETDEWEB)

Kühnel, M.; Kalinin, A. [Institut für Kernphysik, J. W. Goethe-Universität, Max-von-Laue-Str. 1, 60438 Frankfurt am Main (Germany); Fernández, J. M.; Tejeda, G.; Moreno, E.; Montero, S. [Laboratory of Molecular Fluid Dynamics, Instituto de Estructura de la Materia, CSIC, Serrano 121, 28006 Madrid (Spain); Tramonto, F.; Galli, D. E. [Laboratorio di Calcolo Parallelo e di Simulazioni di Materia Condensata, Dipartimento di Fisica, Università degli Studi di Milano, Via Celoria 16, 20133 Milano (Italy); Nava, M. [Laboratorio di Calcolo Parallelo e di Simulazioni di Materia Condensata, Dipartimento di Fisica, Università degli Studi di Milano, Via Celoria 16, 20133 Milano (Italy); Computational Science, Department of Chemistry and Applied Biosciences, ETH Zurich, USI Campus, Via Giuseppe Buffi 13, CH-6900 Lugano (Switzerland); Grisenti, R. E. [Institut für Kernphysik, J. W. Goethe-Universität, Max-von-Laue-Str. 1, 60438 Frankfurt am Main (Germany); GSI - Helmholtzzentrum für Schwerionenforschung, Planckstr. 1, 64291 Darmstadt (Germany)

2015-08-14

By means of Raman spectroscopy of liquid microjets, we have investigated the crystallization process of supercooled quantum liquid mixtures composed of parahydrogen (pH{sub 2}) or orthodeuterium (oD{sub 2}) diluted with small amounts of neon. We show that the introduction of the Ne impurities affects the crystallization kinetics in terms of a significant reduction of the measured pH{sub 2} and oD{sub 2} crystal growth rates, similarly to what found in our previous work on supercooled pH{sub 2}-oD{sub 2} liquid mixtures [Kühnel et al., Phys. Rev. B 89, 180201(R) (2014)]. Our experimental results, in combination with path-integral simulations of the supercooled liquid mixtures, suggest in particular a correlation between the measured growth rates and the ratio of the effective particle sizes originating from quantum delocalization effects. We further show that the crystalline structure of the mixtures is also affected to a large extent by the presence of the Ne impurities, which likely initiate the freezing process through the formation of Ne-rich crystallites.

Glasses

DEFF Research Database (Denmark)

Dyre, Jeppe

2004-01-01

The temperature dependence of the viscosity of most glassforming liquids is known to depart significantly from the classical Arrhenius behaviour of simple fluids. The discovery of an unexpected correlation between the extent of this departure and the Poisson ratio of the resulting glass could lead...... to new understanding of glass ageing and viscous liquid dynamics....

Molecular dynamics study of dynamic and structural properties of supercooled liquid and glassy iron in the rapid-cooling processes

Energy Technology Data Exchange (ETDEWEB)

Cao, Qi-Long; Huang, Duo-Hui; Yang, Jun-Sheng; Wan, Min-Jie; Wang, Fan-Hou, E-mail: eatonch@gmail.com

2014-10-01

Molecular dynamics simulations were applied to study the dynamic and structural properties of supercooled liquid and glassy iron in the rapid-cooling processes. The mean-square displacement and the non-Gaussian parameter were used to describe the dynamic properties. The evolution of structural properties was investigated using the pair distribution functions and bond-angle distribution functions. Results for dynamic and structural relaxations indicate that the dynamic features are consistently correlated with the structure evolution, and there are three temperature regions as the temperature decreases: (1) at higher temperatures (1500 K, 1300 K, and 1100 K), the system remains in the liquid characteristics during the overall relaxation process. (2) At medial temperatures (1050 K, 900 K, and 700 K), a fast β-relaxation is followed by a much slower α-relaxation. There is a little change in the structural properties in the β-relaxation region, while major configuration rearrangements occurred in the α-relaxation range and the crystallization process was completed at the end of α-relaxation region. (3) At lower temperature (500 K), the system shows glassy characteristics during the overall relaxation process. In addition, the melting temperature, glass transition temperature and diffusion coefficients of supercooled liquid iron are also computed.

Crystallization of Cu60Ti20Zr20 metallic glass with and without pressure

DEFF Research Database (Denmark)

Jiang, Jianzhong; Yang, B.; Saksl, K.

2003-01-01

Structural stability of a Cu60Ti20Zr20 metallic glass under-pressure up to 4.5 GPa was investigated by x-ray diffraction. The sample exhibited a supercooled liquid region of 33 K and a ratio of the glass-transition temperature to the liquidus temperature of 0.63. The glass crystallized in two......, structure crystalline phase with a spacing group P6(3)/mmc (194) and lattice parameters a = 5.105 Angstrom and c = 8.231 Angstrom. Both crystallization temperatures increased with pressure having a slope of 19 K/GPa. The increase of the first crystallization temperature with increasing pressure in the glass...... can be explained by the suppression of atomic mobility. No significant structural change was detected in the Cu60Ti20Zr20 glass annealed,in vacuum at 697 K for I h as compared to the as-prepared sample from x-ray diffraction. measurements....

The Influence of Cooling Rates on Paleointensity of Volcanic Glasses: an Experimental Approach on Synthetic Glass

Science.gov (United States)

von Aulock, F. W.; Ferk, A.; Leonhardt, R.; Hess, K.-U.; Dingwell, D. B.

2009-04-01

The suitability of volcanic glass for paleointensity determinations has been proposed in many studies throughout the last years. Besides the mainly single domain magnetic remanence carriers and the pristine character of the volcanic glass, this was also reasoned by the possibility to correct paleointensity data for cooling rate dependency using relaxation geospeedometry. This method gives the cooling rate of a glass at the glass transition interval which marks the change of a ductile supercooled liquid to a brittle glass. In this study the cooling rate correction as carried out for example by Leonhardt et al. 2006 is tested on synthetic volcanic glass. In order to obtain a stable multicomponent glass with ideal magnetic properties, a natural phonolithic glass from Tenerife (Spain) was melted to avoid heterogeneity and degassing. Further it was tempered for 5 hours at 900 °C to yield a sufficient concentration of magnetic remanence carriers. To exclude nucleation or crystallisation 7 samples were then heated to about 50 °C above the glass transition temperature at around 720 °C and quenched at different rates from 0.1 to 15 K/min. After carrying out a paleointensity experiment using a modified Thellier method, which incorporated alteration, additivity and tail checks, the dependence of the thermoremance on cooling rate was investigated. Using the original cooling rates we corrected the data and obtained paleointensities of around 46 T, which is a good approximation of the ambient field of 48 T. Taking into account that the uncorrected mean paleointensity is about 57 T, this suggests that cooling rate correction is not only working, but also a necessary tool to yield the true field value. R. Leonhardt , J. Matzka, A.R.L. Nichols , D.B. Dingwell Cooling rate correction of paleointensity determination for volcanic glasses by relaxation geospeedometry; Earth and Planetary Science Letters 243 (2006) 282-292

Endogenous and exogenous ice-nucleating agents constrain supercooling in the hatchling painted turtle.

Science.gov (United States)

Costanzo, Jon P; Baker, Patrick J; Dinkelacker, Stephen A; Lee, Richard E

2003-02-01

Hatchlings of the painted turtle (Chrysemys picta) commonly hibernate in their shallow, natal nests. Survival at temperatures below the limit of freeze tolerance (approximately -4 degrees C) apparently depends on their ability to remain supercooled, and, whereas previous studies have reported that supercooling capacity improves markedly with cold acclimation, the mechanistic basis for this change is incompletely understood. We report that the crystallization temperature (T(c)) of recently hatched (summer) turtles acclimated to 22 degrees C and reared on a substratum of vermiculite or nesting soil was approximately 5 degrees C higher than the T(c) determined for turtles acclimated to 4 degrees C and tested in winter. This increase in supercooling capacity coincided with elimination of substratum (and, in fewer cases, eggshell) that the hatchlings had ingested; however, this association was not necessarily causal because turtles reared on a paper-covered substratum did not ingest exogenous matter but nevertheless showed a similar increase in supercooling capacity. Our results for turtles reared on paper revealed that seasonal development of supercooling capacity fundamentally requires elimination of ice-nucleating agents (INA) of endogenous origin: summer turtles, but not winter turtles, produced feces (perhaps derived from residual yolk) that expressed ice-nucleating activity. Ingestion of vermiculite or eggshell, which had modest ice-nucleating activity, had no effect on the T(c), whereas ingestion of nesting soil, which contained two classes of potent INA, markedly reduced the supercooling capacity of summer turtles. This effect persisted long after the turtles had purged their guts of soil particles, because the T(c) of winter turtles reared on nesting soil (mean +/- S.E.M.=-11.6+/-1.4 degrees C) was approximately 6 degrees C higher than the T(c) of winter turtles reared on vermiculite or paper. Experiments in which winter turtles were fed INA commonly found in

Calorimetric evidence for two distinct molecular packing arrangements in stable glasses of indomethacin.

Science.gov (United States)

Kearns, Kenneth L; Swallen, Stephen F; Ediger, M D; Sun, Ye; Yu, Lian

2009-02-12

Indomethacin glasses of varying stabilities were prepared by physical vapor deposition onto substrates at 265 K. Enthalpy relaxation and the mobility onset temperature were assessed with differential scanning calorimetry (DSC). Quasi-isothermal temperature-modulated DSC was used to measure the reversing heat capacity during annealing above the glass transition temperature Tg. At deposition rates near 8 A/s, scanning DSC shows two enthalpy relaxation peaks and quasi-isothermal DSC shows a two-step change in the reversing heat capacity. We attribute these features to two distinct local packing structures in the vapor-deposited glass, and this interpretation is supported by the strong correlation between the two calorimetric signatures of the glass to liquid transformation. At lower deposition rates, a larger fraction of the sample is prepared in the more stable local packing. The transformation of the vapor-deposited glasses into the supercooled liquid above Tg is exceedingly slow, as much as 4500 times slower than the structural relaxation time of the liquid.

Scaling parallels in the non-Debye dielectric relaxation of ionic glasses and dipolar supercooled liquids

International Nuclear Information System (INIS)

Sidebottom, D.L.; Green, P.F.; Brow, R.K.

1997-01-01

We compare the dielectric response of ionic glasses and dipolar liquids near the glass transition. Our work is divided into two parts. In the first section we examine ionic glasses and the two prominent approaches to analyzing the dielectric response. The conductivity of ion-conducting glasses displays a power law dispersion σ(ω)∝ω n , where n∼0.67, but frequently the dielectric response is analyzed using the electrical modulus M * (ω)=1/var-epsilon * (ω), where var-epsilon * (ω)=var-epsilon(ω)-iσ(ω)/ω is the complex permittivity. We reexamine two specific examples where the shape of M * (ω) changes in response to changes in (a) temperature and (b) ion concentration, to suggest fundamental changes in ion dynamics are occurring. We show, however, that these changes in the shape of M * (ω) occur in the absence of changes in the scaling properties of σ(ω), for which n remains constant. In the second part, we examine the dielectric relaxation found in dipolar liquids, for which var-epsilon * (ω) likewise exhibits changes in shape on approach to the glass transition. Guided by similarities of M * (ω) in ionic glasses and var-epsilon * (ω) in dipolar liquids, we demonstrate that a recent scaling approach proposed by Dixon and co-workers for var-epsilon * (ω) of dipolar relaxation also appears valid for M * (ω) in the ionic case. While this suggests that the Dixon scaling approach is more universal than previously recognized, we demonstrate how the dielectric response can be scaled in a linear manner using an alternative data representation. copyright 1997 The American Physical Society

Reversible and Irreversible Behavior of Glass-forming Materials from the Standpoint of Hierarchical Dynamical Facilitation

Science.gov (United States)

Keys, Aaron

2013-03-01

Using molecular simulation and coarse-grained lattice models, we study the dynamics of glass-forming liquids above and below the glass transition temperature. In the supercooled regime, we study the structure, statistics, and dynamics of excitations responsible for structural relaxation for several atomistic models of glass-formers. Excitations (or soft spots) are detected in terms of persistent particle displacements. At supercooled conditions, we find that excitations are associated with correlated particle motions that are sparse and localized, and the statistics and dynamics of these excitations are facilitated and hierarchical. Excitations at one point in space facilitate the birth and death of excitations at neighboring locations, and space-time excitation structures are microcosms of heterogeneous dynamics at larger scales. Excitation-energy scales grow logarithmically with the characteristic size of the excitation, giving structural-relaxation times that can be predicted quantitatively from dynamics at short time scales. We demonstrate that these same physical principles govern the dynamics of glass-forming systems driven out-of-equilibrium by time-dependent protocols. For a system cooled and re-heated through the glass transition, non-equilibrium response functions, such as heat capacities, are notably asymmetric in time, and the response to melting a glass depends markedly on the cooling protocol by which the glass was formed. We introduce a quantitative description of this behavior based on the East model, with parameters determined from reversible transport data, that agrees well with irreversible differential scanning calorimetry. We find that the observed hysteresis and asymmetric response is a signature of an underlying dynamical transition between equilibrium melts with no trivial spatial correlations and non-equilibrium glasses with correlation lengths that are both large and dependent upon the rate at which the glass is prepared. The correlation

Mechanical spectra of glass-forming liquids. I. Low-frequency bulk and shear moduli of DC704 and 5-PPE measured by piezoceramic transducers

DEFF Research Database (Denmark)

Hecksher, Tina; Olsen, Niels Boye; Nelson, Keith Adam

2013-01-01

We present dynamic shear and bulk modulus measurements of supercooled tetraphenyl-tetramethyl-trisiloxane (DC704) and 5-phenyl-4-ether over a range of temperatures close to their glass transition. The data are analyzed and compared in terms of time-temperature superposition (TTS), the relaxation ...

New Ti-based Ti–Cu–Zr–Fe–Sn–Si–Ag bulk metallic glass for biomedical applications

Energy Technology Data Exchange (ETDEWEB)

Pang, Shujie; Liu, Ying; Li, Haifei; Sun, Lulu [Key Laboratory of Aerospace Materials and Performance (Ministry of Education), School of Materials Science and Engineering, Beihang University, Beijing 100191 (China); Li, Yan [Key Laboratory of Aerospace Materials and Performance (Ministry of Education), School of Materials Science and Engineering, Beihang University, Beijing 100191 (China); Beijing Key Laboratory for Advanced Functional Materials and Thin Film Technology, Beihang University, Beijing 100191 (China); Zhang, Tao, E-mail: zhangtao@buaa.edu.cn [Key Laboratory of Aerospace Materials and Performance (Ministry of Education), School of Materials Science and Engineering, Beihang University, Beijing 100191 (China)

2015-03-15

Highlights: • Novel Ti{sub 47}Cu{sub 38}Zr{sub 7.5}Fe{sub 2.5}Sn{sub 2}Si{sub 1}Ag{sub 2} (at.%) bulk metallic glass (BMG) with a critical diameter of 7 mm was discovered. • The present BMG is the largest Ni- and Be-free Ti-based BMG containing low content of noble metal reported to date. • The glassy alloy possesses high specific strength, low Young’s modulus, and good corrosion resistance and bio-compatibility. • Combination of high glass-forming ability and good mechano- and bio-compatibility for the Ti-based BMG demonstrates the potential for use in biomedical applications. - Abstract: A novel Ni-free Ti{sub 47}Cu{sub 38}Zr{sub 7.5}Fe{sub 2.5}Sn{sub 2}Si{sub 1}Ag{sub 2} (at.%) bulk metallic glass (BMG) with superior glass-forming ability, good mechanical properties and excellent biocompatibility was discovered. The Ti-based BMG with a diameter of 7 mm can be prepared by copper mold casting and the supercooled liquid region was 52 K. Compressive strength, specific strength, Young’s modulus and microhardness of the Ti-based BMG were about 2.08 GPa, 3.2 × 10{sup 5} N m/kg, 100 GPa and 588 Hv, respectively. Electrochemical measurements indicated that the Ti-based glassy alloy possesses higher corrosion resistance than Ti–6Al–4V alloy in a simulated body fluid environment. Attachment, spreading out and proliferation of MC3T3-E1 cells on the Ti-based BMG surface demonstrated the excellent biocompatibility. Mechanisms of the formation and properties for the Ti-based glassy alloy are also discussed. The combination of high glass-forming ability, excellent mechanical properties, high corrosion resistance and good biocompatibility demonstrates the potential of the Ni-free Ti-based BMG for use in biomedical applications.

New Ti-based Ti–Cu–Zr–Fe–Sn–Si–Ag bulk metallic glass for biomedical applications

International Nuclear Information System (INIS)

Pang, Shujie; Liu, Ying; Li, Haifei; Sun, Lulu; Li, Yan; Zhang, Tao

2015-01-01

Highlights: • Novel Ti 47 Cu 38 Zr 7.5 Fe 2.5 Sn 2 Si 1 Ag 2 (at.%) bulk metallic glass (BMG) with a critical diameter of 7 mm was discovered. • The present BMG is the largest Ni- and Be-free Ti-based BMG containing low content of noble metal reported to date. • The glassy alloy possesses high specific strength, low Young’s modulus, and good corrosion resistance and bio-compatibility. • Combination of high glass-forming ability and good mechano- and bio-compatibility for the Ti-based BMG demonstrates the potential for use in biomedical applications. - Abstract: A novel Ni-free Ti 47 Cu 38 Zr 7.5 Fe 2.5 Sn 2 Si 1 Ag 2 (at.%) bulk metallic glass (BMG) with superior glass-forming ability, good mechanical properties and excellent biocompatibility was discovered. The Ti-based BMG with a diameter of 7 mm can be prepared by copper mold casting and the supercooled liquid region was 52 K. Compressive strength, specific strength, Young’s modulus and microhardness of the Ti-based BMG were about 2.08 GPa, 3.2 × 10 5 N m/kg, 100 GPa and 588 Hv, respectively. Electrochemical measurements indicated that the Ti-based glassy alloy possesses higher corrosion resistance than Ti–6Al–4V alloy in a simulated body fluid environment. Attachment, spreading out and proliferation of MC3T3-E1 cells on the Ti-based BMG surface demonstrated the excellent biocompatibility. Mechanisms of the formation and properties for the Ti-based glassy alloy are also discussed. The combination of high glass-forming ability, excellent mechanical properties, high corrosion resistance and good biocompatibility demonstrates the potential of the Ni-free Ti-based BMG for use in biomedical applications

The length and time scales of water's glass transitions

Science.gov (United States)

Limmer, David T.

2014-06-01

Using a general model for the equilibrium dynamics of supercooled liquids, I compute from molecular properties the emergent length and time scales that govern the nonequilibrium relaxation behavior of amorphous ice prepared by rapid cooling. Upon cooling, the liquid water falls out of equilibrium whereby the temperature dependence of its relaxation time is predicted to change from super-Arrhenius to Arrhenius. A consequence of this crossover is that the location of the apparent glass transition temperature depends logarithmically on cooling rate. Accompanying vitrification is the emergence of a dynamical length-scale, the size of which depends on the cooling rate and varies between angstroms and tens of nanometers. While this protocol dependence clarifies a number of previous experimental observations for amorphous ice, the arguments are general and can be extended to other glass forming liquids.

The length and time scales of water's glass transitions.

Science.gov (United States)

Limmer, David T

2014-06-07

Using a general model for the equilibrium dynamics of supercooled liquids, I compute from molecular properties the emergent length and time scales that govern the nonequilibrium relaxation behavior of amorphous ice prepared by rapid cooling. Upon cooling, the liquid water falls out of equilibrium whereby the temperature dependence of its relaxation time is predicted to change from super-Arrhenius to Arrhenius. A consequence of this crossover is that the location of the apparent glass transition temperature depends logarithmically on cooling rate. Accompanying vitrification is the emergence of a dynamical length-scale, the size of which depends on the cooling rate and varies between angstroms and tens of nanometers. While this protocol dependence clarifies a number of previous experimental observations for amorphous ice, the arguments are general and can be extended to other glass forming liquids.

Probing spatial heterogeneity in supercooled glycerol and temporal heterogeneity with single-molecule FRET in polyprolines

NARCIS (Netherlands)

Xia, Ted

2010-01-01

This thesis presents two lines of research. On the one hand, we investigate heterogeneity in supercooled glycerol by means of rheometry, small-angle neutron scattering, and fluorescence imaging. We find from the rheological experiments that supercooled glycerol can behave like weak solids at

Effects of Artificial Supercooling Followed by Slow Freezing on the Microstructure and Qualities of Pork Loin

OpenAIRE

Kim, Yiseul; Hong, Geun-Pyo

2016-01-01

This study investigated the effects of artificial supercooling followed by still air freezing (SSF) on the qualities of pork loin. The qualities of pork frozen by SSF were compared with the fresh control (CT, stored at 4? for 24 h), slow freezing (SAF, still air freezing) and rapid freezing (EIF, ethanol immersion freezing) treatments. Compared with no supercooling phenomena of SAF and EIF, the extent of supercooling obtained by SSF treatment was 1.4?. Despite that SSF was conducted with the ...

Limited Impact of Subglacial Supercooling Freeze-on for Greenland Ice Sheet Stratigraphy

Science.gov (United States)

Dow, Christine F.; Karlsson, Nanna B.; Werder, Mauro A.

2018-02-01

Large units of disrupted radiostratigraphy (UDR) are visible in many radio-echo sounding data sets from the Greenland Ice Sheet. This study investigates whether supercooling freeze-on rates at the bed can cause the observed UDR. We use a subglacial hydrology model to calculate both freezing and melting rates at the base of the ice sheet in a distributed sheet and within basal channels. We find that while supercooling freeze-on is a phenomenon that occurs in many areas of the ice sheet, there is no discernible correlation with the occurrence of UDR. The supercooling freeze-on rates are so low that it would require tens of thousands of years with minimal downstream ice motion to form the hundreds of meters of disrupted radiostratigraphy. Overall, the melt rates at the base of the ice sheet greatly overwhelm the freeze-on rates, which has implications for mass balance calculations of Greenland ice.

Experimental investigations on cylindrical latent heat storage units with sodium acetate trihydrate composites utilizing supercooling

DEFF Research Database (Denmark)

Dannemand, Mark; Johansen, Jakob Berg; Kong, Weiqiang

2016-01-01

Latent heat storage units utilizing stable supercooling of sodium acetate trihydrate (SAT) composites were tested in a laboratory. The stainless steel units were 1.5 m high cylinders with internal heat exchangers of tubes with fins. One unit was tested with 116 kg SAT with 6% extra water. Another...... in the thickened phase change material after melting. The heat content in the fully charged state and the heat released after solidification of the supercooled SAT mixtures at ambient temperature was higher for the unit with the thickened SAT mixture. The heat discharged after solidification of the supercooled SAT...

Complex bud architecture and cell-specific chemical patterns enable supercooling of Picea abies bud primordial

Science.gov (United States)

Bud primordia of Picea abies, despite a frozen shoot, stay ice free down to -50 °C by a mechanism termed supercooling whose biophysical and biochemical requirements are poorly understood. Bud architecture was assessed by 3D-reconstruction, supercooling and freezing patterns by infrared video thermog...

Laboratory test of a prototype heat storage module based on stable supercooling of sodium acetate trihydrate

DEFF Research Database (Denmark)

Dannemand, Mark; Kong, Weiqiang; Fan, Jianhua

2015-01-01

Laboratory test of a long term heat storage module utilizing the principle of stable supercooling of 199.5 kg of sodium acetate water mixture has been carried out. Avoiding phase separation of the incongruently melting salt hydrate by using the extra water principle increased the heat storage...... capacity. An external expansion vessel minimized the pressure built up in the module while heating and reduced the risk of instable supercooling. The module was stable supercooled at indoor ambient temperature for up to two months after which it was discharged. The energy discharged after activating...

Effect of Ga substitution on the crystallization behaviour and glass forming ability of Zr-Al-Cu-Ni alloys

International Nuclear Information System (INIS)

Singh, Devinder; Yadav, T.P.; Mandal, R.K.; Tiwari, R.S.; Srivastava, O.N.

2010-01-01

The crystallization behaviour of melt spun Zr 69.5 Al 7.5-x Ga x Cu 12 Ni 11 (x = 0-7.5; in at.%) metallic glasses has been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The DSC traces showed changes in crystallization behaviour with substitution of Ga. Formation of single nano-quasicrystalline phase by controlled crystallization of glasses has been found only for 0 ≤ x ≤ 1.5. Further increase of Ga content gives rise to formation of the quasicrystals together with Zr 2 Cu type crystalline phase. In addition to this, the substitution of Ga influences the size and shape of nano-quasicrystals. The glass forming abilities (GFAs) of these metallic glasses were assessed by the recognition of glass forming ability indicators, i.e. reduced glass transition temperature (T rg ) and supercooled liquid region (ΔT x ). The glass transition temperature (T g ) has been observed for all the melt spun ribbons.

METHANE GAS STABILIZES SUPERCOOLED ETHANE DROPLETS IN TITAN'S CLOUDS

International Nuclear Information System (INIS)

Wang, Chia C.; Lang, E. Kathrin; Signorell, Ruth

2010-01-01

Strong evidence for ethane clouds in various regions of Titan's atmosphere has recently been found. Ethane is usually assumed to exist as ice particles in these clouds, although the possible role of liquid and supercooled liquid ethane droplets has been recognized. Here, we report on infrared spectroscopic measurements of ethane aerosols performed in the laboratory under conditions mimicking Titan's lower atmosphere. The results clearly show that liquid ethane droplets are significantly stabilized by methane gas which is ubiquitous in Titan's nitrogen atmosphere-a phenomenon that does not have a counterpart for water droplets in Earth's atmosphere. Our data imply that supercooled ethane droplets are much more abundant in Titan's clouds than previously anticipated. Possibly, these liquid droplets are even more important for cloud processes and the formation of lakes than ethane ice particles.

Improvement of the thermoplastic formability of Zr65Cu17.5Ni10Al7.5 bulk metallic glass by minor addition of Erbium

International Nuclear Information System (INIS)

Hu, Q.; Zeng, X.R.; Fu, M.W.; Chen, S.S.; Jiang, J.

2016-01-01

The softness of Zr 65 Cu 17.5 Ni 10 Al 7.5 bulk metallic glass (BMG) in the super-cooled liquid range (SCLR) is obviously improved by minor addition of 2% Er, which makes (Zr 65 Cu 17.5 Ni 10 Al 7.5 ) 98 Er 2 (Zr65Er2) to be a very formable Be-free Zr-based BMG. It is found the lower glass transition temperature of Zr65Er2 has an important contribution to the improvement of formability, which is contrary to the general understanding that the larger fragility and wider super-cooled liquid region (SCLR) are the major reasons for better thermoplastic formability. This finding is well explained by using the linear simplification of the SCLR in Angell plot. Zr65Er2 also has lower crystallization temperature and melting temperature, which is believed to be related to the formation of short-range ordering with lower transition energy rather than the composition shift to near eutectic. The above results help understand the effect of minor addition of rare-earth to the formability of Zr-based bulk metallic glasses.

Magnetic properties of magnetic glass-like carbon prepared from furan resin alloyed with magnetic fluid

Energy Technology Data Exchange (ETDEWEB)

Nakamura, Kazumasa, E-mail: naka@sss.fukushima-u.ac.jp [Materials Science Area, Graduate School of Symbiotic Systems Science and Technology, Fukushima University, 1 Kanayagawa, Fukushima 960-1296 (Japan); Okuyama, Kyoko [Materials Science Area, Graduate School of Symbiotic Systems Science and Technology, Fukushima University, 1 Kanayagawa, Fukushima 960-1296 (Japan); Takase, Tsugiko [Institute of Environmental Radioactivity (IER), Fukushima University, 1 Kanayagawa, Fukushima 960-1296 (Japan)

2017-03-01

Magnetic glass-like carbons that were heat-treated at different temperatures or were filled with different magnetic nanoparticle contents were prepared from furan resin alloyed with magnetic fluid (MF) or Fe{sub 3}O{sub 4} powder in their liquid-phase states during mixing. Compared to the Fe{sub 3}O{sub 4} powder-alloyed carbon, the MF-alloyed carbon has highly dispersed the nanoparticles, and has the excellent saturation magnetization and coercivity. It is implied that saturation magnetizations are related to changes in the types of phases for the nanoparticles and the relative intensities of X-ray diffraction peaks for iron and iron-containing compounds in the carbons. Additionally, the coercivities are possibly affected by the size and crystallinity of the nanoparticles, the relative amounts of iron, and the existence of amorphous compounds on the carbon surfaces. - Highlights: • Magnetic glass-like carbons were prepared from furan resin alloyed with magnetic fluid. • The nanoparticles of MF-alloyed GLCs were highly dispersed. • MF-alloyed GLCs had excellent magnetic properties compared to powder-alloyed ones. • The magnetic properties changed with treatment temperature and nanoparticle content. • The changes in magnetic properties were investigated with XRD and FE-SEM.

Supercooled smectic nanoparticles

DEFF Research Database (Denmark)

Kuntsche, Judith; Koch, Michel H J; Fahr, Alfred

2009-01-01

Cholesteryl nonanoate (CN), myristate (CM), palmitate (CP) and oleate (CO) alone or in combination were evaluated as matrix lipids for the preparation of supercooled smectic nanoparticles with a high stability against recrystallization during storage. The phase behavior of the cholesterol esters......, laser diffraction combined with polarizing intensity differential scattering, DSC and SAXS. The morphology of selected formulations was studied by freeze-fracture electron microscopy. All smectic nanoparticles with a mixed cholesterol ester matrix were stable against recrystallization when stored...... at room temperature. Nanoparticles with a pure CN and mixed CM/CN matrix with a high fraction of CN (60% of the whole lipid matrix) could even be stored at 4 degrees C for at least 18 months without any recrystallization. As smectic nanoparticles are studied especially with regard to parenteral...

Nucleation and Nanometric Inhomogeneity in Niobiogermanate Glass: In-Situ Inelastic Light Scattering and TEM Studies

International Nuclear Information System (INIS)

Takahashi, Y; Ihara, R; Fujiwara, T; Osada, M; Masai, H

2011-01-01

We performed in-situ inelastic light scattering measurement in KNbGeO 5 glass with a high nucleation ability during heating in order to elucidate nanocrystallization dynamics. The results of the in-situ measurement and TEM observation revealed that nanometric heterogeneous region (∼1-2 nm) consisting of the Nb-richer phase develops, i.e., K 3 Nb 7 O 19 , at the temperature, in which glassy-supercooled-liquid (SCL) phase-transition occurs, i.e., precursive stage of nanocrystallization. This strongly suggests that evolution of the nanometric Nb-richer phase in the SCL phase corresponds to nucleation in the KNbGeO 5 glass.

Raman non-coincidence effect of boroxol ring: The interplay between repulsion and attraction forces in the glassy, supercooled and liquid state

Science.gov (United States)

Kalampounias, Angelos G.; Papatheodorou, George N.

2018-06-01

Temperature dependent Raman spectra of boric oxide have been measured in a temperature range covering the glassy, supercooled and liquid state. The shift of the isotropic band assigned to boroxol rings relative to the anisotropic component upon heating the glass is measured and attributed to the Raman non-coincidence effect. The measured shift is associated with the competition between attraction and repulsion forces with increasing temperature. The relation of dephasing and orientational relaxation times to the non-coincidence effect of the condensed phases has been examined. We discuss our results in the framework of the current phenomenological status of the field in an attempt to separate the attraction and repulsion contributions corresponding to the observed non-coincidence effect.

Effects of Artificial Supercooling Followed by Slow Freezing on the Microstructure and Qualities of Pork Loin

Science.gov (United States)

2016-01-01

This study investigated the effects of artificial supercooling followed by still air freezing (SSF) on the qualities of pork loin. The qualities of pork frozen by SSF were compared with the fresh control (CT, stored at 4℃ for 24 h), slow freezing (SAF, still air freezing) and rapid freezing (EIF, ethanol immersion freezing) treatments. Compared with no supercooling phenomena of SAF and EIF, the extent of supercooling obtained by SSF treatment was 1.4℃. Despite that SSF was conducted with the same method with SAF, application of artificial supercooling accelerated the phase transition (traverse from -0.6℃ to -5℃) from 3.07 h (SAF) to 2.23 h (SSF). The observation of a microstructure indicated that the SSF prevented tissue damage caused by ice crystallization and maintained the structural integrity. The estimated quality parameters reflected that SSF exhibited superior meat quality compared with slow freezing (SAF). SSF showed better water-holding capacity (lower thawing loss, cooking loss and expressible moisture) and tenderness than SAF, and these quality parameters of SSF were not significantly different with ultra-fast freezing treatment (EIF). Consequently, the results demonstrated that the generation of supercooling followed by conventional freezing potentially had the advantage of minimizing the quality deterioration caused by the slow freezing of meat. PMID:27857541

Effects of Artificial Supercooling Followed by Slow Freezing on the Microstructure and Qualities of Pork Loin.

Science.gov (United States)

Kim, Yiseul; Hong, Geun-Pyo

2016-10-31

This study investigated the effects of artificial supercooling followed by still air freezing (SSF) on the qualities of pork loin. The qualities of pork frozen by SSF were compared with the fresh control (CT, stored at 4℃ for 24 h), slow freezing (SAF, still air freezing) and rapid freezing (EIF, ethanol immersion freezing) treatments. Compared with no supercooling phenomena of SAF and EIF, the extent of supercooling obtained by SSF treatment was 1.4℃. Despite that SSF was conducted with the same method with SAF, application of artificial supercooling accelerated the phase transition (traverse from -0.6℃ to -5℃) from 3.07 h (SAF) to 2.23 h (SSF). The observation of a microstructure indicated that the SSF prevented tissue damage caused by ice crystallization and maintained the structural integrity. The estimated quality parameters reflected that SSF exhibited superior meat quality compared with slow freezing (SAF). SSF showed better water-holding capacity (lower thawing loss, cooking loss and expressible moisture) and tenderness than SAF, and these quality parameters of SSF were not significantly different with ultra-fast freezing treatment (EIF). Consequently, the results demonstrated that the generation of supercooling followed by conventional freezing potentially had the advantage of minimizing the quality deterioration caused by the slow freezing of meat.

Determination of Fragility in Organic Small Molecular Glass Forming Liquids: Comparison of Calorimetric and Spectroscopic Data and Commentary on Pharmaceutical Importance.

Science.gov (United States)

Chakravarty, Paroma; Pandya, Keyur; Nagapudi, Karthik

2018-03-05

The fragility index ( m) and conversely the strength parameter ( D) are widely used to categorize glass forming liquids and are used to characterize temperature dependency of viscosity and relaxation time as the supercooled liquid approaches glass transition. The currently used calorimetric methods in pharmaceutical literature lead to wide variability in measured values of m. In this work, a modulated differential scanning calorimetry (DSC) method is introduced that can directly determine m with minimal variability. Although calorimetric fragility is easy to measure due to availability and ease of use of DSC, there is no correlation between calorimetric and dielectric fragility (calculated spectroscopically from relaxation times). In addition, there is also no correlation between calorimetric fragility and the so-called "thermodynamic fragility" that can be calculated using only thermodynamic parameters. No relationship can be found between the crystallization propensity in the supercooled liquid state and D. However, the crystallization propensity shows a reasonable correlation with the Kohlrausch distribution parameter β k , which defines the breadth of the relaxation time distribution.

Evolution of the dynamic susceptibility of simple glass formers in the strongly supercooled regime

International Nuclear Information System (INIS)

Adichtchev, S; Blochowicz, T; Gainaru, C; Novikov, V N; Roessler, E A; Tschirwitz, C

2003-01-01

We discuss dielectric and light scattering susceptibility spectra of simple glass formers at temperatures above as well as below the critical temperature of the mode coupling theory (MCT). Close to T g the systems are characterized by the presence of a pronounced excess wing (type A glass formers). The data are analysed within a phenomenological approach, on the one hand, and within MCT, on the other. Among other work we present a complete interpolation of the dielectric data for glycerol (Lunkenheimer et al2000 Contemp. Phys. 41 15). The crossover temperature T x , defined by the emergence of the excess wing upon cooling, is extracted from the phenomenological analysis and found to agree well with the critical temperature T c , extracted from the MCT analysis at high temperatures. Below T x the evolution of the susceptibility is characterized by a universal appearance of the excess wing. No difference is observed for the non-fragile system with respect to fragile glass formers provided that the wing parameters are studied as a function of the correlation time τ α . Finally, a generalized scaling for the susceptibility minimum is proposed which is a phenomenological extension of that of MCT but now also includes the data below T c

Effect of instantaneous and continuous quenches on the density of vibrational modes in model glasses

Science.gov (United States)

Lerner, Edan; Bouchbinder, Eran

2017-08-01

Computational studies of supercooled liquids often focus on various analyses of their "underlying inherent states"—the glassy configurations at zero temperature obtained by an infinitely fast (instantaneous) quench from equilibrium supercooled states. Similar protocols are also regularly employed in investigations of the unjamming transition at which the rigidity of decompressed soft-sphere packings is lost. Here we investigate the statistics and localization properties of low-frequency vibrational modes of glassy configurations obtained by such instantaneous quenches. We show that the density of vibrational modes grows as ωβ with β depending on the parent temperature T0 from which the glassy configurations were instantaneously quenched. For quenches from high temperature liquid states we find β ≈3 , whereas β appears to approach the previously observed value β =4 as T0 approaches the glass transition temperature. We discuss the consistency of our findings with the theoretical framework of the soft potential model, and contrast them with similar measurements performed on configurations obtained by continuous quenches at finite cooling rates. Our results suggest that any physical quench at rates sufficiently slower than the inverse vibrational time scale—including all physically realistic quenching rates of molecular or atomistic glasses—would result in a glass whose density of vibrational modes is universally characterized by β =4 .

Alloy with metallic glass and quasi-crystalline properties

Science.gov (United States)

Xing, Li-Qian; Hufnagel, Todd C.; Ramesh, Kaliat T.

2004-02-17

An alloy is described that is capable of forming a metallic glass at moderate cooling rates and exhibits large plastic flow at ambient temperature. Preferably, the alloy has a composition of (Zr, Hf).sub.a Ta.sub.b Ti.sub.c Cu.sub.d Ni.sub.e Al.sub.f, where the composition ranges (in atomic percent) are 45.ltoreq.a.ltoreq.70, 3.ltoreq.b.ltoreq.7.5, 0.ltoreq.c.ltoreq.4, 3.ltoreq.b+c.ltoreq.10, 10.ltoreq.d.ltoreq.30, 0.ltoreq.e.ltoreq.20, 10.ltoreq.d+e.ltoreq.35, and 5.ltoreq.f.ltoreq.15. The alloy may be cast into a bulk solid with disordered atomic-scale structure, i.e., a metallic glass, by a variety of techniques including copper mold die casting and planar flow casting. The as-cast amorphous solid has good ductility while retaining all of the characteristic features of known metallic glasses, including a distinct glass transition, a supercooled liquid region, and an absence of long-range atomic order. The alloy may be used to form a composite structure including quasi-crystals embedded in an amorphous matrix. Such a composite quasi-crystalline structure has much higher mechanical strength than a crystalline structure.

SHORT COMMUNICATION: Recognition of supercooled dew in a quartz crystal microbalance dew-point sensor by slip phenomena

Science.gov (United States)

Kwon, Su-Yong; Kim, Jong-Chul; Choi, Byung-Il

2007-10-01

Distinguishing between a supercooled dew and frost below 0 °C in dew/frost-point measurements is an important and challenging problem that has not yet been completely solved. This study presents a new method for the recognition of a supercooled dew in a dew/frost-point sensor. A quartz crystal microbalance (QCM) sensor was used as a dew/frost-point sensor to detect a dew and a supercooled dew as well as frost. The slip phenomenon occurring at an interface between the water droplet and the surface of the quartz crystal resonator of the QCM sensor gives a simple and accurate way of distinguishing between a supercooled dew and frost below 0 °C. This method can give a highly accurate measurement of the dew or the frost point without misreading in the dew-point sensor at temperatures below 0 °C.

Communication: Minimum in the thermal conductivity of supercooled water: A computer simulation study

Energy Technology Data Exchange (ETDEWEB)

Bresme, F., E-mail: f.bresme@imperial.ac.uk [Chemical Physics Section, Department of Chemistry, Imperial College, London SW7 2AZ, United Kingdom and Department of Chemistry, Norwegian University of Science and Technology, Trondheim 7491 (Norway); Biddle, J. W.; Sengers, J. V.; Anisimov, M. A. [Institute for Physical Science and Technology, and Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742 (United States)

2014-04-28

We report the results of a computer simulation study of the thermodynamic properties and the thermal conductivity of supercooled water as a function of pressure and temperature using the TIP4P-2005 water model. The thermodynamic properties can be represented by a two-structure equation of state consistent with the presence of a liquid-liquid critical point in the supercooled region. Our simulations confirm the presence of a minimum in the thermal conductivity, not only at atmospheric pressure, as previously found for the TIP5P water model, but also at elevated pressures. This anomalous behavior of the thermal conductivity of supercooled water appears to be related to the maximum of the isothermal compressibility or the minimum of the speed of sound. However, the magnitudes of the simulated thermal conductivities are sensitive to the water model adopted and appear to be significantly larger than the experimental thermal conductivities of real water at low temperatures.

Communication: Minimum in the thermal conductivity of supercooled water: A computer simulation study

International Nuclear Information System (INIS)

Bresme, F.; Biddle, J. W.; Sengers, J. V.; Anisimov, M. A.

2014-01-01

We report the results of a computer simulation study of the thermodynamic properties and the thermal conductivity of supercooled water as a function of pressure and temperature using the TIP4P-2005 water model. The thermodynamic properties can be represented by a two-structure equation of state consistent with the presence of a liquid-liquid critical point in the supercooled region. Our simulations confirm the presence of a minimum in the thermal conductivity, not only at atmospheric pressure, as previously found for the TIP5P water model, but also at elevated pressures. This anomalous behavior of the thermal conductivity of supercooled water appears to be related to the maximum of the isothermal compressibility or the minimum of the speed of sound. However, the magnitudes of the simulated thermal conductivities are sensitive to the water model adopted and appear to be significantly larger than the experimental thermal conductivities of real water at low temperatures

Experimental evidence for excess entropy discontinuities in glass-forming solutions.

Science.gov (United States)

Lienhard, Daniel M; Zobrist, Bernhard; Zuend, Andreas; Krieger, Ulrich K; Peter, Thomas

2012-02-21

Glass transition temperatures T(g) are investigated in aqueous binary and multi-component solutions consisting of citric acid, calcium nitrate (Ca(NO(3))(2)), malonic acid, raffinose, and ammonium bisulfate (NH(4)HSO(4)) using a differential scanning calorimeter. Based on measured glass transition temperatures of binary aqueous mixtures and fitted binary coefficients, the T(g) of multi-component systems can be predicted using mixing rules. However, the experimentally observed T(g) in multi-component solutions show considerable deviations from two theoretical approaches considered. The deviations from these predictions are explained in terms of the molar excess mixing entropy difference between the supercooled liquid and glassy state at T(g). The multi-component mixtures involve contributions to these excess mixing entropies that the mixing rules do not take into account. © 2012 American Institute of Physics

Collision of the glass shards with the eye: A computational fluid-structure interaction model.

Science.gov (United States)

Karimi, Alireza; Razaghi, Reza; Biglari, Hasan; Sera, Toshihiro; Kudo, Susumu

2017-12-27

The main stream of blunt trauma injuries has been reported to be related to the automobile crashes, sporting activities, and military operations. Glass shards, which can be induced due to car accident, earthquake, gunshot, etc., might collide with the eye and trigger substantial scarring and, consequently, permanently affect the vision. The complications as a result of the collision with the eye and its following injuries on each component of the eye are difficult to be diagnosed. The objective of this study was to employ a Three-Dimensional (3D) computational Fluid-Structure Interaction (FSI) model of the human eye to assess the results of the glass shards collision with the eye. To do this, a rigid steel-based object hit a Smoothed-Particle Hydrodynamics (SPH) glass wall at the velocities of 100, 150, and 200 m/s and, subsequently, the resultant glass shards moved toward the eye. The amount of injury, then, quantified in terms of the stresses and strains. The results revealed the highest amount of stress in the cornea while the lowest one was observed in the vitreous body. It was also found that increasing the speed of the glass shards amplifies the amount of the stress in the components which are located in the central anterior zone of the eye, such as the cornea, aqueous body, and iris. However, regarding those components located in the peripheral/posterior side of the eye, especially the optic nerve, by increasing the amount of velocity a reduction in the stresses was observed and the optic nerve is hardly damaged. These findings have associations not only for understanding the amount of stresses/strains in the eye components at three different velocities, but also for providing preliminary information for the ophthalmologists to have a better diagnosis after glass shards (small objects impact) injuries to the eye. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of freeze-thaw repetitions upon the supercooling release ability of ice-nucleating bacteria

International Nuclear Information System (INIS)

Tsuchiya, Yooko; Hasegawa, Hiromi; Sasaki, Kazuhiro

2004-01-01

We have studied the durability of ice-nucleating bacteria with a potent supercooling release capacity through repeated freeze-thaw cycles. Through experiment, we confirmed that UV sterilized Erwinia ananas maintains a superior supercooling release capacity at around -1degC through 2000 freeze-thaw cycles. We also found that γ-ray sterilization, which is more suitable than UV for large-scale sterilization treatment, has a similar effect at appropriately selected doses. (author)

Pressure effect on crystallization kinetics in Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk glass

DEFF Research Database (Denmark)

Jiang, Jianzhong; Gerward, Leif; Xu, Y.S.

2002-01-01

Crystallization kinetics of a Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk glass in the supercooled liquid region have been investigated by performing in situ high-temperature and high-pressure x-ray diffraction measurements using synchrotron radiation. A pressure-time-temperature-transformation diagram......, describing the onset of crystallization as a function of time during isothermal annealing under pressure, is presented. Different pressure dependences of crystallization kinetics in the temperature range for the glass have been observed and further be explained by a model of competing processes...

Improvement of the thermoplastic formability of Zr{sub 65}Cu{sub 17.5}Ni{sub 10}Al{sub 7.5} bulk metallic glass by minor addition of Erbium

Energy Technology Data Exchange (ETDEWEB)

Hu, Q. [Shenzhen Key Laboratory of Special Functional Materials, College of Materials Science and Engineering, Shenzhen 518060 (China); Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060 (China); Zeng, X.R., E-mail: zengxier@szu.edu.cn [Shenzhen Key Laboratory of Special Functional Materials, College of Materials Science and Engineering, Shenzhen 518060 (China); Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060 (China); JANUS Precision Components Co., LTD., Dongguan 523000 (China); Fu, M.W., E-mail: mmmwfu@polyu.edu.hk [Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (China); Chen, S.S. [Shenzhen Key Laboratory of Special Functional Materials, College of Materials Science and Engineering, Shenzhen 518060 (China); Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060 (China); Jiang, J. [Institute of Applied Physics, Jiangxi Academy of Sciences, Nanchang 330029 (China)

2016-12-01

The softness of Zr{sub 65}Cu{sub 17.5}Ni{sub 10}Al{sub 7.5} bulk metallic glass (BMG) in the super-cooled liquid range (SCLR) is obviously improved by minor addition of 2% Er, which makes (Zr{sub 65}Cu{sub 17.5}Ni{sub 10}Al{sub 7.5}){sub 98}Er{sub 2} (Zr65Er2) to be a very formable Be-free Zr-based BMG. It is found the lower glass transition temperature of Zr65Er2 has an important contribution to the improvement of formability, which is contrary to the general understanding that the larger fragility and wider super-cooled liquid region (SCLR) are the major reasons for better thermoplastic formability. This finding is well explained by using the linear simplification of the SCLR in Angell plot. Zr65Er2 also has lower crystallization temperature and melting temperature, which is believed to be related to the formation of short-range ordering with lower transition energy rather than the composition shift to near eutectic. The above results help understand the effect of minor addition of rare-earth to the formability of Zr-based bulk metallic glasses.

Glass transitions in one-, two-, three-, and four-dimensional binary Lennard-Jones systems

Energy Technology Data Exchange (ETDEWEB)

Bruening, Ralf; St-Onge, Denis A; Patterson, Steve [Physics Department, Mount Allison University, Sackville, NB, E4L 1E6 (Canada); Kob, Walter [Laboratoire des Colloides, Verres et Nanomateriaux, UMR5587, Universite Montpellier II and CNRS, 34095 Montpellier Cedex (France)], E-mail: rbruening@mta.ca

2009-01-21

We investigate the calorimetric liquid-glass transition by performing simulations of a binary Lennard-Jones mixture in one through four dimensions. Starting at a high temperature, the systems are cooled to T = 0 and heated back to the ergodic liquid state at constant rates. Glass transitions are observed in two, three and four dimensions as a hysteresis between the cooling and heating curves. This hysteresis appears in the energy and pressure diagrams, and the scanning rate dependence of the area and height of the hysteresis can be described using power laws. The one-dimensional system does not experience a glass transition but its specific heat curve resembles the shape of the D{>=}2 results in the supercooled liquid regime above the glass transition. As D increases, the radial distribution functions reflect reduced geometric constraints. Nearest neighbor distances become smaller with increasing D due to interactions between nearest and next-nearest neighbors. Simulation data for the glasses are compared with crystal and melting data obtained with a Lennard-Jones system with only one type of particle and we find that with increasing D crystallization becomes increasingly more difficult.

Correlation between relaxations and plastic deformation, and elastic model of flow in metallic glasses and glass-forming liquids

International Nuclear Information System (INIS)

Wang Weihua

2011-01-01

We study the similarity and correlations between relaxations and plastic deformation in metallic glasses (MGs) and MG-forming liquids. It is shown that the microscope plastic events, the initiation and formation of shear bands, and the mechanical yield in MGs where the atomic sites are topologically unstable induced by applied stress, can be treated as the glass to supercooled liquid state transition induced by external shear stress. On the other hand, the glass transition, the primary and secondary relaxations, plastic deformation and yield can be attributed to the free volume increase induced flow, and the flow can be modeled as the activated hopping between the inherent states in the potential energy landscape. We then propose an extended elastic model to describe the flow based on the energy landscape theory. That is, the flow activation energy density is linear proportional to the instantaneous elastic moduli, and the activation energy density ρ E is determined to be a simple expression of ρ E =(10/11)G+(1/11)K. The model indicates that both shear and bulk moduli are critical parameters accounting for both the homogeneous and inhomogeneous flows in MGs and MG-forming liquids. The elastic model is experimentally certified. We show that the elastic perspectives offers a simple scenario for the flow in MGs and MG-forming liquids and are suggestive for understanding the glass transition, plastic deformation, and nature and characteristics of MGs

Corrosion study of resorbable Ca60Mg15Zn25 bulk metallic glasses in physiological fluids

Directory of Open Access Journals (Sweden)

Rafał Babilas

2017-10-01

Full Text Available The corrosion activity of amorphous plates of Ca60Mg15Zn25 alloy was investigated. The biocompatible elements were selected for the alloy composition. The electrochemical corrosion and immersion tests were carried out in a multi-electrolyte fluid and Ringer's solution. Better corrosion behavior was observed for the samples tested in a multi-electrolyte fluid despite the active dissolution of Ca and Mg in Ringer's solution. The experimental results indicated that reducing concentration of NaCl from 8.6 g/dm3 for Ringer's solution to 5.75 g/dm3 caused the decrease of the corrosion rate. The volume of the hydrogen evolved after 480 min in Ringer's solution (40.1 ml/cm2 was higher in comparison with that obtained in a multi-electrolyte fluid (24.4 ml/cm2. The values of open-circuit potential (EOCP for the Ca60Mg15Zn25 glass after 1 h incubation in Ringer's solution and a multi-electrolyte fluid were determined to be −1553 and −1536 mV vs. a saturated calomel electrode (SCE. The electrochemical measurements indicated a shift of the corrosion current density (jcorr from 1062 μA/cm2 for the sample tested in Ringer's solution to 788 μA/cm2 for the specimen immersed in a multi-electrolyte fluid. The corrosion products analysis was conducted by using the X-ray photoelectron spectroscopy (XPS. The corrosion products were identified to be CaCO3, Mg(OH2, CaO, MgO and ZnO. The mechanism of corrosion process was proposed and described based on the microscopic observations. The X-ray diffraction and Fourier transform infrared spectroscopy (FTIR also indicated that Ca(OH2, CaCO3, Zn(OH2 and Ca(Zn(OH32·2H2O mainly formed on the surface of the studied alloy. Keywords: Ca-based metallic glasses, X-ray photoelectron spectroscopy, FTIR spectroscopy, X-ray diffraction, Corrosion resistance, Hydrogen evaluation

Friction welding of bulk metallic glasses to different ones

International Nuclear Information System (INIS)

Shoji, Takuo; Kawamura, Yoshihito; Ohno, Yasuhide

2004-01-01

For application of bulk metallic glasses (BMGs) as industrial materials, it is necessary to establish the metallurgical bonding technology. The BMGs exhibit high-strain-rate superplasticity in the supercooled liquid state. It has been reported that bulk metallic glasses were successfully welded together by friction, pulse-current, explosion and electron-beam methods. In this study, friction welding of the BMGs to different ones were tried for Pd 40 Ni 40 P 20 , Pd 40 Cu 30 P 20 Ni 10 , Zr 55 Cu 30 Al 10 Ni 5 and Zr 41 Be 23 Ti 14 Cu 12 Ni 10 BMGs. Successful welding was obtained in the combinations of the Pd 40 Ni 40 P 20 and Pd 40 Cu 30 P 20 Ni 10 BMGs, and the Zr 55 Cu 30 Al 10 Ni 5 and Zr 41 Be 23 Ti 14 Cu 12 Ni 10 ones. No crystallization was observed and no visible defect was recognized in the interface. The joining strength of the welded BMGs was the same as that of the parent BMG or more. BMGs seem to be successfully welded to the different ones with a difference below about 50 K in glass transition temperature

Pressure dependence of glass transition in As2Te3 glass.

Science.gov (United States)

Ramesh, K

2014-07-24

Amorphous solids prepared from their melt state exhibit glass transition phenomenon upon heating. Viscosity, specific heat, and thermal expansion coefficient of the amorphous solids show rapid changes at the glass transition temperature (Tg). Generally, application of high pressure increases the Tg and this increase (a positive dT(g)/dP) has been understood adequately with free volume and entropy models which are purely thermodynamic in origin. In this study, the electrical resistivity of semiconducting As(2)Te(3) glass at high pressures as a function of temperature has been measured in a Bridgman anvil apparatus. Electrical resistivity showed a pronounced change at Tg. The Tg estimated from the slope change in the resistivity-temperature plot shows a decreasing trend (negative dT(g)/dP). The dT(g)/dP was found to be -2.36 °C/kbar for a linear fit and -2.99 °C/kbar for a polynomial fit in the pressure range 1 bar to 9 kbar. Chalcogenide glasses like Se, As(2)Se(3), and As(30)Se(30)Te(40) show a positive dT(g)/dP which is very well understood in terms of the thermodynamic models. The negative dT(g)/dP (which is generally uncommon in liquids) observed for As(2)Te(3) glass is against the predictions of the thermodynamic models. The Adam-Gibbs model of viscosity suggests a direct relationship between the isothermal pressure derivative of viscosity and the relaxational expansion coefficient. When the sign of the thermal expansion coefficient is negative, dT(g)/dP = Δk/Δα will be less than zero, which can result in a negative dT(g)/dP. In general, chalcogenides rich in tellurium show a negative thermal expansion coefficient (NTE) in the supercooled and stable liquid states. Hence, the negative dT(g)/dP observed in this study can be understood on the basis of the Adams-Gibbs model. An electronic model proposed by deNeufville and Rockstad finds a linear relation between Tg and the optical band gap (Eg) for covalent semiconducting glasses when they are grouped

Acoustic and thermal anomalies in a liquid-glass transition of racemic S(+)-R(-) ketoprofen

Science.gov (United States)

Shibata, Tomohiko; Takayama, Haruki; Kim, Tae Hyun; Kojima, Seiji

2014-01-01

Acoustic and thermal properties of pharmaceutical racemic S(+)-R(-) ketoprofen were investigated in wide temperature range including glassy, supercooled liquid and liquid states by Brillouin scattering and temperature modulated DSC. Sound velocity and acoustic attenuation exhibited clear changes at 265 K indicating a liquid-glass transition and showed the typical structural relaxation above Tg. The high value of the fragility index m = 71 was determined by the dispersion of the complex heat capacity. New relaxation map was suggested in combination with previous study of dielectric measurement.

Fabrication and characterization of microencapsulated phase change material with low supercooling for thermal energy storage

International Nuclear Information System (INIS)

Tang, Xiaofen; Li, Wei; Zhang, Xingxiang; Shi, Haifeng

2014-01-01

Microencapsulated phase change material with a low supercooling degree is one of the increasing important researches as well as industrial application for thermal energy storage. This study develops a novel and low supercooling microencapsulated n-octadecane (MicroC18) with n-octadecyl methacrylate (ODMA)–methacrylic acid (MAA) copolymer as shell using suspension-like polymerization. The fabrication and properties of MicroC18 were characterized by using a field-emission scanning electron microscope (FE-SEM), Fourier transformed infrared spectroscopy (FTIR), particle size distribution analysis, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The MicroC18 with spherical shapes and an average diameter of 1.60–1.68 μm are fabricated. The onset crystallizing temperatures of MicroC18 are only 4 °C below that of n-octadecane. The unique copolymer shell has a significant impact on the low supercooling of MicroC18. The n-octadecane in all of the samples crystalizes by heterogeneous nucleation. The content of n-octadecane in the microcapsules is low; however, the microcapsules still exhibit high enthalpy through the contribution of the shells. At a monomers/n-octadecane mass ratio is 2:1, as used in the recipes, the MicroC18 with highest phase change enthalpy was obtained. The temperature of thermal resistant of MicroC18 is approximately 235.6 °C, which is affected by the thickness of the polymer shell. - Highlights: • Microencapsulated n-octadecane with comb-like copolymer shell has low supercooling. • The unique shell plays a significant role in suppressing supercooling. • The types of cross-linker affect morphologies and heat enthalpies of microcapsules. • Microcapsules exhibit high phase change enthalpies and thermal stabilities

Simulation of Cu-Mg metallic glass: Thermodynamics and structure

International Nuclear Information System (INIS)

Bailey, Nicholas P.; Schioetz, Jakob; Jacobsen, Karsten W.

2004-01-01

We have obtained effective medium theory interatomic potential parameters suitable for studying Cu-Mg metallic glasses. We present thermodynamic and structural results from simulations of such glasses over a range of compositions. We have produced low-temperature configurations by cooling from the melt at as slow a rate as practical, using constant temperature and pressure molecular dynamics. During the cooling process we have carried out thermodynamic analyses based on the temperature dependence of the enthalpy and its derivative, the specific heat, from which the glass transition temperature may be determined. We have also carried out structural analyses using the radial distribution function (RDF) and common neighbor analysis (CNA). Our analysis suggests that the splitting of the second peak, commonly associated with metallic glasses, in fact, has little to do with the glass transition itself, but is simply a consequence of the narrowing of peaks associated with structural features present in the liquid state. In fact, the splitting temperature for the Cu-Cu RDF is well above T g . The CNA also highlights a strong similarity between the structure of the intermetallic alloys and the amorphous alloys of similar composition. We have also investigated the diffusivity in the supercooled regime. Its temperature dependence indicates fragile-liquid behavior, typical of binary metallic glasses. On the other hand, the relatively low specific-heat jump of around 1.5k B /atom indicates apparent strong-liquid behavior, but this can be explained by the width of the transition due to the high cooling rates

Enhancement of plasticity of Fe-based bulk metallic glass by Ni substitution for Fe

Energy Technology Data Exchange (ETDEWEB)

Guo, S.F. [State Key Laboratory of Material Processing and Die and Mould Technology, Huazhong University of Science and Technology, 430074 Wuhan (China); State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083 (China); Li, N.; Zhang, C. [State Key Laboratory of Material Processing and Die and Mould Technology, Huazhong University of Science and Technology, 430074 Wuhan (China); Liu, L., E-mail: sfguo2005@163.co [State Key Laboratory of Material Processing and Die and Mould Technology, Huazhong University of Science and Technology, 430074 Wuhan (China)

2010-08-15

Bulk metallic glasses (BMGs) (Fe{sub 1-x}Ni{sub x}){sub 71}Mo{sub 5}P{sub 12}C{sub 10}B{sub 2} (x = 0, 0.1 and 0.2) with a diameter of 3 mm were synthesized by copper mold casting. The effect of Ni substitution for Fe on the structure, thermal and mechanical properties has been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and compressive testing. It was found that the substitution of Ni for Fe enhances the glass forming ability, and improves the plasticity of Fe{sub 71}Mo{sub 5}P{sub 12}C{sub 10}B{sub 2} BMG as indicated by the increase in the plastic strain from 3.1% (x = 0) to 5.2% (x = 0.2). The improvement of the plasticity is discussed in term of the reduction of glass transition temperature and the supercooled liquid region due to the substitution of Ni for Fe.

Thermodynamics of Fluid Polyamorphism

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Mikhail A. Anisimov

2018-01-01

Full Text Available Fluid polyamorphism is the existence of different condensed amorphous states in a single-component fluid. It is either found or predicted, usually at extreme conditions, for a broad group of very different substances, including helium, carbon, silicon, phosphorous, sulfur, tellurium, cerium, hydrogen, and tin tetraiodide. This phenomenon is also hypothesized for metastable and deeply supercooled water, presumably located a few degrees below the experimental limit of homogeneous ice formation. We present a generic phenomenological approach to describe polyamorphism in a single-component fluid, which is completely independent of the molecular origin of the phenomenon. We show that fluid polyamorphism may occur either in the presence or in the absence of fluid phase separation depending on the symmetry of the order parameter. In the latter case, it is associated with a second-order transition, such as in liquid helium or liquid sulfur. To specify the phenomenology, we consider a fluid with thermodynamic equilibrium between two distinct interconvertible states or molecular structures. A fundamental signature of this concept is the identification of the equilibrium fraction of molecules involved in each of these alternative states. However, the existence of the alternative structures may result in polyamorphic fluid phase separation only if mixing of these structures is not ideal. The two-state thermodynamics unifies all the debated scenarios of fluid polyamorphism in different areas of condensed-matter physics, with or without phase separation, and even goes beyond the phenomenon of polyamorphism by generically describing the anomalous properties of fluids exhibiting interconversion of alternative molecular states.

An energy landscape based approach for studying supercooled liquid and glassy thin films

Science.gov (United States)

Shah, Pooja; Mittal, Jeetain; Truskett, Thomas M.

2004-03-01

Materials in confined spaces are important in science and technology. Examples include biological fluids in membranes, liquids trapped in porous rocks, and thin-film materials used in high-resolution patterning technologies. However, few reliable rules exist to predict how the properties of materials will be affected by thin-film confinement. We have recently shown that the potential energy landscape formalism can be used to study, by both theory [1] and simulation [2], how the behavior of thin-film materials depends on sample dimensions and film-substrate interactions. Our landscape-based mean-field theory [1] can be used to study both the thermodynamic properties and the ideal glass transition of thin films. It predicts that, in the case of neutral or repulsive walls, the ideal glass transition temperature is lowered by decreasing film thickness. This is in qualitative agreement with experimental trends for the kinetic glass transition in confined fluids. Landscape-based approaches are also valuable for understanding the structural and mechanical properties of thin-film glasses. We demonstrate how the concept of an "equation of state of the energy landscape" [3] can be generalized to thin films [1, 2], where it gives insights into potential molecular mechanisms of tensile strength. [1] T. M. Truskett and V. Ganesan, J. Chem. Phys. 119, 1897-1900(2003); J. Mittal, P. Shah and T. M. Truskett, to be submitted to Langmuir. [2] P. Shah and T. M. Truskett, to be submitted to J. Phys. Chem. B. [3] S. Sastry, P. G. Debenedetti and F. H. Stillinger, Phys. Rev. E 56, 5533 (1997)

Ideal glass transitions in thin films: An energy landscape perspective

OpenAIRE

Truskett, Thomas M.; Ganesan, Venkat

2003-01-01

We introduce a mean-field model for the potential energy landscape of a thin fluid film confined between parallel substrates. The model predicts how the number of accessible basins on the energy landscape and, consequently, the film's ideal glass transition temperature depend on bulk pressure, film thickness, and the strength of the fluid-fluid and fluid-substrate interactions. The predictions are in qualitative agreement with the experimental trends for the kinetic glass transition temperatu...

Stress overshoot in stress-strain curves of Zr65Al10Ni10Cu15 metallic glass

International Nuclear Information System (INIS)

Kawamura, Y.; Shibata, T.; Inoue, A.; Masumoto, T.

1997-01-01

The essential features of the stress overshoot in the stress-strain curves of Zr 65 Al 10 Ni 10 Cu 15 (at.%) metallic glass that has a wide supercooled liquid region were revealed. The stress overshoot was dependent on temperature, strain rate, and stress relaxation. During the stretch, a change in strain rate gave rise to stress overshoot or undershoot which was sensitive to the variable quantities in the strain rate. copyright 1997 American Institute of Physics

Preparation and Supercooling Modification of Salt Hydrate Phase Change Materials Based on CaCl₂·2H₂O/CaCl₂.

Science.gov (United States)

Xu, Xiaoxiao; Dong, Zhijun; Memon, Shazim Ali; Bao, Xiaohua; Cui, Hongzhi

2017-06-23

Salt hydrates have issues of supercooling when they are utilized as phase change materials (PCMs). In this research, a new method was adopted to prepare a salt hydrate PCM (based on a mixture of calcium chloride dihydrate and calcium chloride anhydrous) as a novel PCM system to reduce the supercooling phenomenon existing in CaCl₂·6H₂O. Six samples with different compositions of CaCl₂ were prepared. The relationship between the performance and the proportion of calcium chloride dihydrate (CaCl₂·2H₂O) and calcium chloride anhydrous (CaCl₂) was also investigated. The supercooling degree of the final PCM reduced with the increase in volume of CaCl₂·2H₂O during its preparation. The PCM obtained with 66.21 wt % CaCl₂·2H₂O reduced the supercooling degree by about 96.8%. All six samples, whose ratio of CaCl₂·2H₂O to (CaCl₂ plus CaCl₂·2H₂O) was 0%, 34.03%, 53.82%, 76.56%, 90.74%, and 100% respectively, showed relatively higher enthalpy (greater than 155.29 J/g), and have the possibility to be applied in buildings for thermal energy storage purposes. Hence, CaCl₂·2H₂O plays an important role in reducing supercooling and it can be helpful in adjusting the solidification enthalpy. Thereafter, the influence of adding different percentages of Nano-SiO₂ (0.1 wt %, 0.3 wt %, 0.5 wt %) in reducing the supercooling degree of some PCM samples was investigated. The test results showed that the supercooling of the salt hydrate PCM in Samples 6 and 5 reduced to 0.2 °C and 0.4 °C respectively. Finally, the effect of the different cooling conditions, including frozen storage (-20 °C) and cold storage (5 °C), that were used to prepare the salt hydrate PCM was considered. It was found that both cooling conditions are effective in reducing the supercooling degree of the salt hydrate PCM. With the synergistic action of the two materials, the performance and properties of the newly developed PCM systems were better especially in terms of reducing

On melting dynamics and the glass transition. II. Glassy dynamics as a melting process.

Science.gov (United States)

Krzakala, Florent; Zdeborová, Lenka

2011-01-21

There are deep analogies between the melting dynamics in systems with a first-order phase transition and the dynamics from equilibrium in super-cooled liquids. For a class of Ising spin models undergoing a first-order transition--namely p-spin models on the so-called Nishimori line--it can be shown that the melting dynamics can be exactly mapped to the equilibrium dynamics. In this mapping the dynamical--or mode-coupling--glass transition corresponds to the spinodal point, while the Kauzmann transition corresponds to the first-order phase transition itself. Both in mean field and finite dimensional models this mapping provides an exact realization of the random first-order theory scenario for the glass transition. The corresponding glassy phenomenology can then be understood in the framework of a standard first-order phase transition.

Development of seasonal heat storage based on stable supercooling of a sodium acetate water mixture

DEFF Research Database (Denmark)

Furbo, Simon; Fan, Jianhua; Andersen, Elsa

2012-01-01

A number of heat storage modules for seasonal heat storages based on stable supercooling of a sodium acetate water mixture have been tested by means of experiments in a heat storage test facility. The modules had different volumes and designs. Further, different methods were used to transfer heat...... to and from the sodium acetate water mixture in the modules. By means of the experiments: • The heat exchange capacity rates to and from the sodium acetate water mixture in the heat storage modules were determined for different volume flow rates. • The heat content of the heat storage modules were determined....... • The reliability of the supercooling was elucidated for the heat storage modules for different operation conditions. • The reliability of a cooling method used to start solidification of the supercooled sodium acetate water mixture was elucidated. The method is making use of boiling CO2 in a small tank in good...

Energy landscapes in proteins and glasses

Science.gov (United States)

Singh, Sadanand

Soft materials are ubiquitous in our day-to-day life. They include liquids, colloids, polymers, foams, gels, granular systems, and a number of biological materials. While these materials exhibit a wide range of textures and morphologies, many of their properties have common physicochemical origins. A better understanding of such origins would lead to rational design and engineering of functional soft materials. A common feature of soft materials is the wide range of time and length scales that characterizes their behavior. Unfortunately, available molecular modeling techniques are often ill-suited for problems that exhibit multiple length and time scales. In this thesis, we introduce and implement new simulation methods that have enabled molecular-level studies of soft materials. Such methods permit calculation of free energy surfaces, and we demonstrate their usefulness in the context of proteins and glasses, both of which exhibit rugged free energy landscapes. A first application is concerned with human amylin, a protein associated with Type II diabetes. Patients with Type II diabetes exhibit fibrillar deposits of human amylin protein in the pancreas. By applying the advanced simulation methods and algorithms developed in this work, we investigate the structure and folding dynamics of human amylin. A detailed mechanism is presented at the atomic-level for the nucleation and aggregation of the peptide. The results presented in this work could help in development of therapeutic strategies for Type II diabetes. The second application is concerned with the study of vapor-deposited ultrastable glasses. These stable glasses have, far below the conventional glass transition temperature, the properties expected from the equilibrium supercooled liquid state. Our results indicate that optimal stability is attained when deposition occurs near the Kauzmann temperature. We also show that the extraordinary stability of model vapor deposited glasses is associated with distinct

Qualitative and quantitative analysis of different fluid phase in samples of glass beads by X-ray microtomography

International Nuclear Information System (INIS)

Marques, Leonardo C.; Nagata, Rodrigo; Appoloni, Carlos R.; Moreira, Anderson C.; Fernanades, Celso P.

2011-01-01

The X-ray microtomography has showed to be a useful tool for studies of inner structure of reservoir rocks. Moreover recent works have used this methodology to visualize different fluid phases present in these microstructures. In this paper X-ray microtomography has been applied to visualize three fluid phases, separately or simultaneously, in addition to a solid phase (glass beads). Two glass beads samples were manufactured and scanned, one with 0.8 mm (GB1) and other with 0.6 mm (GB2) diameter, respectively. The three fluid phases used were air, oil and a water-salt-potassium iodine solution. Two Skyscan scanners were used, both a 1172 model, which employs X-ray tube with W anode and cone beam. This laboratory based equipment is able to provide images of until 1 μm spatial resolution. One microtomograph is located at CENPES/PETROBRAS and has a CCD camera of 10 mega pixels resolution. It was used to measure the GB1 sample at 4.84 μm spatial resolution. The other one is located at LAMIR/UFPR and has a CCD camera of 11 mega pixels resolution. It was used to measure the GB2 sample at 4.99 μm spatial resolution. GB1 sample was set up with three fluid phases and presented 38.0 (2.7) % of total porosity before fluid presence and 3.5 % and 19.8 %, as lower and higher average porosity values, respectively, after to be filled with them. GB2 sample was set up with oil and water-salt-potassium iodine solution separated. It presented 36.7 (1.9) % of total porosity when dried, 18.7 (2.0) % when filled with oil and 0 % when filled with the solution. The 2D images clearly show the presence of the solution in addition to the air and solid phases. They also show that the presence of oil phase is less clear than the solution. When all the phases are present together in the sample it is possible to differentiate all of them. Individual 3D images are shown for each phase present in the sample. The 3D image containing all the phases is also shown. (author)

On abnormal decomposition of supercooled austenite in carbon and alloy steels

International Nuclear Information System (INIS)

Parusov, V.V.; Dolzhenkov, I.I.; Podobedov, L.V.; Vakulenko, I.A.

1980-01-01

Residual stresses which appear as a result of thermal cycling in the temperature range of 300-700 deg C are investigated in an austenitic class steel (03Kh18N11) to ground the assumption on the effect of plastic deformation, appearing due to thermal stresses, on the mechanism of supercooled austenite decomposition. The determination of residual stresses is carried out with the help of X-ray diffraction analysis. It is established that the deformation brings about an increase in density of dislocation the interaction of which leads to the formation of a typical austenite substructure which conditions the proceeding of the eutectoid transformation according to an abnormal mechanism. It is noted, that the grain pearlite formation due to plastic and microplastic deformation of supercooled austenite induced by thermal stresses should be taken into account when developing steel heat treatment shedules [ru

Ideal glass transitions in thin films: An energy landscape perspective

Science.gov (United States)

Truskett, Thomas M.; Ganesan, Venkat

2003-07-01

We introduce a mean-field model for the potential energy landscape of a thin fluid film confined between parallel substrates. The model predicts how the number of accessible basins on the energy landscape and, consequently, the film's ideal glass transition temperature depend on bulk pressure, film thickness, and the strength of the fluid-fluid and fluid-substrate interactions. The predictions are in qualitative agreement with the experimental trends for the kinetic glass transition temperature of thin films, suggesting the utility of landscape-based approaches for studying the behavior of confined fluids.

Enzyme kinetics in acoustically levitated droplets of supercooled water: a novel approach to cryoenzymology.

Science.gov (United States)

Weis, David D; Nardozzi, Jonathan D

2005-04-15

The rate of the alkaline phosphatase-catalyzed hydrolysis of 4-methylumbelliferone phosphate was measured in acoustically levitated droplets of aqueous tris (50 mM) at pH 8.5 at 22 +/- 2 degrees C and in supercooled solution at -6 +/- 2 degrees C. At 22 degrees C, the rate of product formation was in excellent agreement with the rate observed in bulk solution in a cuvette, indicating that the acoustic levitation process does not alter the enzyme activity. The rate of the reaction decreased 6-fold in supercooled solution at -6 +/- 2 degrees C. The acoustic levitator apparatus is described in detail.

Microstructure of bonding interface for resistance welding of Zr-based metallic glass sheets

International Nuclear Information System (INIS)

Kuroda, Toshio; Ikeuchi, Kenji; Shimada, Masahiro; Kobayashi, Akira; Kimura, Hisamichi; Inoue, Akihisa

2009-01-01

Resistance welding of Zr 55 Cu 30 Al 10 Ni 5 metallic glass sheets was investigated at 723 K in a supercooled liquid region. The welding time was changed from 5 s to 20 s at 723 K. The joint interface of the metallic glass was no defect and no crack. X-ray diffraction technique of the bonding interface of specimens was performed. The specimens showed halo patterns showing existence of only glassy phase, when the welding time was 5 s and 10 s. X-ray diffraction patterns of specimen bonded for 20 s showed crystalline peaks with halo patterns for the welding for 20 s. The crystalline phase at the bonding interface was small. Transmission electron micrograph at the bonding interface showed nanostructures of NiZr 2 and Al 5 Ni 3 Zr 2 . (author)

Thermodynamics of Supercooled and Glassy Water

Science.gov (United States)

Debenedetti, Pablo G.

1998-03-01

The behavior of metastable water at low temperatures is unusual. The isothermal compressibility, the isobaric heat capacity, and the magnitude of the thermal expansion coefficient increase sharply upon supercooling, and structural relaxation becomes extremely sluggish at temperatures far above the glass transition(Angell, C.A., Annu. Rev. Phys. Chem., 34, 593, 1983)(Debenedetti, P.G., Metastable Liquids. Concepts and Principles, Princeton University Press, 1996). Water has two distinct glassy phases, low- and high-density amorphous ice (LDA, HDA). The transition between LDA and HDA is accompanied by sharp volume and enthalpy changes, and appears to be first-order(Mishima, O., L.D.Calvert, and E. Whalley, Nature, 314, 76, 1985)(Mishima, O., J. Chem. Phys., 100, 5910, 1994). The understanding of these observations in terms of an underlying global phase behavior remains incomplete(Speedy, R.J., J. Phys. Chem., 86, 982, 1982)(Poole, P.H., F. Sciortino, U. Essman, and H.E. Stanley, Nature, 360, 324, 1992)(Sastry, S., P.G. Debenedetti, F. Sciortino, and H.E. Stanley, Phys. Rev. E, 53, 6144, 1996)(Tanaka, H., Nature, 380, 328, 1996)(Xie, Y., K.F. Ludwig, G. Morales, D.E. Hare, and C.M. Sorensen, Phys. Rev. Lett., 71, 2050, 1993). Microscopic theories and computer simulations suggest several scenarios that can reproduce some experimental observations. Interesting and novel ideas have resulted from this body of theoretical work, such as the possibility of liquid-liquid immiscibility in a pure substance(Poole, P.H., F.Sciortino, T.Grande, H.E. Stanley, and C.A. Angell, Phys. Rev. Lett., 73, 1632, 1994)(Roberts, C.J., and P.G. Debenedetti, J. Chem. Phys., 105, 658, 1996)(Roberts, C.J., P.G. Debenedetti, and A.Z. Panagiotopoulos, Phys. Rev. Lett., 77, 4386, 1996)(Harrington, S., R. Zhang, P.H. Poole, F. Sciortino, and H.E. Stanley, Phys. Rev. Lett., 78, 2409, 1997). In this talk I will review the experimental facts, discuss their theoretical interpretation, and identify key

Correlation between thermodynamic anomalies and pathways of ice nucleation in supercooled water

International Nuclear Information System (INIS)

Singh, Rakesh S.; Bagchi, Biman

2014-01-01

The well-known classical nucleation theory (CNT) for the free energy barrier towards formation of a nucleus of critical size of the new stable phase within the parent metastable phase fails to take into account the influence of other metastable phases having density/order intermediate between the parent metastable phase and the final stable phase. This lacuna can be more serious than capillary approximation or spherical shape assumption made in CNT. This issue is particularly significant in ice nucleation because liquid water shows rich phase diagram consisting of two (high and low density) liquid phases in supercooled state. The explanations of thermodynamic and dynamic anomalies of supercooled water often invoke the possible influence of a liquid-liquid transition between two metastable liquid phases. To investigate both the role of thermodynamic anomalies and presence of distinct metastable liquid phases in supercooled water on ice nucleation, we employ density functional theoretical approach to find nucleation free energy barrier in different regions of phase diagram. The theory makes a number of striking predictions, such as a dramatic lowering of nucleation barrier due to presence of a metastable intermediate phase and crossover in the dependence of free energy barrier on temperature near liquid-liquid critical point. These predictions can be tested by computer simulations as well as by controlled experiments

Simple Theory for the Dynamics of Mean-Field-Like Models of Glass-Forming Fluids

Science.gov (United States)

Szamel, Grzegorz

2017-10-01

We propose a simple theory for the dynamics of model glass-forming fluids, which should be solvable using a mean-field-like approach. The theory is based on transparent physical assumptions, which can be tested in computer simulations. The theory predicts an ergodicity-breaking transition that is identical to the so-called dynamic transition predicted within the replica approach. Thus, it can provide the missing dynamic component of the random first order transition framework. In the large-dimensional limit the theory reproduces the result of a recent exact calculation of Maimbourg et al. [Phys. Rev. Lett. 116, 015902 (2016), 10.1103/PhysRevLett.116.015902]. Our approach provides an alternative, physically motivated derivation of this result.

Dynamics of supercooled confined water measured by deep inelastic neutron scattering

Science.gov (United States)

De Michele, Vincenzo; Romanelli, Giovanni; Cupane, Antonio

2018-02-01

In this paper, we present the results of deep inelastic neutron scattering (DINS) measurements on supercooled water confined within the pores (average pore diameter 20 Å) of a disordered hydrophilic silica matrix obtained through hydrolysis and polycondensation of the alkoxide precursor Tetra-Methyl-Ortho-Silicate via the sol-gel method. Experiments were performed at two temperatures (250 K and 210 K, i.e., before and after the putative liquid-liquid transition of supercooled confined water) on a "wet" sample with hydration h 40% w/w, which is high enough to have water-filled pores but low enough to avoid water crystallization. A virtually "dry" sample at h 7% was also investigated to measure the contribution of the silica matrix to the neutron scattering signal. As is well known, DINS measurements allow the determination of the mean kinetic energy and the momentum distribution of the hydrogen atoms in the system and therefore, allow researchers to probe the local structure of supercooled confined water. The main result obtained is that at 210 K the hydrogen mean kinetic energy is equal or even slightly higher than at 250 K. This is at odds with the predictions of a semiempirical harmonic model recently proposed to describe the temperature dependence of the kinetic energy of hydrogen in water. This is a new and very interesting result, which suggests that at 210 K, the water hydrogens experience a stiffer intermolecular potential than at 250 K. This is in agreement with the liquid-liquid transition hypothesis.

Crystallization in diblock copolymer thin films at different degrees of supercooling

DEFF Research Database (Denmark)

Darko, C.; Botiz, I.; Reiter, G.

2009-01-01

The crystalline structures in thin films of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers were studied in dependence on the degree of supercooling. Atomic force microscopy showed that the crystalline domains (lamellae) consist of grains, which are macroscopic at low and interme...

Linking density functional and mode coupling models for supercooled liquids.

Science.gov (United States)

Premkumar, Leishangthem; Bidhoodi, Neeta; Das, Shankar P

2016-03-28

We compare predictions from two familiar models of the metastable supercooled liquid, respectively, constructed with thermodynamic and dynamic approaches. In the so called density functional theory the free energy F[ρ] of the liquid is a functional of the inhomogeneous density ρ(r). The metastable state is identified as a local minimum of F[ρ]. The sharp density profile characterizing ρ(r) is identified as a single particle oscillator, whose frequency is obtained from the parameters of the optimum density function. On the other hand, a dynamic approach to supercooled liquids is taken in the mode coupling theory (MCT) which predict a sharp ergodicity-non-ergodicity transition at a critical density. The single particle dynamics in the non-ergodic state, treated approximately, represents a propagating mode whose characteristic frequency is computed from the corresponding memory function of the MCT. The mass localization parameters in the above two models (treated in their simplest forms) are obtained, respectively, in terms of the corresponding natural frequencies depicted and are shown to have comparable magnitudes.

Linking density functional and mode coupling models for supercooled liquids

Energy Technology Data Exchange (ETDEWEB)

Premkumar, Leishangthem; Bidhoodi, Neeta; Das, Shankar P. [School of Physical Sciences, Jawaharlal Nehru University, New Delhi 110067 (India)

2016-03-28

We compare predictions from two familiar models of the metastable supercooled liquid, respectively, constructed with thermodynamic and dynamic approaches. In the so called density functional theory the free energy F[ρ] of the liquid is a functional of the inhomogeneous density ρ(r). The metastable state is identified as a local minimum of F[ρ]. The sharp density profile characterizing ρ(r) is identified as a single particle oscillator, whose frequency is obtained from the parameters of the optimum density function. On the other hand, a dynamic approach to supercooled liquids is taken in the mode coupling theory (MCT) which predict a sharp ergodicity-non-ergodicity transition at a critical density. The single particle dynamics in the non-ergodic state, treated approximately, represents a propagating mode whose characteristic frequency is computed from the corresponding memory function of the MCT. The mass localization parameters in the above two models (treated in their simplest forms) are obtained, respectively, in terms of the corresponding natural frequencies depicted and are shown to have comparable magnitudes.

Nonthermal ice nucleation observed at distorted contact lines of supercooled water drops.

Science.gov (United States)

Yang, Fan; Cruikshank, Owen; He, Weilue; Kostinski, Alex; Shaw, Raymond A

2018-02-01

Ice nucleation is the crucial step for ice formation in atmospheric clouds and therefore underlies climatologically relevant precipitation and radiative properties. Progress has been made in understanding the roles of temperature, supersaturation, and material properties, but an explanation for the efficient ice nucleation occurring when a particle contacts a supercooled water drop has been elusive for over half a century. Here, we explore ice nucleation initiated at constant temperature and observe that mechanical agitation induces freezing of supercooled water drops at distorted contact lines. Results show that symmetric motion of supercooled water on a vertically oscillating substrate does not freeze, no matter how we agitate it. However, when the moving contact line is distorted with the help of trace amounts of oil or inhomogeneous pinning on the substrate, freezing can occur at temperatures much higher than in a static droplet, equivalent to ∼10^{10} increase in nucleation rate. Several possible mechanisms are proposed to explain the observations. One plausible explanation among them, decreased pressure due to interface curvature, is explored theoretically and compared with the observational results quasiquantitatively. Indeed, the observed freezing-temperature increase scales with contact line speed in a manner consistent with the pressure hypothesis. Whatever the mechanism, the experiments demonstrate a strong preference for ice nucleation at three-phase contact lines compared to the two-phase interface, and they also show that movement and distortion of the contact line are necessary contributions to stimulating the nucleation process.

Structural relaxation and crystallisation of bulk metallic glasses Zr41Ti14Cu12.5Ni10-xBe22.5Fex (x = 0 or 2) studied by mechanical spectroscopy

International Nuclear Information System (INIS)

Wang, Q.; Pelletier, J.M.; Dong, Y.D.; Ji, Y.F.

2004-01-01

The measurements of the internal friction and dynamic shear modulus as well as differential scanning calorimetry have been performed in order to investigate the structural relaxation and crystallization of Zr 41 Ti 14 Cu 12.5 Ni 10-x Be 22.5 Fe x (x=0 or 2) bulk metallic glasses. It is found that the glass transition is retarded and the thermal stability of supercooled liquid is increased by the Fe addition. The experimental results are well analyzed using a physical model, which can characterize atomic mobility and mechanical response of disordered condensed materials

Crystallization in Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass under pressure

DEFF Research Database (Denmark)

Jiang, Jianzhong; Zhou, T.J.; Rasmussen, Helge Kildahl

2000-01-01

The effect of pressure on the crystallization behavior of the bulk metallic glass-forming Zr41.2Ti13.8Cu12.5Ni10Be22.5 alloy with a wide supercooled liquid region has been investigated by in situ high-pressure and high-temperature x-ray powder diffraction measurements using synchrotron radiation......)], reporting a decrease of the crystallization temperature under pressure in a pressure range of 0-6 GPa for the bulk glass Zr41Ti14Cu12.5Ni9Be22.5C1 alloy. Compressibility with a volume reduction of approximately 22% at room temperature does not induce crystallization in the Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk...... glass alloy. This indicates that the densification effect induced by pressure in the pressure range investigated plays a minor role in the crystallization behavior of this bulk glass alloy. The different crystallization behavior of the carbon-free and the carbon-containing glassy alloys has been...

A review of glass-ionomers: From conventional glass-ionomer to bioactive glass-ionomer

Directory of Open Access Journals (Sweden)

Maryam Khoroushi

2013-01-01

Full Text Available Materials used in the body, especially the materials used in various oral cavity regions should be stable and passive without any interactions with the body tissues or fluids. Dental amalgam, composite resins and dental cements are the materials of choice with such properties. The first attempts to produce active materials, which could interact with the human body tissues and fluids were prompted by the concept that fluoride-releasing materials exert useful effects in the body. The concept of using the "smart" materials in dentistry has attracted a lot of attention in recent years. Conventional glass-ionomer (GI cements have a large number of applications in dentistry. They are biocompatible with the dental pulp to some extent. GI is predominantly used as cements in dentistry; however, they have some disadvantages, the most important of which is lack of adequate strength and toughness. In an attempt to improve the mechanical properties of the conventional GI, resin-modified glass-ionomers have been marketed, with hydrophilic monomers, such as hydroxyethyl methacrylated (HEMA. Some recent studies have evaluated GI with bioactive glass in its structure to validate the claims that such a combination will improve tooth bioactivity, regeneration capacity and restoration. There is ever-increasing interest in the application of bioactive materials in the dental field in an attempt to remineralize affected dentin. The aim of this review article is to evaluate these materials and their characteristics and applications.

Alkali-free bioactive glasses for bone regeneration =

Science.gov (United States)

Kapoor, Saurabh

Bioactive glasses and glass-ceramics are a class of third generation biomaterials which elicit a special response on their surface when in contact with biological fluids, leading to strong bonding to living tissues. The purpose of the present study was to develop diopside based alkali-free bioactive glasses in order to achieve good sintering behaviour, high bioactivity, and a dissolution/ degradation rates compatible with the target applications in bone regeneration and tissue engineering. Another aim was to understand the structure-property relationships in the investigated bioactive glasses. In this quest, various glass compositions within the Diopside (CaMgSi2O6) - Fluorapatite (Ca5(PO4)3F) - Tricalcium phosphate (3CaO•P2O5) system have been investigated. All the glasses were prepared by melt-quenching technique and characterized by a wide array of complementary characterization techniques. The glass-ceramics were produced by sintering of glass powders compacts followed by a suitable heat treatment to promote the nucleation and crystallization phenomena. Furthermore, selected parent glass compositions were doped with several functional ions and an attempt to understand their effects on the glass structure, sintering ability and on the in vitro bio-degradation and biomineralization behaviours of the glasses was made. The effects of the same variables on the devitrification (nucleation and crystallization) behaviour of glasses to form bioactive glass-ceramics were also investigated. Some of the glasses exhibited high bio-mineralization rates, expressed by the formation of a surface hydroxyapatite layer within 1-12 h of immersion in a simulated body fluid (SBF) solution. All the glasses showed relatively lower degradation rates in comparison to that of 45S5 Bioglass. Some of the glasses showed very good in vitro behaviour and the glasses co-doped with zinc and strontium showed an in vitro dose dependent behaviour. The as-designed bioactive glasses and glass

Predicting glass-forming compositions in the Al-La and Al-La-Ni systems

International Nuclear Information System (INIS)

Gargarella, P.; de Oliveira, M.F.; Kiminami, C.S.; Pauly, S.; Kuehn, U.; Bolfarini, C.; Botta, W.J.; Eckert, J.

2011-01-01

Research highlights: → The glass-forming ability of the Al-La and Al-La-Ni systems was studied using the λ* and the λ.Δe criteria. → Both criteria predicted with just 1% at. of error the best glass-former verified so far in the Al-La system. → Four new glass-former compositions could be predicted in the Al-La-Ni system using the λ.Δe criterion. → The best glass-former reported so far in the Al-La-Ni system was found. - Abstract: In this work, a criterion considering the topological instability (λ) and the differences in the electronegativity of the constituent elements (Δe) was applied to the Al-La and Al-Ni-La systems in order to predict the best glass-forming compositions. The results were compared with literature data and with our own experimental data for the Al-La-Ni system. The alloy described in the literature as the best glass former in the Al-La system is located near the point with local maximum for the λ.Δe criterion. A good agreement was found between the predictions of the λ.Δe criterion and literature data in the Al-La-Ni system, with the region of the best glass-forming ability (GFA) and largest supercooled liquid region (ΔT x ) coinciding with the best compositional region for amorphization indicated by the λ.Δe criterion. Four new glassy compositions were found in the Al-La-Ni system, with the best predicted composition presenting the best glass-forming ability observed so far for this system. Although the λ.Δe criterion needs further refinements for completely describe the glass-forming ability in the Al-La and Al-La-Ni systems, the results demonstrated that this criterion is a good tool to predict new glass-forming compositions.

Contact freezing of supercooled cloud droplets on collision with mineral dust particles: effect of particle size

Science.gov (United States)

Hoffmann, Nadine; Duft, Denis; Kiselev, Alexei; Leisner, Thomas

2013-04-01

The contact freezing of supercooled cloud droplets is one of the potentially important and the least investigated heterogeneous mechanism of ice formation in the tropospheric clouds [1]. On the time scales of cloud lifetime the freezing of supercooled water droplets via contact mechanism may occur at higher temperature compared to the same IN immersed in the droplet. However, the laboratory experiments of contact freezing are very challenging due to the number of factors affecting the probability of ice formation. In our experiment we study single water droplets freely levitated in the laminar flow of mineral dust particles acting as the contact freezing nuclei. By repeating the freezing experiment sufficient number of times we are able to reproduce statistical freezing behavior of large ensembles of supercooled droplets and measure the average rate of freezing events. We show that the rate of freezing at given temperature is governed only by the rate of droplet -particle collision and by the properties of the contact ice nuclei. In this contribution we investigate the relationship between the freezing probability and the size of mineral dust particle (represented by illite) and show that their IN efficiency scales with the particle size. Based on this observation, we discuss the similarity between the freezing of supercooled water droplets in immersion and contact modes and possible mechanisms of apparent enhancement of the contact freezing efficiency. [1] - K.C. Young, The role of contact nucleation in ice phase initiation in clouds, Journal of the Atmospheric Sciences 31, 1974

Tensorial analysis of Eshelby stresses in 3D supercooled liquids

Science.gov (United States)

Lemaître, Anaël

2015-10-01

It was recently proposed that the local rearrangements governing relaxation in supercooled liquids impress on the liquid medium long-ranged (Eshelby) stress fluctuations that accumulate over time. From this viewpoint, events must be characterized by elastic dipoles, which are second order tensors, and Eshelby fields are expected to show up in stress and stress increment correlations, which are fourth order tensor fields. We construct here an analytical framework that permits analyzing such tensorial correlations in isotropic media in view of accessing Eshelby fields. Two spherical bases are introduced, which correspond to Cartesian and spherical coordinates for tensors. We show how they can be used to decompose stress correlations and thus test such properties as isotropy and power-law scalings. Eshelby fields and the predicted stress correlations in an infinite medium are shown to belong to an algebra that can conveniently be described using the spherical tensor bases. Using this formalism, we demonstrate that the inherent stress field of 3D supercooled liquids is power law correlated and carries the signature of Eshelby fields, thus supporting the idea that relaxation events give rise to Eshelby stresses that accumulate over time.

Effect of plastic deformation on the supercooled austenite transformations of the Cr-Mo steel with Nb, Ti and B microadditions

International Nuclear Information System (INIS)

Adamczyk, J.; Opiela, M.

1998-01-01

Effect of plastic deformation at austenizing temperature was investigated on phase transformations, structure and hardness of the supercooled austenite transformation products of the Cr-Mo constructional steel with Nb, Ti and B microadditions. Basing on the analysis of the phase transformation plots of the supercooled undeformed austenite and of the supercooled and plastically deformed one, it was found out that direct cooling of specimens after completing their plastic deformation in the above mentioned conditions, results in significant acceleration of the α→β, and ferritic and pearlitic transformations, and in the decrease of transformation products hardness. These phenomena are of great importance for working out of the thermo-mechanical treatment of products made from the heat-treated microalloyed steel. (author)

Exactly solvable spin–glass models with ferromagnetic couplings: The spherical multi-p-spin model in a self-induced field

International Nuclear Information System (INIS)

Crisanti, Andrea; Leuzzi, Luca

2013-01-01

We report some results on the quenched disordered Spherical multi-p-Spin Model in presence of ferromagnetic couplings. In particular, we present the phase diagrams of some representative cases that schematically describe, in the mean-field approximation, the behavior of most known transitions in glassy materials, including dynamic arrest in super-cooled liquids, amorphous–amorphous transitions and spin–glass transitions. A simplified notation is introduced in order to compute systems properties in terms of an effective, self-induced, field encoding the whole ferromagnetic information

On the dynamics of liquids in their viscous regime approaching the glass transition.

Science.gov (United States)

Chen, Z; Angell, C A; Richert, R

2012-07-01

Recently, Mallamace et al. (Eur. Phys. J. E 34, 94 (2011)) proposed a crossover temperature, T(×), and claimed that the dynamics of many supercooled liquids follow an Arrhenius-type temperature dependence between T(×) and the glass transition temperature T(g). The opposite, namely super-Arrhenius behavior in this viscous regime, has been demonstrated repeatedly for molecular glass-former, for polymers, and for the majority of the exhaustively studied inorganic glasses of technological interest. Therefore, we subject the molecular systems of the Mallamace et al. study to a "residuals" analysis and include not only viscosity data but also the more precise data available from dielectric relaxation experiments over the same temperature range. Although many viscosity data sets are inconclusive due to their noise level, we find that Arrhenius behavior is not a general feature of viscosity in the T(g) to T(×) range. Moreover, the residuals of dielectric relaxation times with respect to an Arrhenius law clearly reveal systematic curvature consistent with super-Arrhenius behavior being an endemic feature of transport properties in this viscous regime. We also observe a common pattern of how dielectric relaxation times decouple slightly from viscosity.

Recent advances on glass-forming systems driven far from equilibrium. Special issue marking the completion of the Research Unit FOR 1394 `Nonlinear response to probe vitrification'

Science.gov (United States)

Fuchs, Matthias

2017-08-01

The nature of the glass transition is one of the frontier questions in Statistical Physics and Materials Science. Highly cooperative structural processes develop in glass-forming melts exhibiting relaxational dynamics which is spread out over many decades in time. While considerable progress has been made in recent decades towards understanding dynamical slowing-down in quiescent systems, the interplay of glassy dynamics with external fields reveals a wealth of novel phenomena yet to be explored. This special issue focuses on recent results obtained by the Research Unit FOR 1394 `Nonlinear response to probe vitrification' which was funded by the German Science Foundation (DFG). In the projects of the research unit, strong external fields were used in order to gain insights into the complex structural and transport phenomena at the glass transition under far-from-equilibrium conditions. This aimed inter alia to test theories of the glass transition developed for quiescent systems by pushing them beyond their original regime. Combining experimental, simulational, and theoretical efforts, the eight projects within the FOR 1394 measured and determined aspects of the nonlinear response of supercooled metallic, polymeric, and silica melts, of colloidal dispersions, and of ionic liquids. Applied fields included electric and mechanic fields, and forced active probing (`micro-rheology'), where a single probe is forced through the glass-forming host. Nonlinear stress-strain and force-velocity relations as well as nonlinear dielectric susceptibilities and conductivities were observed. While the physical manipulation of melts and glasses is interesting in its own right, especially technologically, the investigations performed by the FOR 1394 suggest to use the response to strong homogeneous and inhomogeneous fields as technique to explore on the microscopic level the cooperative mechanisms in dense melts of strongly interacting constituents. Questions considered concern the

Structure and Degradation Behaviour of Calcium Phosphate Glasses

International Nuclear Information System (INIS)

Silva, A M B; Correia, R N; Fernandes, M H V; Oliveira, J M M

2011-01-01

Some studies have shown a relationship between glass structure and in vitro mineralization, generally associated with the rate of glass degradation, nature of released ions and subsequent Ca-P precipitation on glass surfaces when immersed in a Simulated Body Fluid (SBF). The knowledge of the ionic species distribution in glasses and of the involved bond strengths can be used to assess the in vitro behaviour of a glass. The role of ions such as silicon or titanium is of major importance for the development of new compositions and also for the control of glass degradation behaviour. A comparative study with two calcium phosphate glasses series was performed: Both glasses series - one with Si and another with Ti - include P 2 O 5 and alkaline earth ions in their compositions. Surface reactivity of glasses from the SiO 2 -containing system have been studied in SBF showing the precipitation of a Ca-P surface layer that increases with increasing MgO/CaO ratio. In glasses from the TiO 2 -containing series it is shown that the increase of TiO 2 contributes for the stabilization of the glass network thus allowing the control of their degradation rate when immersed in SBF. The relationship between structural features of these calcium-phosphate glasses and their degradation behaviour in SBF is discussed in terms of the structural role of Si and Ti ions. It is concluded that glasses with less interconnected species favour the Ca-P surface precipitation. The understanding of this relationship in synthetic physiological fluids is expected to allow the tailoring of glass degradation rates in complex biological systems.

Freezing avoidance by supercooling in Olea europaea cultivars: the role of apoplastic water, solute content and cell wall rigidity.

Science.gov (United States)

Arias, Nadia S; Bucci, Sandra J; Scholz, Fabian G; Goldstein, Guillermo

2015-10-01

Plants can avoid freezing damage by preventing extracellular ice formation below the equilibrium freezing temperature (supercooling). We used Olea europaea cultivars to assess which traits contribute to avoid ice nucleation at sub-zero temperatures. Seasonal leaf water relations, non-structural carbohydrates, nitrogen and tissue damage and ice nucleation temperatures in different plant parts were determined in five cultivars growing in the Patagonian cold desert. Ice seeding in roots occurred at higher temperatures than in stems and leaves. Leaves of cold acclimated cultivars supercooled down to -13 °C, substantially lower than the minimum air temperatures observed in the study site. During winter, leaf ice nucleation and leaf freezing damage (LT50 ) occurred at similar temperatures, typical of plant tissues that supercool. Higher leaf density and cell wall rigidity were observed during winter, consistent with a substantial acclimation to sub-zero temperatures. Larger supercooling capacity and lower LT50 were observed in cold-acclimated cultivars with higher osmotically active solute content, higher tissue elastic adjustments and lower apoplastic water. Irreversible leaf damage was only observed in laboratory experiments at very low temperatures, but not in the field. A comparative analysis of closely related plants avoids phylogenetic independence bias in a comparative study of adaptations to survive low temperatures. © 2015 John Wiley & Sons Ltd.

Brazing of Cu with Pd-based metallic glass filler

Energy Technology Data Exchange (ETDEWEB)

Terajima, Takeshi [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan)], E-mail: terajima@jwri.osaka-u.ac.jp; Nakata, Kazuhiro [Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Matsumoto, Yuji [Materials and Structures Laboratory, Tokyo Institute of Technology (Japan); Zhang, Wei; Kimura, Hisamichi; Inoue, Akihisa [Institute for Materials Research, Tohoku University (Japan)

2008-02-25

Metallic glass has several unique properties, including high mechanical strength, small solidification shrinkage, small elastic modulus and supercooling state, all of which are well suited as a residual stress buffer for metal and ceramic joining. In the present preliminary study, we demonstrated brazing of Cu rods with Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} metallic glass filler. The brazing was carried out at 873 K for 1 min in a vacuum atmosphere (1 x 10{sup -3} Pa), and then the specimens were quenched at the rate of 30 K/s by blowing He. The metallic glass brazing of Cu using Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler was successful, with the exception that several voids remained in the filler. According to micro-focused X-ray diffraction, no diffraction patterns were observed at both the center of the Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler and the Cu/Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} interface. The result showed that the Cu specimens were joined with Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler in the glassy state. The tensile fracture strength of the brazed specimens ranged from 20 to 250 MPa. The crack extension from the voids in the Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} filler may have caused the results to be uneven and very low compared to the strength of Pd-based bulk metallic glass.

Revealing Hidden Structural Order Controlling Both Fast and Slow Glassy Dynamics in Supercooled Liquids

Directory of Open Access Journals (Sweden)

Hua Tong

2018-03-01

Full Text Available The dynamics of a supercooled liquid near the glass transition is characterized by two-step relaxation, fast β and slow α relaxations. Because of the apparently disordered nature of glassy structures, there have been long debates over whether the origin of drastic slowing-down of the α relaxation accompanied by heterogeneous dynamics is thermodynamic or dynamic. Furthermore, it has been elusive whether there is any deep connection between fast β and slow α modes. To settle these issues, here we introduce a set of new structural order parameters characterizing sterically favored structures with high local packing capability, and then access structure-dynamics correlation by a novel nonlocal approach. We find that the particle mobility is under control of the static order parameter field. The fast β process is controlled by the instantaneous order parameter field locally, resulting in short-time particle-scale dynamics. Then the mobility field progressively develops with time t, following the initial order parameter field from disorder to more ordered regions. As is well known, the heterogeneity in the mobility field (dynamic heterogeneity is maximized with a characteristic length ξ_{4}, when t reaches the relaxation time τ_{α}. We discover that this mobility pattern can be predicted solely by a spatial coarse graining of the initial order parameter field at t=0 over a length ξ without any dynamical information. Furthermore, we find a relation ξ∼ξ_{4}, indicating that the static length ξ grows coherently with the dynamic one ξ_{4} upon cooling. This further suggests an intrinsic link between τ_{α} and ξ: the growth of the static length ξ is the origin of dynamical slowing-down. These we confirm for the first time in binary glass formers both in two and three spatial dimensions. Thus, a static structure has two intrinsic characteristic lengths, particle size and ξ, which control dynamics in local and nonlocal manners, resulting

Revealing Hidden Structural Order Controlling Both Fast and Slow Glassy Dynamics in Supercooled Liquids

Science.gov (United States)

Tong, Hua; Tanaka, Hajime

2018-01-01

The dynamics of a supercooled liquid near the glass transition is characterized by two-step relaxation, fast β and slow α relaxations. Because of the apparently disordered nature of glassy structures, there have been long debates over whether the origin of drastic slowing-down of the α relaxation accompanied by heterogeneous dynamics is thermodynamic or dynamic. Furthermore, it has been elusive whether there is any deep connection between fast β and slow α modes. To settle these issues, here we introduce a set of new structural order parameters characterizing sterically favored structures with high local packing capability, and then access structure-dynamics correlation by a novel nonlocal approach. We find that the particle mobility is under control of the static order parameter field. The fast β process is controlled by the instantaneous order parameter field locally, resulting in short-time particle-scale dynamics. Then the mobility field progressively develops with time t , following the initial order parameter field from disorder to more ordered regions. As is well known, the heterogeneity in the mobility field (dynamic heterogeneity) is maximized with a characteristic length ξ4, when t reaches the relaxation time τα. We discover that this mobility pattern can be predicted solely by a spatial coarse graining of the initial order parameter field at t =0 over a length ξ without any dynamical information. Furthermore, we find a relation ξ ˜ξ4, indicating that the static length ξ grows coherently with the dynamic one ξ4 upon cooling. This further suggests an intrinsic link between τα and ξ : the growth of the static length ξ is the origin of dynamical slowing-down. These we confirm for the first time in binary glass formers both in two and three spatial dimensions. Thus, a static structure has two intrinsic characteristic lengths, particle size and ξ , which control dynamics in local and nonlocal manners, resulting in the emergence of the two

Glass transition behavior of octyl β-D-glucoside and octyl β-D-thioglucoside/water binary mixtures.

Science.gov (United States)

Ogawa, Shigesaburo; Asakura, Kouichi; Osanai, Shuichi

2010-11-22

The lyotropic behavior and glass-forming properties of octyl β-D-glucoside (C8Glu) and octyl β-D-thioglucoside (C8SGlu)/water binary mixtures were evaluated using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The results clearly indicate that the mixture forms a glass in the supercooling state of liquid crystalline phases such as cubic, lamellar, and smectic. The glass transition temperature (T(g)) of the mixture was strongly dependent on solute concentration, with a higher concentration correlating with a higher T(g). The experimental T(g) was consistent with the predicted value calculated using the Couchman-Karasz equation in both the C8Glu and C8SGlu/water mixtures. The change of heat capacity at T(g) showed the two bending points under variation of concentrations. And the highest temperature of phase transition from lamellar to isotropic solution was observed at around 50% molar concentration. It was expected that non-percolated state of water existed in extremely higher concentration ranges. Copyright © 2010 Elsevier Ltd. All rights reserved.

Glass transition near the free surface studied by synchrotron radiation

Energy Technology Data Exchange (ETDEWEB)

Sikorski, M.

2008-06-15

A comprehensive picture of the glass transition near the liquid/vapor interface of the model organic glass former dibutyl phthalate is presented in this work. Several surface-sensitive techniques using x-ray synchrotron radiation were applied to investigate the static and dynamic aspects of the formation of the glassy state from the supercooled liquid. The amorphous nature of dibutyl phthalate close to the free surface was confirmed by grazing incidence X-ray diffraction studies. Results from X-ray reflectivity measurements indicate a uniform electron density distribution close to the interface excluding the possibility of surface freezing down to 175 K. Dynamics on sub-{mu}m length-scales at the surface was studied with coherent synchrotron radiation via x-ray photon correlation spectroscopy. From the analysis of the dispersion relation of the surface modes, viscoelastic properties of the dibutyl phthalate are deduced. The Kelvin-Voigt model of viscoelastic media was found to describe well the properties of the liquid/vapor interface below room temperature. The data show that the viscosity at the interface matches the values reported for bulk dibutyl phthalate. The scaled relaxation rate at the surface agrees with the bulk data above 210 K. Upon approaching the glass transition temperature the free surface was observed to relax considerably faster close to the liquid/vapor interface than in bulk. The concept of higher relaxation rate at the free surface is also supported by the results of the quasielastic nuclear forward scattering experiment, during which dynamics on molecular length scales around the calorimetric glass transition temperature is studied. The data were analyzed using mode-coupling theory of the glass transition and the model of the liquid(glass)/vapor interface, predicting inhomogeneous dynamics near the surface. The quasielastic nuclear forward scattering data can be explained when the molecular mobility is assumed to decrease with the increasing

Glass transition near the free surface studied by synchrotron radiation

International Nuclear Information System (INIS)

Sikorski, M.

2008-06-01

A comprehensive picture of the glass transition near the liquid/vapor interface of the model organic glass former dibutyl phthalate is presented in this work. Several surface-sensitive techniques using x-ray synchrotron radiation were applied to investigate the static and dynamic aspects of the formation of the glassy state from the supercooled liquid. The amorphous nature of dibutyl phthalate close to the free surface was confirmed by grazing incidence X-ray diffraction studies. Results from X-ray reflectivity measurements indicate a uniform electron density distribution close to the interface excluding the possibility of surface freezing down to 175 K. Dynamics on sub-μm length-scales at the surface was studied with coherent synchrotron radiation via x-ray photon correlation spectroscopy. From the analysis of the dispersion relation of the surface modes, viscoelastic properties of the dibutyl phthalate are deduced. The Kelvin-Voigt model of viscoelastic media was found to describe well the properties of the liquid/vapor interface below room temperature. The data show that the viscosity at the interface matches the values reported for bulk dibutyl phthalate. The scaled relaxation rate at the surface agrees with the bulk data above 210 K. Upon approaching the glass transition temperature the free surface was observed to relax considerably faster close to the liquid/vapor interface than in bulk. The concept of higher relaxation rate at the free surface is also supported by the results of the quasielastic nuclear forward scattering experiment, during which dynamics on molecular length scales around the calorimetric glass transition temperature is studied. The data were analyzed using mode-coupling theory of the glass transition and the model of the liquid(glass)/vapor interface, predicting inhomogeneous dynamics near the surface. The quasielastic nuclear forward scattering data can be explained when the molecular mobility is assumed to decrease with the increasing

Fast and slow crystal growth kinetics in glass-forming melts

Energy Technology Data Exchange (ETDEWEB)

Orava, J.; Greer, A. L., E-mail: alg13@cam.ac.uk [WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan and Department of Materials Science and Metallurgy, 27 Charles Babbage Road, University of Cambridge, Cambridge CB3 0FS (United Kingdom)

2014-06-07

Published values of crystal growth rates are compared for supercooled glass-forming liquids undergoing congruent freezing at a planar crystal-liquid interface. For the purposes of comparison pure metals are considered to be glass-forming systems, using data from molecular-dynamics simulations. For each system, the growth rate has a maximum value U{sub max} at a temperature T{sub max} that lies between the glass-transition temperature T{sub g} and the melting temperature T{sub m}. A classification is suggested, based on the lability (specifically, the propensity for fast crystallization), of the liquid. High-lability systems show “fast” growth characterized by a high U{sub max}, a low T{sub max} / T{sub m}, and a very broad peak in U vs. T / T{sub m}. In contrast, systems showing “slow” growth have a low U{sub max}, a high T{sub max} / T{sub m}, and a sharp peak in U vs. T / T{sub m}. Despite the difference of more than 11 orders of magnitude in U{sub max} seen in pure metals and in silica, the range of glass-forming systems surveyed fit into a common pattern in which the lability increases with lower reduced glass-transition temperature (T{sub g} / T{sub m}) and higher fragility of the liquid. A single parameter, a linear combination of T{sub g} / T{sub m} and fragility, can show a good correlation with U{sub max}. For all the systems, growth at U{sub max} is coupled to the atomic/molecular mobility in the liquid. It is found that, across the diversity of glass-forming systems, T{sub max} / T{sub g} = 1.48 ± 0.15.

Stretched exponential relaxation in molecular and electronic glasses

International Nuclear Information System (INIS)

Phillips, J.C.

1996-01-01

Stretched exponential relaxation, exp[-(t/τ) β ], fits many relaxation processes in disordered and quenched electronic and molecular systems, but it is widely believed that this function has no microscopic basis, especially in the case of molecular relaxation. For electronic relaxation the appearance of the stretched exponential is often described in the context of dispersive transport, where β is treated as an adjustable parameter, but in almost all cases it is generally assumed that no microscopic meaning can be assigned to 0 g , a glass transition temperature. We show that for molecular relaxation β(T g ) can be understood, providing that one separates extrinsic and intrinsic effects, and that the intrinsic effects are dominated by two magic numbers, β SR =3/5 for short-range forces, and β K =3/7 for long-range Coulomb forces, as originally observed by Kohlrausch for the decay of residual charge on a Leyden jar. Our mathematical model treats relaxation kinetics using the Lifshitz-Kac-Luttinger diffusion to traps depletion model in a configuration space of effective dimensionality, the latter being determined using axiomatic set theory and Phillips-Thorpe constraint theory. The experiments discussed include ns neutron scattering experiments, particularly those based on neutron spin echoes which measure S(Q, t) directly, and the traditional linear response measurements which span the range from μs to s, as collected and analysed phenomenologically by Angell, Ngai, Boehmer and others. The electronic materials discussed include a-Si:H, granular C 60 , semiconductor nanocrystallites, charge density waves in TaS 3 , spin glasses, and vortex glasses in high-temperature semiconductors. The molecular materials discussed include polymers, network glasses, electrolytes and alcohols, Van der Waals supercooled liquids and glasses, orientational glasses, water, fused salts, and heme proteins. In the intrinsic cases the theory of β(T g ) is often accurate to 2%, which

Alkali-free bioactive glasses for bone regeneration

OpenAIRE

Kapoor, Saurabh

2014-01-01

Bioactive glasses and glass-ceramics are a class of third generation biomaterials which elicit a special response on their surface when in contact with biological fluids, leading to strong bonding to living tissues. The purpose of the present study was to develop diopside based alkali-free bioactive glasses in order to achieve good sintering behaviour, high bioactivity, and a dissolution/ degradation rates compatible with the target applications in bone regeneration and tiss...

The relationship between gut contents and supercooling capacity in hatchling painted turtles (Chrysemys picta).

Science.gov (United States)

Packard, Gary C; Packard, Mary J

2006-05-01

Painted turtles (Chrysemys picta) typically spend their first winter of life in a shallow, subterranean hibernaculum (the natal nest) where they seemingly withstand exposure to ice and cold by resisting freezing and becoming supercooled. However, turtles ingest soil and fragments of eggshell as they are hatching from their eggs, and the ingestate usually contains efficient nucleating agents that cause water to freeze at high subzero temperatures. Consequently, neonatal painted turtles have only a modest ability to undergo supercooling in the period immediately after hatching. We studied the limit for supercooling (SCP) in hatchlings that were acclimating to different thermal regimes and then related SCPs of the turtles to the amount of particulate matter in their gastrointestinal (GI) tract. Turtles that were transferred directly from 26 degrees C (the incubation temperature) to 2 degrees C did not purge soil from their gut, and SCPs for these animals remained near -4 degrees C for the 60 days of the study. Animals that were held at 26 degrees C for the duration of the experiment usually cleared soil from their GI tract within 24 days, but SCPs for these turtles were only slightly lower after 60 days than they were at the outset of the experiment. Hatchlings that were acclimating slowly to 2 degrees C cleared soil from their gut within 24 days and realized a modest reduction in their SCP. However, the limit of supercooling in the slowly acclimating animals continued to decline even after all particulate material had been removed from their GI tract, thereby indicating that factors intrinsic to the nucleating agents themselves also may have been involved in the acclimation of hatchlings to low temperature. The lowest SCPs for turtles that were acclimating slowly to 2 degrees C were similar to SCPs recorded in an earlier study of animals taken from natural nests in late autumn, so the current findings affirm the importance of seasonally declining temperatures in

Microstructure and Rheology near an Attractive Colloidal Glass Transition

International Nuclear Information System (INIS)

Narayanan, T.; Sztucki, M.; Belina, G.; Pignon, F.

2006-01-01

Microstructure and rheological properties of a thermally reversible short-ranged attractive colloidal system are studied in the vicinity of the attractive glass transition line. At high volume fractions, the static structure factor changes very little but the low frequency shear moduli varies over several orders of magnitude across the transition. From the frequency dependence of shear moduli, fluid-attractive glass and repulsive glass-attractive glass transitions are identified

Analysis on the phase transition behavior of Cu base bulk metallic glass by electrical resistivity measurement

International Nuclear Information System (INIS)

Ji, Young Su; Chung, Sung Jae; Ok, Myoung-Ryul; Hong, Kyung Tae; Suh, Jin-Yoo; Byeon, Jai Won; Yoon, Jin-Kook; Lee, Kyung Hwan; Lee, Kyung Sub

2007-01-01

The crystallization behavior of Cu 43 Zr 43 Al 7 Ag 7 (numbers indicate at.%) bulk metallic glass was investigated using the isothermal electrical resistivity measurements at 450 deg. C in the supercooled liquid region. The crystallization process is a single step phase transformation. To analyze the electrical resistivity reduction, microstructure evolutions were analyzed using differential scanning calorimetry, X-ray diffraction, transmission electron microscopy and small-angle X-ray scattering. The Avrami parameter of the electrical resistivity reduction step was 1.73, indicating that the crystallization process is a diffusion-controlled growth of intermetallic compounds with decreasing nucleation rate

Transport properties of supercooled confined water

International Nuclear Information System (INIS)

Mallamace, F.; Baglioni, P.; Corsaro, C.; Spooren, J.; Stanley, H.E.; Chen, S.-H.

2011-01-01

We present an overview of recent experiments performed on water in the deeply supercooled region, a temperature region of fundamental importance in the science of water. We examine data generated by nuclear magnetic resonance, quasi-elastic neutron scattering, Fourier-transform infrared spectroscopy, and Raman spectroscopy, and study water confined in nanometer-scale environments. When contained within small pores, water does not crystallize and can be supercooled well below its homogeneous nucleation temperature T H. On this basis, it is possible to carry out a careful analysis of the well-known thermodynamic anomalies of water. Studying the temperature and pressure dependencies of water dynamics, we show that the liquid-liquid phase transition (LLPT) hypothesis represents a reliable model for describing liquid water. In this model, liquid water is a mixture of two different local structures: a low density liquid (LDL) and a high-density liquid (HDL). The LLPT line terminates at a low-T liquid-liquid critical point. We discuss the following experimental findings: 1.) the crossover from non-Arrhenius behavior at high T to Arrhenius behavior at low T in transport parameters; 2.) the breakdown of the Stokes-Einstein relation; 3.) the existence of a Widom line, which is the locus of points corresponding to a maximum correlation length in the P-T phase diagram and which ends in the liquid-liquid critical point; 4.) the direct observation of the LDL phase; and 5.) the minimum in the density at approximately 70 K below the temperature of the density maximum. In our opinion these results strongly support the LLPT hypothesis. All of the basic science and technology community should be impressed by the fact that, although the few ideas (apparently elementary) developed concerning water approximately 27 centuries ago have changed very little up to now, because of the current expansion in our knowledge in this area, they can begin to change in the near future.

Abnormal devitrification behavior and mechanical response of cold-rolled Mg-rich Mg-Cu-Gd metallic glasses

International Nuclear Information System (INIS)

Lee, J.I.; Kim, J.W.; Oh, H.S.; Park, J.S.; Park, E.S.

2016-01-01

Abnormal devitrification behavior and mechanical response of Mg 75 Cu 15 Gd 10 (relatively strong glass former with higher structural stability) and Mg 85 Cu 5 Gd 10 (relatively fragile glass former with lower structural stability) metallic glasses, fabricated by repeated forced cold rolling, have been investigated. When metallic glasses were cold-rolled up to a thickness reduction ratio of ∼33%, the heat of relaxation (ΔH relax. ) below T g of the cold-rolled specimens was reduced, which indicates the formation of local structural ordering via cold rolling due to stress-induced relaxation. The local structural ordering results in abnormal devitrification behavior, such as higher resistance of glass-to-supercooled liquid transition and delayed growth, in the following heat treatment due to increased nuclei density and pinning site. In particular, the fragility index, m, could assist in understanding structural stability and local structural variation by mechanical processing as well as compositional tuning. Indeed, we examine the shear avalanche size to rationalize the variation of the deformation unit size depending on the structural instability before and after cold rolling. The deformation mode in Mg 85 Cu 5 Gd 10 metallic glass might change from self-organized critical state to chaotic state by cold rolling, which results in unique hardening behavior under the condition for coexisting well distributed local structural ordering and numerous thinner shear deformed areas. These results would give us a guideline for atomic scale structural manipulation of metallic glasses, and help develop novel metallic glass matrix composites with optimal properties through effective mechanical processing as well as heat treatment.

Development of friction welding process of Zr-based bulk metallic glasses

International Nuclear Information System (INIS)

Shin, Hyung Seop; Jeong, Young Jin; Kim, Ki Hyun

2004-01-01

Bulk Metallic Glasses(BMG) with good mechanical properties have problems that engineering application fields have been limited because of limitation of the alloy size. In order to solving this problem, the friction welding of BMG has been tried using the superplastic-like deformation behavior under the supercooled liquid region. The apparatus for friction welding test was designed and constructed using pneumatic cylinder and gripper based on a conventional lathe. Friction welding have been tried to combination of same BMG alloy and crystalline alloys. The results of welding test were evaluated by X-ray diffraction, measurement of hardness and mechanical properties test. In order to obtain the optimized welding test conditions the temperature of friction interface was measured using Infrared thermal imager

Thermal stability and glass-forming ability of amorphous Nd-Al-TM (TM=Fe, Co, Ni or Cu) alloys

International Nuclear Information System (INIS)

Inoue, A.; Zhang Tao

1997-01-01

Bulk amorphous alloys were prepared for Nd 70 Al 10 TM 20 and Nd 60 Al 10 TM 30 (TM=Fe or Co) alloys by copper mold casting. The maximum sample thickness for glass formation reaches 15 mm for the Nd-Al-Fe alloys and 5 mm for the Nd-Al-Co alloys. A significant difference in the phase transition upon heating is recognized between the Fe- and Co-containing alloys. No glass transition before crystallization is observed for the Nd-Al-Fe alloys, but the Nd-Al-Co alloys exhibit the glass transition. The ΔT x (=T x -T g ) and T g /T m are 40-55 K and 0.65-0.67, respectively, for the latter alloys. The absence of supercooled liquid for the former alloys is different from those for all bulk amorphous alloys reported up to date. The T x /T m and ΔT m (=T m -T x ) are 0.85-0.89 and 88-137 K, respectively, for the Nd-Al-Fe alloys and, hence, the large glass-forming ability is presumably due to the high T x /T m and small ΔT m values. (orig.)

An interactive visualisation tool applied to the simulation of glass pressing

NARCIS (Netherlands)

Laevsky, K.; Telea, A.; Mattheij, R.M.M.

2001-01-01

An interactive numerical simulation approach to the process of glass pressing is presented. Glass is modelled as a strongly viscous Newtonian fluid whose deformation under pressure is described by a Stokes equation. Modelling the evolution of the glass free boundary in time poses a particular

On the temperature dependence of the Adam-Gibbs equation around the crossover region in the glass transition

Science.gov (United States)

Duque, Michel; Andraca, Adriana; Goldstein, Patricia; del Castillo, Luis Felipe

2018-04-01

The Adam-Gibbs equation has been used for more than five decades, and still a question remains unanswered on the temperature dependence of the chemical potential it includes. Nowadays, it is a well-known fact that in fragile glass formers, actually the behavior of the system depends on the temperature region it is being studied. Transport coefficients change due to the appearance of heterogeneity in the liquid as it is supercooled. Using the different forms for the logarithmic shift factor and the form of the configurational entropy, we evaluate this temperature dependence and present a discussion on our results.

Glass transition of soft colloids

Science.gov (United States)

Philippe, Adrian-Marie; Truzzolillo, Domenico; Galvan-Myoshi, Julian; Dieudonné-George, Philippe; Trappe, Véronique; Berthier, Ludovic; Cipelletti, Luca

2018-04-01

We explore the glassy dynamics of soft colloids using microgels and charged particles interacting by steric and screened Coulomb interactions, respectively. In the supercooled regime, the structural relaxation time τα of both systems grows steeply with volume fraction, reminiscent of the behavior of colloidal hard spheres. Computer simulations confirm that the growth of τα on approaching the glass transition is independent of particle softness. By contrast, softness becomes relevant at very large packing fractions when the system falls out of equilibrium. In this nonequilibrium regime, τα depends surprisingly weakly on packing fraction, and time correlation functions exhibit a compressed exponential decay consistent with stress-driven relaxation. The transition to this novel regime coincides with the onset of an anomalous decrease in local order with increasing density typical of ultrasoft systems. We propose that these peculiar dynamics results from the combination of the nonequilibrium aging dynamics expected in the glassy state and the tendency of colloids interacting through soft potentials to refluidize at high packing fractions.

Bioactive Glasses in Dentistry: A Review

Directory of Open Access Journals (Sweden)

Abbasi Z

2015-03-01

Full Text Available Bioactive glasses are silicate-based and can form a strong chemical bond with the tissues. These biomaterials are highly biocompatible and can form a hydroxyapatite layer when implanted in the body or soaked in the simulated body fluid. Due to several disadvantages, conventional glass processing method including melting of glass components, is replaced by sol-gel method with a large number of benefits such as low processing temperature, higher purity and homogeneity and therefore better control of bioactivity. Bioactive glasses have a wide range of applications, particularly in dentistry. These glasses can be used as particulates or monolithic shapes and porous or dense constructs in different applications such as remineralization or hypersensitivity treatment. Some properties of bioactive glasses such as antibacterial properties can be promoted by adding different elements into the glass. Bioactive glasses can also be used to modify different biocompatible materials that need to be bioactive. This study reviews the significant developments of bioactive glasses in clinical application, especially dentistry. Furthermore, we will discuss the field of bioactive glasses from beginning to the current developments, which includes processing methods, applications, and properties of these glasses.

Mineralogical textural and compositional data on the alteration of basaltic glass from Kilauea, Hawaii to 300 degrees C: Insights to the corrosion of a borosilicate glass waste-form

International Nuclear Information System (INIS)

Smith, D.K.

1990-01-01

Mineralogical, textural and compositional data accompanying greenschist facies metamorphism (to 300 degrees C) of basalts of the East Rift Zone (ERZ), Kilauea, Hawaii may be evaluated relative to published and experimental results for the surface corrosion of borosilicate glass. The ERZ alteration sequence is dominated by intermittent palagonite, interlayered smectite-chlorite, chlorite, and actinolite-epidote-anhydrite. Alteration is best developed in fractures and vesicles where surface reaction layers root on the glass matrix forming rinds in excess of 100 microns thick. Fractures control fluid circulation and the alteration sequence. Proximal to the glass surface, palagonite, Fe-Ti oxides and clays replace fresh glass as the surface reaction layer migrates inwards; away from the surface, amphibole, anhydrite, quartz and calcite crystallize from hydrothermal fluids in contact with the glass. The texture and composition of basaltic glass surfaces are similar to those of a SRL-165 glass leached statically for sixty days at 150 degrees C. While the ERZ reservoir is a complex open system, conservative comparisons between the alteration of ERZ and synthetic borosilicate glass are warranted. 31 refs., 2 figs

Structure of B2O3 and alkali borates in glass-like and melted states

International Nuclear Information System (INIS)

Golubkov, V.V.

1992-01-01

Structure of boron oxide and alkali-borate oxide and alkali-borate glasses and melts at temperatures up to 100 deg C was investigated using method of x-ray scattering at small angles (RSA). Specified and detailed concentration dependences were given for the main parameters of the structure: sizes of non-uniformity regions, values of surface interface, data of average square of difference of electron densities. Uppearance of ordered structures at sharp drop of temperature of B 2 O 3 sample was shown. Interference effects connected with this phenomenon significantly influence on value of RSA intensity in the field of small angles and correspondingly on light diffusion intensity. Conclusion on existence of structural differences between liquids and supercooled liquids was confirmed. Narrow temperature range of transition from one state to another esisted. Submicrononuniform structure of alkaliborate glasses wasn't connected with critical phenomenon. In the fields of non-uniformity 25-50% of alkali ions were concentrated

Substrate Dependence of the Freezing Dynamics of Supercooled Water Films: A High-Speed Optical Microscope Study.

Science.gov (United States)

Pach, E; Rodriguez, L; Verdaguer, A

2018-01-18

The freezing of supercooled water films on different substrates was investigated using a high-speed camera coupled to an optical microscope, obtaining details of the freezing process not described in the literature before. We observed the two well known freezing stages (fast dendritic growth and slow freezing of the water liquid left after the dendritic growth), but we separated the process into different phenomena that were studied separately: two-dimensional dendrite growth on the substrate interface, vertical dendrite growth, formation and evolution of ice domains, trapping of air bubbles and freezing of the water film surface. We found all of these processes to be dependent on both the supercooling temperature and the substrate used. Ice dendrite (or ice front) growth during the first stage was found to be dependent on thermal properties of the substrate but could not be unequivocally related to them. Finally, for low supercooling, a direct relationship was observed between the morphology of the dendrites formed in the first stage, which depends on the substrate, and the roughness and the shape of the surface of the ice, when freezing of the film was completed. This opens the possibility of using surfaces and coatings to control ice morphology beyond anti-icing properties.

Glass forming ability and magnetic properties of Co(40.2−x)Fe(20.1+x)Ni6.7B22.7Si5.3Nb5 (x=0–10) bulk metallic glasses produced by suction casting

International Nuclear Information System (INIS)

Sarlar, Kagan; Kucuk, Ilker

2015-01-01

The effect of Fe concentration on the glass forming ability (GFA) and magnetic properties in Co (40.2−x) Fe (20.1+x) Ni 6.7 B 22.7 Si 5.3 Nb 5 (x=0–10) bulk metallic glasses were investigated. By suction casting method, the bulk metallic glasses with diameters up to 2 mm were produced. We try to find out which Fe concentration makes an influence on Co based system's magnetic properties and glass forming ability. The curves of thermal analysis, obtained using differential scanning calorimetry (DSC), show that the Co (40.2−x) Fe (20.1+x) Ni 6.7 B 22.7 Si 5.3 Nb 5 (x=0–10) have a supercooled liquid region (∆T x ) of about 44 K. The saturation magnetizations (J s ) for as-cast BMG alloys were in the range of 0.62 T−0.81 T. - Highlights: • The effect of Fe concentration on the glass forming ability. • The substitution of an appropriate amount of Fe can enhance the GFA. • The substitution of Fe for Co also improves soft magnetic properties of the BMGs. • The high of J s 0.62−0.81 T with a low H c of 2−289 A/m of the alloys

Controlling the Release of Indomethacin from Glass Solutions Layered with a Rate Controlling Membrane Using Fluid-Bed Processing. Part 1: Surface and Cross-Sectional Chemical Analysis.

Science.gov (United States)

Dereymaker, Aswin; Scurr, David J; Steer, Elisabeth D; Roberts, Clive J; Van den Mooter, Guy

2017-04-03

Fluid bed coating has been shown to be a suitable manufacturing technique to formulate poorly soluble drugs in glass solutions. Layering inert carriers with a drug-polymer mixture enables these beads to be immediately filled into capsules, thus avoiding additional, potentially destabilizing, downstream processing. In this study, fluid bed coating is proposed for the production of controlled release dosage forms of glass solutions by applying a second, rate controlling membrane on top of the glass solution. Adding a second coating layer adds to the physical and chemical complexity of the drug delivery system, so a thorough understanding of the physical structure and phase behavior of the different coating layers is needed. This study aimed to investigate the surface and cross-sectional characteristics (employing scanning electron microscopy (SEM) and time of flight secondary ion mass spectrometry (ToF-SIMS)) of an indomethacin-polyvinylpyrrolidone (PVP) glass solution, top-coated with a release rate controlling membrane consisting of either ethyl cellulose or Eudragit RL. The implications of the addition of a pore former (PVP) and the coating medium (ethanol or water) were also considered. In addition, polymer miscibility and the phase analysis of the underlying glass solution were investigated. Significant differences in surface and cross-sectional topography of the different rate controlling membranes or the way they are applied (solution vs dispersion) were observed. These observations can be linked to the polymer miscibility differences. The presence of PVP was observed in all rate controlling membranes, even if it is not part of the coating solution. This could be attributed to residual powder presence in the coating chamber. The distribution of PVP among the sample surfaces depends on the concentration and the rate controlling polymer used. Differences can again be linked to polymer miscibility. Finally, it was shown that the underlying glass solution layer

Formation of quasicrystals and amorphous-to-quasicrystalline phase transformation kinetics in Zr65Al7.5Ni10Cu7.5Ag10 metallic glass under pressure

DEFF Research Database (Denmark)

Jiang, Jianzhong; Zhuang, Yanxin; Rasmussen, Helge Kildahl

2001-01-01

The effect of pressure on the formation of quasicrystals and the amorphous-to-quasicrystalline phase transformation kinetics in the supercooled liquid region for a Zr65Al7.5Ni10Cu7.5Ag10 metallic glass have been investigated by in situ high-pressure and high-temperature nonisothermal and isothermal...... of quasicrystals decrease, Atomic mobility is important for the formation of quasicrystals from the metallic glass whereas the relationship of the crystallization temperature vs pressure for the transition from the quasicrystalline state to intermetallic compounds may mainly depend on the thermodynamic potential...... energy barrier. To study the amorphous-to-quasicrystalline phase transformation kinetics in the metallic glass, relative volume fractions of the transferred quasicrystalline phase as a function of annealing time, obtained at 663, 673, 683, and 693 K, have been analyzed in details using 14 nucleation...

Preparation, thermal stability, and magnetic properties of Fe-Zr-Mo-W-B bulk metallic glass

International Nuclear Information System (INIS)

Liu, D.Y.; Sun, W.S.; Wang, A.M.; Zhang, H.F.; Hu, Z.Q.

2004-01-01

A bulk metallic glass (BMG) cylinder of Fe 60 Co 8 Zr 10 Mo 5 W 2 B 15 with a diameter of 1.5 mm was prepared by copper mould casting of industrial raw materials. The amorphous state and the crystallization behavior were investigated by X-ray diffraction (XRD). The thermal stability parameters, such as glass transition temperature (T g ), crystallization temperature (T x ), supercooled liquid region (ΔT x ) between T g and T x , and reduced glass transition temperature T rg (T g /T m ) were measured by differential scanning calorimetry (DSC) to be 891, 950, 59 K, and 0.62, respectively. The crystallization process took place through a single stage, and involved crystallization of the phases α-Fe, ZrFe 2 , Fe 3 B, MoB 2 , Mo 2 FeB 2 , and an unknown phase, as determined by X-ray analysis of the sample annealed for 1.5 ks at 1023 K, 50 K above the DSC peak temperature of crystallization. Moessbauer spectroscopy was studied for this alloy. The spectra exhibit a broadened and asymmetric doublet-like structure that indicated paramagnetic behavior and a fully amorphous structure. α-Fe was found in the amorphous matrix for a cylinder with a diameter of 2.5 mm. The success of synthesis of the Fe-based bulk metallic glass from industrial materials is important for the future progress in research and practical application of new bulk metallic glasses

Thermal stability of the French nuclear waste glass - long term behavior modeling

International Nuclear Information System (INIS)

Orlhac, X.

2000-01-01

The thermal stability of the French nuclear waste glass was investigated experimentally and by modeling to predict its long-term evolution at low temperature. The crystallization mechanisms were analyzed by studying devitrification in the supercooled liquid. Three main crystalline phases were characterized (CaMoO 4 , CeCO 2 , ZnCr 2 O 4 ). Their crystallisation was TO 4.24 wt%, due to the low concentration of the constituent elements. The nucleation and growth curves showed that platinoid elements catalysed nucleation but did not affect growth, which was governed by volume diffusion. The criteria of classic nucleation theory were applied to determine the thermodynamic and diffusional activation energies. Viscosity measurements illustrate the analogy between the activation energy of viscous flow and diffusion, indicating control of crystallization by viscous flow phenomena. The combined action of nucleation and growth was assessed by TTT plots, revealing a crystallization equilibrium line that enables the crystallized fractions to be predicted over the long term. The authors show that hetero-genetics catalyze the transformation without modifying the maximum crystallized fraction. A kinetic model was developed to describe devitrification in the glass based on the nucleation and growth curves alone. The authors show that the low-temperature growth exhibits scale behavior (between time and temperature) similar to thermo-rheological simplicity. The analogy between the resulting activation energy and that of the viscosity was used to model growth on the basis of viscosity. After validation with a simplified (BaO 2 SiO 2 ) glass, the model was applied to the containment glass. The result indicated that the glass remained completely vitreous after a cooling scenario with the one measured at the glass core. Under isothermal conditions, several million years would be required to reach the maximum theoretical crystallization fraction. (author)

Piezoelectricity of a ferroelectric liquid crystal with a glass transition.

Science.gov (United States)

Jákli, A; Tóth-Katona, T; Scharf, T; Schadt, M; Saupe, A

2002-07-01

Pressure-electric (hydrostatic piezoelectric) measurements are reported on bookshelf textures of a ferroelectric smectic-C (Sm C*) liquid crystal with a glass transition. The continuous variation of a partially fluid state to the solid glass enables one to trace how the piezoelectric effect depends on the consistency of the material. It was observed that in the Sm C* samples with poled glass the piezoelectric constants are comparable to conventional piezoelectric crystals and poled piezoelectric polymers. This implies their application possibilities. The magnitude of the piezoelectric constant in the glassy state depends very much on the poling conditions. The studies indicate that there are two counteracting effects, which cancel each other out in the Sm C* phase near the glass transition. Our analysis indicates that the pressure-induced director tilt change has a dominating effect both in the fluid and the glassy Sm C* states.

Aging of the Johari-Goldstein relaxation in the glass-forming liquids sorbitol and xylitol

Science.gov (United States)

Yardimci, Hasan; Leheny, Robert L.

2006-06-01

Employing frequency-dependent dielectric susceptibility we characterize the aging in two supercooled liquids, sorbitol and xylitol, below their calorimetric glass transition temperatures. In addition to the alpha relaxation that tracks the structural dynamics, the susceptibility of both liquids possesses a secondary Johari-Goldstein relaxation at higher frequencies. Following a quench through the glass transition, the susceptibility slowly approaches the equilibrium behavior. For both liquids, the magnitude of the Johari-Goldstein relaxation displays a dependence on the time since the quench, or aging time, that is quantitatively very similar to the age dependence of the alpha peak frequency. The Johari-Goldstein relaxation time remains constant during aging for sorbitol while it decreases slightly with age for xylitol. Hence, one cannot sensibly assign a fictive temperature to the Johari-Goldstein relaxation. This behavior contrasts with that of liquids lacking distinct Johari-Goldstein peaks for which the excess wing of the alpha peak tracks the main part of the peak during aging, enabling the assignment of a single fictive temperature to the entire spectrum. The aging behavior of the Johari-Goldstein relaxation time further calls into question the possibility that the relaxation time possesses stronger temperature dependence in equilibrium than is observed in the out-of-equilibrium state below the glass transition.

Effect of ZnO on phase emergence, microstructure and surface modifications of calcium phosphosilicate glass/glass-ceramics having iron oxide

Energy Technology Data Exchange (ETDEWEB)

Sharma, K.; Dixit, A.; Bhattacharya, S.; Jagannath [Technical Physics and Prototype Engineering Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Deo, M.N. [High Pressure Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Kothiyal, G.P., E-mail: gpkoth@barc.gov.in [Technical Physics and Prototype Engineering Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

2010-03-01

The effect of ZnO on phase emergence and microstructure properties of glass and glass-ceramics with composition 25SiO{sub 2}-50CaO-15P{sub 2}O{sub 5}-(10 - x)Fe{sub 2}O{sub 3}-xZnO (where x = 0, 2, 5, 7 mol%) has been studied. They have been characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Surface modifications of these glass-ceramics in simulated body fluid have been studied using Fourier transform infrared reflection spectroscopy (FTIR), XPS and SEM. Results have shown a decrease in the fraction of non-bridging oxygen with increase in zinc oxide content. Emergence of crystalline phases in glass-ceramics at different heat treatment temperatures was studied using XRD. When glass is heat treated at 800 deg. C calcium phosphate, hematite and magnetite are developed as major phases in the glass-ceramics samples with ZnO up to 5 mol%. In addition to these, calcium silicate (Ca{sub 3}Si{sub 2}O{sub 7}) phase is also observed when glass is heat treated at 1000 deg. C. The microstructure of the glass-ceramics heat treated at 800 deg. C exhibits the formation of nano-size (40-50 nm) grains. On heat treatment at 1000 deg. C crystallites grow to above 50 nm size and more than one phase are observed in the microstructure. The formation of thin flake-like structure with coarse particles is observed at high zinc oxide concentration (x = 7 mol%). In vitro studies have shown the surface modifications and formation of Ca-P-rich layer on the glass-ceramics when immersed in simulated body fluids (SBF) for different durations. The bioactive response was found to depend on ZnO content.

Effect of ZnO on phase emergence, microstructure and surface modifications of calcium phosphosilicate glass/glass-ceramics having iron oxide

International Nuclear Information System (INIS)

Sharma, K.; Dixit, A.; Bhattacharya, S.; Jagannath; Deo, M.N.; Kothiyal, G.P.

2010-01-01

The effect of ZnO on phase emergence and microstructure properties of glass and glass-ceramics with composition 25SiO 2 -50CaO-15P 2 O 5 -(10 - x)Fe 2 O 3 -xZnO (where x = 0, 2, 5, 7 mol%) has been studied. They have been characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Surface modifications of these glass-ceramics in simulated body fluid have been studied using Fourier transform infrared reflection spectroscopy (FTIR), XPS and SEM. Results have shown a decrease in the fraction of non-bridging oxygen with increase in zinc oxide content. Emergence of crystalline phases in glass-ceramics at different heat treatment temperatures was studied using XRD. When glass is heat treated at 800 deg. C calcium phosphate, hematite and magnetite are developed as major phases in the glass-ceramics samples with ZnO up to 5 mol%. In addition to these, calcium silicate (Ca 3 Si 2 O 7 ) phase is also observed when glass is heat treated at 1000 deg. C. The microstructure of the glass-ceramics heat treated at 800 deg. C exhibits the formation of nano-size (40-50 nm) grains. On heat treatment at 1000 deg. C crystallites grow to above 50 nm size and more than one phase are observed in the microstructure. The formation of thin flake-like structure with coarse particles is observed at high zinc oxide concentration (x = 7 mol%). In vitro studies have shown the surface modifications and formation of Ca-P-rich layer on the glass-ceramics when immersed in simulated body fluids (SBF) for different durations. The bioactive response was found to depend on ZnO content.

Theoretical prediction of crystallization kinetics of a supercooled Lennard-Jones fluid

Science.gov (United States)

Gunawardana, K. G. S. H.; Song, Xueyu

2018-05-01

The first order curvature correction to the crystal-liquid interfacial free energy is calculated using a theoretical model based on the interfacial excess thermodynamic properties. The correction parameter (δ), which is analogous to the Tolman length at a liquid-vapor interface, is found to be 0.48 ± 0.05 for a Lennard-Jones (LJ) fluid. We show that this curvature correction is crucial in predicting the nucleation barrier when the size of the crystal nucleus is small. The thermodynamic driving force (Δμ) corresponding to available simulated nucleation conditions is also calculated by combining the simulated data with a classical density functional theory. In this paper, we show that the classical nucleation theory is capable of predicting the nucleation barrier with excellent agreement to the simulated results when the curvature correction to the interfacial free energy is accounted for.

Correlation between microstructure and internal friction in a Zr41.2-Ti13.8-Cu12.5-Ni8- Be22.5-Fe2 bulk metallic glass

International Nuclear Information System (INIS)

Wang, Q.; Pelletier, J.M.; Da Dong, Y.; Ji, Y.F.; Xiu, H.

2004-01-01

The microstructural evolution in a Zr-Ti-Cu-Ni-Be-Fe bulk metallic glass (BMG) has been investigated by measurements of dynamical shear modulus and internal friction combined with other analytical methods such as differential scanning calorimetry (DSC), X-ray diffraction (XRD) and high resolution transmission electron microscopy (TEM). When heated from room temperature up to 873 K, the as-received BMG exhibits an exponential increase in internal friction accompanying the strong decrease of storage modulus and the presence of the first loss modulus peak during the dynamic glass transition, which can be well described using quasi-point defect model. The correlative changes of the mechanical response at higher temperature are associated with the crystallisation process of the supercooled liquid phase, which occurs in four different stages. It is shown that the main crystallisation process is completed in the first two stages. With further increasing temperature, the remaining amorphous phases crystallise and/or the metastable crystalline phases are transformed into the stable ones. Isothermal annealing were also performed at temperatures in the supercooled liquid region far below the onset temperature of the crystallisation process (T x ). Their influence on microstucture and internal friction behaviour of the BMG is also presented in this paper. The most striking result is that the internal friction is very sensitive to the local atomic short range ordering induced by the preheating treatment

Diopside-Fluorapatite-Wollastonite Based Bioactive Glasses and Glass-ceramics =

Science.gov (United States)

Kansal, Ishu

Bioactive glasses and glass-ceramics are a class of biomaterials which elicit special response on their surface when in contact with biological fluids, leading to strong bonding to living tissue. This particular trait along with good sintering ability and high mechanical strength make them ideal materials for scaffold fabrication. The work presented in this thesis is directed towards understanding the composition-structure-property relationships in potentially bioactive glasses designed in CaO-MgO-P2O5-SiO2-F system, in some cases with added Na2O. The main emphasis has been on unearthing the influence of glass composition on molecular structure, sintering ability and bioactivity of phosphosilicate glasses. The parent glass compositions have been designed in the primary crystallization field of the pseudo-ternary system of diopside (CaO•MgO•2SiO2) - fluorapatite (9CaO•3P2O5•CaF2) - wollastonite (CaO•SiO2), followed by studying the impact of compositional variations on the structure-property relationships and sintering ability of these glasses. All the glasses investigated in this work have been synthesized via melt-quenching route and have been characterized for their molecular structure, sintering ability, chemical degradation and bioactivity using wide array of experimental tools and techniques. It has been shown that in all investigated glass compositions the silicate network was mainly dominated by Q2 units while phosphate in all the glasses was found to be coordinated in orthophosphate environment. The glass compositions designed in alkali-free region of diopside - fluorapatite system demonstrated excellent sintering ability and good bioactivity in order to qualify them as potential materials for scaffold fabrication while alkali-rich bioactive glasses not only hinder the densification during sintering but also induce cytotoxicity in vitro, thus, are not ideal candidates for in vitro tissue engineering. One of our bioglass compositions with low sodium

Behavior of supercooled aqueous solutions stemming from hidden liquid-liquid transition in water.

Science.gov (United States)

Biddle, John W; Holten, Vincent; Anisimov, Mikhail A

2014-08-21

A popular hypothesis that explains the anomalies of supercooled water is the existence of a metastable liquid-liquid transition hidden below the line of homogeneous nucleation. If this transition exists and if it is terminated by a critical point, the addition of a solute should generate a line of liquid-liquid critical points emanating from the critical point of pure metastable water. We have analyzed thermodynamic consequences of this scenario. In particular, we consider the behavior of two systems, H2O-NaCl and H2O-glycerol. We find the behavior of the heat capacity in supercooled aqueous solutions of NaCl, as reported by Archer and Carter [J. Phys. Chem. B 104, 8563 (2000)], to be consistent with the presence of the metastable liquid-liquid transition. We elucidate the non-conserved nature of the order parameter (extent of "reaction" between two alternative structures of water) and the consequences of its coupling with conserved properties (density and concentration). We also show how the shape of the critical line in a solution controls the difference in concentration of the coexisting liquid phases.

An apparatus with a horizontal capillary tube intended for measurement of the surface tension of supercooled liquids

Science.gov (United States)

Vinš, Václav; Hošek, Jan; Hykl, Jiří; Hrubý, Jan

2015-05-01

New experimental apparatus for measurement of the surface tension of liquids under the metastable supercooled state has been designed and assembled in the study. The measuring technique is similar to the method employed by P.T. Hacker [NACA TN 2510] in 1951. A short liquid thread of the liquid sample was sucked inside a horizontal capillary tube partly placed in a temperature-controlled glass chamber. One end of the capillary tube was connected to a setup with inert gas which allowed for precise tuning of the gas overpressure in order of hundreds of Pa. The open end of the capillary tube was precisely grinded and polished before the measurement in order to assure planarity and perpendicularity of the outer surface. The liquid meniscus at the open end was illuminated by a laser beam and observed by a digital camera. Application of an increasing overpressure of the inert gas at the inner meniscus of the liquid thread caused variation of the outer meniscus such that it gradually changed from concave to flat and subsequently convex shape. The surface tension at the temperature of the inner meniscus could be evaluated from the overpressure corresponding to exactly planar outer meniscus. Detailed description of the new setup together with results of the preliminary tests is provided in the study.

Computational Fluid Dynamics Modeling of Bubbling in a Viscous Fluid for Validation of Waste Glass Melter Modeling

Energy Technology Data Exchange (ETDEWEB)

Abboud, Alexander William [Idaho National Laboratory; Guillen, Donna Post [Idaho National Laboratory

2016-01-01

At the Hanford site, radioactive waste stored in underground tanks is slated for vitrification for final disposal. A comprehensive knowledge of the glass batch melting process will be useful in optimizing the process, which could potentially reduce the cost and duration of this multi-billion dollar cleanup effort. We are developing a high-fidelity heat transfer model of a Joule-heated ceramic lined melter to improve the understanding of the complex, inter-related processes occurring with the melter. The glass conversion rates in the cold cap layer are dependent on promoting efficient heat transfer. In practice, heat transfer is augmented by inserting air bubblers into the molten glass. However, the computational simulations must be validated to provide confidence in the solutions. As part of a larger validation procedure, it is beneficial to split the physics of the melter into smaller systems to validate individually. The substitution of molten glass for a simulant liquid with similar density and viscosity at room temperature provides a way to study mixing through bubbling as an isolated effect without considering the heat transfer dynamics. The simulation results are compared to experimental data obtained by the Vitreous State Laboratory at the Catholic University of America using bubblers placed within a large acrylic tank that is similar in scale to a pilot glass waste melter. Comparisons are made for surface area of the rising air bubbles between experiments and CFD simulations for a variety of air flow rates and bubble injection depths. Also, computed bubble rise velocity is compared to a well-accepted expression for bubble terminal velocity.

Empirical Formulae for The Calculation of Austenite Supercooled Transformation Temperatures

Directory of Open Access Journals (Sweden)

Trzaska J.

2015-04-01

Full Text Available The paper presents empirical formulae for the calculation of austenite supercooled transformation temperatures, basing on the chemical composition, austenitising temperature and cooling rate. The multiple regression method was used. Four equations were established allowing to calculate temperature of the start area of ferrite, perlite, bainite and martensite at the given cooling rate. The calculation results obtained do not allow to determine the cooling rate range of ferritic, pearlitic, bainitic and martensite transformations. Classifiers based on logistic regression or neural network were established to solve this problem.

Effect of solute atoms on glass-forming ability for Fe–Y–B alloy: An ab initio molecular dynamics study

International Nuclear Information System (INIS)

Han, J.J.; Wang, W.Y.; Liu, X.J.; Wang, C.P.; Hui, X.D.; Liu, Z.K.

2014-01-01

The glass-forming abilities of Fe 78 B 22 , Fe 70 Y 6 B 24 , Fe 72 Y 6 B 22 and Fe 72.5 Y 3.5 B 24 alloys were characterized comprehensively using ab initio molecular dynamics simulations. The calculated results were correlated with the properties and atomic structures. It was found that the Fe 72 Y 6 B 22 alloy consists of both the most stable and the least deformed body centered cubic atomic packing structures in the supercooled liquid and glassy states. It was observed that the local compositions in the Fe 72 Y 6 B 22 alloy significantly deviate from the compositions of stable crystalline phases, indicating that the Fe 72 Y 6 B 22 alloy has the best glass-forming ability among the alloys studied. However, Fe 72 Y 6 B 22 alloy has two flaws in terms of glass-forming ability, i.e. relatively large atomic diffusivity and insufficiently close atomic packing. The best performance in these two aspects is observed in the Fe 72.5 Y 3.5 B 24 alloy. Thus, the theoretical study predicts that the best glass former for the Fe–Y–B system is within the compositional range of 22–24 at.% B and 3.5–6 at.% Y

Simplified model for a ventilated glass window under forced air flow conditions

International Nuclear Information System (INIS)

Ismail, K.A.R.; Henriquez, J.R.

2006-01-01

This paper presents a study on a ventilated window composed of two glass sheets separated by a spacing through which air is forced to flow. The proposed model is one dimensional and unsteady based upon global energy balance over the glass sheets and the flowing fluid. The external glass sheet of the cavity is subjected to variable heat flow due to the solar radiation as well as variable external ambient temperature. The exchange of radiation energy (infrared radiation) between the glass sheets is also included in the formulation. Effects of the spacing between the glass sheets, variation of the forced mass flow rate on the total heat gain and the shading coefficients are investigated. The results show that the effect of the increase of the mass flow rate is found to reduce the mean solar heat gain and the shading coefficients while the increase of the fluid entry temperature is found to deteriorate the window thermal performance

Simplified model for a ventilated glass window under forced air flow conditions

Energy Technology Data Exchange (ETDEWEB)

Ismail, K.A.R. [Depto. de Engenharia Termica e de Fluidos-FEM-UNICAMP CP: 6122 CEP 13083-970 Campinas, SP (Brazil); Henriquez, J.R. [Depto. de Eng. Mecanica-DEMEC, UFPE Av. Academico Helio Ramos, S/N CEP 50740-530, Recife, PE (Brazil)

2006-02-01

This paper presents a study on a ventilated window composed of two glass sheets separated by a spacing through which air is forced to flow. The proposed model is one dimensional and unsteady based upon global energy balance over the glass sheets and the flowing fluid. The external glass sheet of the cavity is subjected to variable heat flow due to the solar radiation as well as variable external ambient temperature. The exchange of radiation energy (infrared radiation) between the glass sheets is also included in the formulation. Effects of the spacing between the glass sheets, variation of the forced mass flow rate on the total heat gain and the shading coefficients are investigated. The results show that the effect of the increase of the mass flow rate is found to reduce the mean solar heat gain and the shading coefficients while the increase of the fluid entry temperature is found to deteriorate the window thermal performance. (author)

COMPARISON OF BIOACTIVITY IN VITRO OF GLASS AND GLASS CERAMIC MATERIALS DURING SOAKING IN SBF AND DMEM MEDIUM

Directory of Open Access Journals (Sweden)

GABRIELA LUTIŠANOVÁ

2011-09-01

Full Text Available This paper investigated the surface reactivity of two sets of glasses and glass ceramic materials belonging to the Li2O–SiO2–CaO–P2O5–CaF2 system. The in vitro bioactivity of coatings was evaluated using simulated body fluid (SBF and Dulbecco’s Modified Eagle’s Medium (DMEM soaking test in static regime for up to 28 days at 36.5°C in microincubator. The surface structure changes were examined by scanning electron microscopy (SEM and electron probe micro-analyzer (EPMA methods. The functional groups of the silicate and phosphates were identified by infrared spectroscopy (IR. The crystal phases of the glasses and glass ceramics were identified by X-ray diffraction analysis (XRD. The results suggest the bioactivity behavior for all compositions of glasses as well as glass ceramic samples after 28 days in the SBF and DMEM medium. The surface characterization and in vitro tests revealed a few variations in the reactivity of the different glasses and glass ceramic samples in their pristine form. The best results show the samples of glass and glass ceramic samples with higher content of fluorapatite (FA. The use of the acellular culture medium DMEM resulted in a delay at the start of precipitation.

Amorphous physics and materials: Interstitialcy theory of condensed matter states and its application to non-crystalline metallic materials

International Nuclear Information System (INIS)

Khonik, V A

2017-01-01

A comprehensive review of a novel promising framework for the understanding of non-crystalline metallic materials, i.e., interstitialcy theory of condensed matter states (ITCM), is presented. The background of the ITCM and its basic results for equilibrium/supercooled liquids and glasses are given. It is emphasized that the ITCM provides a new consistent, clear, and testable approach, which uncovers the generic relationship between the properties of the maternal crystal, equilibrium/supercooled liquid and glass obtained by melt quenching. (topical review)

Numerical Study on Mass Transfer of a Vapor Bubble Rising in Very High Viscous Fluid

Directory of Open Access Journals (Sweden)

T. Kunugi

2014-09-01

Full Text Available This study focused on a bubble rising behavior in a molten glass because it is important to improve the efficiency of removal of bubbles from the molten glass. On the other hand, it is expected that some gas species which exists in a bubble are transferred into the molten glass through the bubble interface, i.e., the mass transfer, subsequently, it may cause a bubble contraction in the molten glass. In this paper, in order to understand the bubble rising behavior with its contraction caused by the mass transfer through the bubble interface in the very high viscous fluid such as the molten glass, a bubble contraction model has been developed. The direct numerical simulations based on the MARS (Multi-interface Advection and Reconstruction Solver coupled with the mass transfer equation and the bubble contraction model regarding the mass transfer from the rising bubble in very high viscous fluid have been performed. Here, the working fluids were water vapor as the gas species and the molten glass as the very high viscous fluid. Also, the jump conditions at the bubble interface for the mass transfer were examined. Furthermore, the influence of the bubble contraction for the bubble rising compared to that in the water as a normal viscous fluid was investigated. From the result of the numerical simulations, it was found that the bubble rising behavior was strongly affected not only by the viscosity of the working fluid but also by the bubble contraction due to the mass transfer through the bubble interface.

The effect of additives on the speed of the crystallization front of xylitol with various degrees of supercooling

Energy Technology Data Exchange (ETDEWEB)

Seppaelae, Ari; Merilaeinen, Arttu [Helsinki University of Technology, Department of Energy Technology, Applied Thermodynamics, P.O. Box 4400, 02015 TKK (Finland); Wikstroem, Lisa; Kauranen, Pertti [VTT Technical Research Centre of Finland, Advanced Materials, P.O. Box 1300, 33101 Tampere (Finland)

2010-07-15

Some liquids can be kept in a supercooled or supersaturated metastable state for substantially long periods. Such liquids can be applied as long-term heat storage where the latent heat can be released when needed. As xylitol possesses a relatively high value of latent heat and as it can be easily supercooled, it has promising properties for this application. However, the speed of the crystallization of xylitol is low, leading to a low release rate of latent heat. Several additives have been experimentally tested for the purpose of accelerating the crystallization speed. The effect of the additives on the latent heat, on the melting temperatures, and on the long-term durability of the supercooled state was also measured. The highest speeds of the crystallization front, at a temperature of 22 C, were achieved with methanol as an additive leading to speeds 33 times higher in vertical experiments and in 170 times higher in horizontal ones than with pure xylitol. The improved speed of the crystallization front is mostly caused by the methanol flow currents generated as a result of the separation of methanol during crystallization, and to a lesser extent, as a result of the increase in the speed of the growth of the crystals. (author)

Surface Tension of Supercooled Water Determined by Using a Counterpressure Capillary Rise Method

Czech Academy of Sciences Publication Activity Database

Vinš, Václav; Fransen, M. A. L. J.; Hykl, Jiří; Hrubý, Jan

2015-01-01

Roč. 119, č. 17 (2015), s. 5567-5575 ISSN 1520-6106 R&D Projects: GA MŠk LG13056; GA ČR GJ15-07129Y Institutional support: RVO:61388998 Keywords : capillary tube * interfacial tension * metastable liquid * supercooled liquid Subject RIV: BJ - Thermodynamics Impact factor: 3.187, year: 2015 http://pubs.acs.org/doi/abs/10.1021/acs.jpcb.5b00545

The freezing and supercooling of garlic (Allium sativum L.)

Energy Technology Data Exchange (ETDEWEB)

James, Christian; Seignemartin, Violaine; James, Stephen J. [Food Refrigeration and Process Engineering Research Centre (FRPERC), University of Bristol, Churchill Building, Langford, Bristol BS40 5DU (United Kingdom)

2009-03-15

This work shows that peeled garlic cloves demonstrate significant supercooling during freezing under standard conditions and can be stored at temperatures well below their freezing point (-2.7 C) without freezing. The nucleation point or 'metastable limit temperature' (the point at which ice crystal nucleation is initiated) of peeled garlic cloves was found to be between -7.7 and -14.6 C. Peeled garlic cloves were stored under static air conditions at temperatures between -6 and -9 C for up to 69 h without freezing, and unpeeled whole garlic bulbs and cloves were stored for 1 week at -6 C without freezing. (author)

Supercooling as a viable non-freezing cell preservation method of rat hepatocytes.

Directory of Open Access Journals (Sweden)

O Berk Usta

Full Text Available Supercooling preservation holds the potential to drastically extend the preservation time of organs, tissues and engineered tissue products, and fragile cell types that do not lend themselves well to cryopreservation or vitrification. Here, we investigate the effects of supercooling preservation (SCP at -4(oC on primary rat hepatocytes stored in cryovials and compare its success (high viability and good functional characteristics to that of static cold storage (CS at +4(oC and cryopreservation. We consider two prominent preservation solutions a Hypothermosol (HTS-FRS and b University of Wisconsin solution (UW and a range of preservation temperatures (-4 to -10 (oC. We find that there exists an optimum temperature (-4(oC for SCP of rat hepatocytes which yields the highest viability; at this temperature HTS-FRS significantly outperforms UW solution in terms of viability and functional characteristics (secretions and enzymatic activity in suspension and plate culture. With the HTS-FRS solution we show that the cells can be stored for up to a week with high viability (~56%; moreover we also show that the preservation can be performed in large batches (50 million cells with equal or better viability and no loss of functionality as compared to smaller batches (1.5 million cells performed in cryovials.

Space resolved x-ray diffraction measurements of the supercooled state of polymers

International Nuclear Information System (INIS)

Asano, Tsutomu; Yoshida, Shinya; Nishida, Akira; Mina, M.F.

2002-01-01

In order to measure an ordering process of polymers, the supercooled state near the crystallizing surface was observed by a space resolved X-ray diffraction method at Photon Factory (PF). Using temperature slope crystallization, low density polyethylene and even-number paraffins were examined during crystallization from the melt state. The results indicate that polyethylene shows a sharp b-axis orientation where the lamellar normal and crystalline c-axis are perpendicular to the temperature slope. The crystalline lamellae are well-developed with lamellar thickness of 180 A. The supercooled melt state just above the crystallizing plane shows some diffraction in the small angle region without any crystalline reflection in the wide angle. This fact suggests that a long-range ordering (lamellar structure) appears prior to the short-range one (crystalline structure). The in-situ crystallizing surface was observed by an optical microscope connected to a TV system. The crystallizing surface of even-number paraffins moves to upwards in the temperature slope. In-situ X-ray measurements at PF revealed that the crystalline c-axis and lamellar normal of the even number paraffins are parallel to the temperature slope. From these results, the crystalline ordering and the surface movement of even number paraffins are explained using special nucleation mechanism including a screw dislocation. (author)

Crystallization Behavior and Relaxation Dynamics of Supercooled S‑Ketoprofen and the Racemic Mixture along an Isochrone

DEFF Research Database (Denmark)

Adrjanowicz, Karolina; Kaminski, Kamil; Paluch, Marian

2015-01-01

In this paper, we study crystallization behavior and molecular dynamics in the supercooled liquid state of the pharmaceutically important compound ketoprofen at various thermodynamic conditions. Dielectric relaxation for a racemic mixture was investigated in a wide range of temperatures and press...

The highly fragile glass former Decalin

International Nuclear Information System (INIS)

Eibl, Stefan

2009-01-01

Systems exhibiting the glass transition can be classified by fragility. In this work we studied structural and dynamical aspects of highly fragile C 10 H 18 Decalin. Trans Decalin is locked into a pseudo-flat centrosymmetric conformation, while cis Decalin interchanges dynamically between chiral, pseudo-spherical ground states. On investigation of the phase behaviour trans Decalin was found to crystallise rapidly and cleanly; its crystal structure could be determined. From the crystal structure the dynamics of crystalline trans Decalin could be calculated using ab-initio lattice energy calculations and compared to measurements. Using neutron diffraction and molecular dynamics simulations the amorphous structure of Decalin was investigated. The difference in structure to the common molecular liquid Cumene is significant. The features of the amorphous structure of sphere-like cis Decalin show strong resemblance to the ones of Argon and metallic glasses. The dynamics of Decalin were investigated in the slightly supercooled liquid range. Using neutron scattering and optical spectroscopy, data was collected for a wide spectral range and several temperatures. The data suggests high fragility for the generic Decalin mixture, which is in agreement with the reported results. By contrast to previous estimations, an extrapolation of our data indicates cis Decalin to be only slightly less fragile than the generic mixture. Finally a lower limit to the four point susceptibility function χ 4 could be calculated and the number of correlated molecules determined. The evolution of this value as a function of T g /T and relaxation time are in agreement with literature. (author) [fr

Microviscosity of supercooled water confined within aminopropyl-modified mesoporous silica as studied by time-resolved fluorescence spectroscopy.

Science.gov (United States)

Yamaguchi, Akira; Namekawa, Manato; Itoh, Tetsuji; Teramae, Norio

2012-01-01

The fluorescence dynamics of rhodamine B (RhB) immobilized on the pore surface of aminopropyl (AP)-modified mesoporous silica (diameter of the silica framework, 3.1 nm) was examined at temperatures between 293 and 193 K to study the microviscosity of supercooled water confined inside the pores. The mesoporous silica specimen with a dense AP layer (2.1 molecules nm(-2)) was prepared, and RhB isothiocyanate was covalently bound to part of the surface AP groups. The fluorescence lifetime of the surface RhB increased with decreasing temperature from 293 to 223 K, indicating that freezing of the confined water did not occur in this temperature range. The microviscosity of the supercooled confined water was evaluated from an analysis of the lifetime data based on a frequency-dependent friction model.

Behavior of supercooled aqueous solutions stemming from hidden liquid–liquid transition in water

Energy Technology Data Exchange (ETDEWEB)

Biddle, John W.; Holten, Vincent; Anisimov, Mikhail A., E-mail: anisimov@umd.edu [Institute for Physical Science and Technology and Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742 (United States)

2014-08-21

A popular hypothesis that explains the anomalies of supercooled water is the existence of a metastable liquid–liquid transition hidden below the line of homogeneous nucleation. If this transition exists and if it is terminated by a critical point, the addition of a solute should generate a line of liquid–liquid critical points emanating from the critical point of pure metastable water. We have analyzed thermodynamic consequences of this scenario. In particular, we consider the behavior of two systems, H{sub 2}O-NaCl and H{sub 2}O-glycerol. We find the behavior of the heat capacity in supercooled aqueous solutions of NaCl, as reported by Archer and Carter [J. Phys. Chem. B 104, 8563 (2000)], to be consistent with the presence of the metastable liquid–liquid transition. We elucidate the non-conserved nature of the order parameter (extent of “reaction” between two alternative structures of water) and the consequences of its coupling with conserved properties (density and concentration). We also show how the shape of the critical line in a solution controls the difference in concentration of the coexisting liquid phases.

Behavior of supercooled aqueous solutions stemming from hidden liquid–liquid transition in water

International Nuclear Information System (INIS)

Biddle, John W.; Holten, Vincent; Anisimov, Mikhail A.

2014-01-01

A popular hypothesis that explains the anomalies of supercooled water is the existence of a metastable liquid–liquid transition hidden below the line of homogeneous nucleation. If this transition exists and if it is terminated by a critical point, the addition of a solute should generate a line of liquid–liquid critical points emanating from the critical point of pure metastable water. We have analyzed thermodynamic consequences of this scenario. In particular, we consider the behavior of two systems, H 2 O-NaCl and H 2 O-glycerol. We find the behavior of the heat capacity in supercooled aqueous solutions of NaCl, as reported by Archer and Carter [J. Phys. Chem. B 104, 8563 (2000)], to be consistent with the presence of the metastable liquid–liquid transition. We elucidate the non-conserved nature of the order parameter (extent of “reaction” between two alternative structures of water) and the consequences of its coupling with conserved properties (density and concentration). We also show how the shape of the critical line in a solution controls the difference in concentration of the coexisting liquid phases

Stretched exponential relaxation in molecular and electronic glasses

Science.gov (United States)

Phillips, J. C.

1996-09-01

der Waals supercooled liquids and glasses, orientational glasses, water, fused salts, and heme proteins. In the intrinsic cases the theory of 0034-4885/59/9/003/img5 is often accurate to 2%, which is often better than the quoted experimental accuracies 0034-4885/59/9/003/img12. The extrinsic cases are identified by explicit structural signatures which are discussed at length. The discussion also includes recent molecular dynamical simulations for metallic glasses, spin glasses, quasicrystals and polymers which have achieved the intermediate relaxed Kohlrausch state and which have obtained values of 0034-4885/59/9/003/img2 in excellent agreement with the prediction of the microscopic theory.

Characterization of the glass transition of water predicted by molecular dynamics simulations using nonpolarizable intermolecular potentials.

Science.gov (United States)

Kreck, Cara A; Mancera, Ricardo L

2014-02-20

Molecular dynamics simulations allow detailed study of the experimentally inaccessible liquid state of supercooled water below its homogeneous nucleation temperature and the characterization of the glass transition. Simple, nonpolarizable intermolecular potentials are commonly used in classical molecular dynamics simulations of water and aqueous systems due to their lower computational cost and their ability to reproduce a wide range of properties. Because the quality of these predictions varies between the potentials, the predicted glass transition of water is likely to be influenced by the choice of potential. We have thus conducted an extensive comparative investigation of various three-, four-, five-, and six-point water potentials in both the NPT and NVT ensembles. The T(g) predicted from NPT simulations is strongly correlated with the temperature of minimum density, whereas the maximum in the heat capacity plot corresponds to the minimum in the thermal expansion coefficient. In the NVT ensemble, these points are instead related to the maximum in the internal pressure and the minimum of its derivative, respectively. A detailed analysis of the hydrogen-bonding properties at the glass transition reveals that the extent of hydrogen-bonds lost upon the melting of the glassy state is related to the height of the heat capacity peak and varies between water potentials.

Evolution of short range order in Ar: Liquid to glass and solid transitions-A computational study

Science.gov (United States)

Shor, Stanislav; Yahel, Eyal; Makov, Guy

2018-04-01

The evolution of the short range order (SRO) as a function of temperature in a Lennard-Jones model liquid with Ar parameters was determined and juxtaposed with thermodynamic and kinetic properties obtained as the liquid was cooled (heated) and transformed between crystalline solid or glassy states and an undercooled liquid. The Lennard-Jones system was studied by non-equilibrium molecular dynamics simulations of large supercells (approximately 20000 atoms) rapidly cooled or heated at selected quenching rates and at constant pressure. The liquid to solid transition was identified by discontinuities in the atomic volume and molar enthalpy; the glass transition temperature range was identified from the temperature dependence of the self-diffusion. The SRO was studied within the quasi-crystalline model (QCM) framework and compared with the Steinhardt bond order parameters. Within the QCM it was found that the SRO evolves from a bcc-like order in the liquid through a bct-like short range order (c/a=1.2) in the supercooled liquid which persists into the glass and finally to a fcc-like ordering in the crystalline solid. The variation of the SRO that results from the QCM compares well with that obtained with Steinhardt's bond order parameters. The hypothesis of icosahedral order in liquids and glasses is not supported by our results.

Bioactive glass 45S5 from diatom biosilica

Directory of Open Access Journals (Sweden)

Luqman A. Adams

2017-12-01

Full Text Available A major draw-back to large scale production of bioactive glasses is the high cost of the standard silica precursor, usually tetraethyl orthosilicate (TEOS. The current study describes a novel sol–gel preparation of 45S5 bioactive glass using diatom biosilica from cultured cells of the diatom, Aulacoseira granulata as substitute to TEOS. The glass formed was characterized using mechanical tester, scanning electron microscopy (SEM, energy dispersive X-ray analysis (EDX, X-ray diffraction (XRD and Fourier transform infrared (FTIR spectroscopy. Results showed that the glass possessed a compressive strength of 3.75 ± 0.18 and formed carbonated hydroxyapatite (HCA within 7 days in simulated body fluid (SBF, attributable to good surface chemistry. The performance of the glass was compared with that of those formed using TEOS. Diatom biosilica could be a potential economically friendly starting material for large scale fabrication of bioactive glasses.

Theory of terahertz electric oscillations by supercooled superconductors

Energy Technology Data Exchange (ETDEWEB)

Mishonov, Todor M; Mishonov, Mihail T [Department of Theoretical Physics, Faculty of Physics, University of Sofia St Kliment Ohridski, 5 J Bourchier Boulevard, 1164 Sofia (Bulgaria); Laboratorium voor Vaste-Stoffysica en Magnetisme, Katholieke Universiteit Leuven, Celestijnenlaan 200 D B-3001 Leuven (Belgium)

2005-11-15

We predict that below T{sub c} a regime of negative differential conductivity (NDC) can be reached. The superconductor should be supercooled to Tsupercooled superconductors to be used as an active medium for generation of electric oscillations. Such generators can be used in the superconducting electronics as a new type THz source of radiation. Oscillations can be modulated by the change of the bias voltage, electrostatic doping by a gate electrode when the superconductor is the channel of a field effect transistor, or by light. When small amplitude oscillations are stabilized near the critical temperature T{sub c} the generator can be used as a bolometer. NDC, which is essential for the applications, is predicted on the basis of analysis of known results for fluctuation conductivity, obtained in previous papers by solving the Boltzmann kinetic equation for the Cooper pairs metastable in the normal phase. The Boltzmann equation for fluctuation Cooper pairs is a result of state-of-the-art application of the microscopic theory of superconductivity. Our theoretical conclusions are based on some approximations like time dependent Ginzburg-Landau theory initially derived for gapless superconductors, but nevertheless can reliably predict the appearance of NDC. NDC is the main ingredient of the proposed technical applications. The maximal frequency at which superconductors can operate as generators is determined by the critical temperature {Dirac_h}/2{pi}{omega}{sub max} {approx} k{sub B}T{sub c}. For high-T{sub c} superconductors this maximal frequency falls well inside the terahertz range. Technical conditions to avoid nucleation of the superconducting phase are briefly discussed. We suggest that nanostructured high-T{sub c} superconductors patterned in a single chip can

Experimental investigations on prototype heat storage units utilizing stable supercooling of sodium acetate trihydrate mixtures

DEFF Research Database (Denmark)

Dannemand, Mark; Dragsted, Janne; Fan, Jianhua

2016-01-01

Laboratory tests of two heat storage units based on the principle of stable supercooling of sodium acetate trihydrate (SAT) mixtures were carried out. One unit was filled with 199.5 kg of SAT with 9% extra water to avoid phase separation of the incongruently melting salt hydrate. The other unit...

Sonocrystallization of Interesterified Soybean Oil: Effect of Saturation Level and Supercooling.

Science.gov (United States)

Lee, Juhee; Claro da Silva, Roberta; Gibon, Veronique; Martini, Silvana

2018-04-01

The aim of this study was to investigate the effects of supercooling and degree of saturation on lipid sonocrystallization under similar driving force of crystallization. Samples consisting of 100%, 50%, and 20% interesterified soybean oil (IESBO) diluted in high-oleic sunflower oil (HOSFO) were crystallized with and without high-intensity ultrasound (HIU). Two power levels were used by changing the amplitude of vibration of the tip (24 μm and 108 μm of tip amplitude). HIU operating at a frequency of 20 kHz was applied for 10 s. Sonication induced crystallization in the 100% IESBO sample and sonication power did not affect the results. A greater induction in crystallization was observed when higher power levels were used in the 50% IESBO sample, while no effect was observed in the crystallization kinetics of the 20% IESBO samples. Changes in the crystallization kinetics affected physical properties of the material, influencing elasticity. For example, sonication increased the elasticity of the 100% IESBO sample for both tip amplitudes from 435.9 ± 173.3 Pa to 72735.0 ± 9547.9 Pa for the nonsonicated and sonicated samples using 108 μm of amplitude, respectively. However, sonication only increased the elasticity in the 50% sample when used at the higher power level of 108 μm from 564.2 ± 175.2 Pa to 21774.0 ± 5694.9 Pa, and it did not affect the elasticity of the 20% IESBO samples. These results show that the level of saturation and the degree of supercooling affect sonication efficiency. High-intensity ultrasound (HIU) has been used as a novel method for changing the crystallization behavior of fats. HIU can be used to improve the physical properties of trans-free fats that are low in saturated fatty acids. Although recent studies have proven the effectiveness of this method to induce crystallization, the process must still be optimized to the industrial setting. All process parameters should be considered during the application of HIU, as they directly

Women's Career Development at the Glass Ceiling.

Science.gov (United States)

Inman, Pamela L.

1998-01-01

For women, success in shattering the glass ceiling lies not in adapting to a male workplace culture but in using career strategies such as self-knowledge, multiple mentors, integration of body and soul, and fluid, customized careers. (SK)

Fabrication and characterization of bioactive glass-ceramic using soda-lime-silica waste glass.

Science.gov (United States)

Abbasi, Mojtaba; Hashemi, Babak

2014-04-01

Soda-lime-silica waste glass was used to synthesize a bioactive glass-ceramic through solid-state reactions. In comparison with the conventional route, that is, the melt-quenching and subsequent heat treatment, the present work is an economical technique. Structural and thermal properties of the samples were examined by X-ray diffraction (XRD) and differential thermal analysis (DTA). The in vitro test was utilized to assess the bioactivity level of the samples by Hanks' solution as simulated body fluid (SBF). Bioactivity assessment by atomic absorption spectroscopy (AAS) and scanning electron microscopy (SEM) was revealed that the samples with smaller amount of crystalline phase had a higher level of bioactivity. Copyright © 2014 Elsevier B.V. All rights reserved.

The occurrence of ice production in slightly supercooled Arctic stratiform clouds as observed by ground-based remote sensors at the ARM NSA site

Science.gov (United States)

Zhang, Damao; Wang, Zhien; Luo, Tao; Yin, Yan; Flynn, Connor

2017-03-01

Ice particle formation in slightly supercooled stratiform clouds is not well documented or understood. In this study, 4 years of combined lidar depolarization and radar reflectivity (Ze) measurements are analyzed to distinguish between cold drizzle and ice crystal formations in slightly supercooled Arctic stratiform clouds over the Atmospheric Radiation Measurement Program Climate Research Facility North Slope of Alaska Utqiaġvik ("Barrow") site. Ice particles are detected and statistically shown to be responsible for the strong precipitation in slightly supercooled Arctic stratiform clouds at cloud top temperatures as high as -4°C. For ice precipitating Arctic stratiform clouds, the lidar particulate linear depolarization ratio (δpar_lin) correlates well with radar Ze at each temperature range, but the δpar_lin-Ze relationship varies with temperature ranges. In addition, lidar depolarization and radar Ze observations of ice generation characteristics in Arctic stratiform clouds are consistent with laboratory-measured temperature-dependent ice growth habits.

Bond orientational ordering in a metastable supercooled liquid: a shadow of crystallization and liquid–liquid transition

International Nuclear Information System (INIS)

Tanaka, Hajime

2010-01-01

It is widely believed that a liquid state can be characterized by a single order parameter, density, and that a transition from a liquid to solid can be described by density ordering (translational ordering). For example, this type of theory has had great success in describing the phase behaviour of hard spheres. However, there are some features that cannot be captured by such theories. For example, hard spheres crystallize into either hcp or fcc structures, without a tendency of bcc ordering which is expected by the Alexander–McTague theory based on the Landau-type free energy of the density order parameter. We also found hcp-like bond orientational ordering in a metastable supercooled liquid, which promotes nucleation of hcp crystals. Furthermore, theories based on the single order parameter cannot explain water-like thermodynamic and kinetic anomalies of a liquid and liquid–liquid transition in a single-component liquid. Based on these facts, we argue that we need an additional order parameter to describe a liquid state. It is bond orientational order, which is induced by dense packing in hard spheres or by directional bonding in molecular and atomic liquids. Bond orientational order is intrinsically of local nature, unlike translational order which is of global nature. This feature plays a unique role in crystallization and quasicrystal formation. We also reveal that bond orientational ordering is a cause of dynamic heterogeneity near a glass transition and is linked to slow dynamics. In relation to this, we note that, for describing the structuring of a highly disordered liquid, we need a structural signature of low configurational entropy, which is more general than bond orientational order. Finally, the water-like anomaly and liquid–liquid transition can be explained by bond orientational ordering due to hydrogen or covalent bonding and its cooperativity, respectively. So we argue that bond orientational ordering is a key to the physical understanding

Immobilization of enzymes by radiation-induced polymerization of glass-forming monomers

International Nuclear Information System (INIS)

Yoshida, M.; Kumakura, M.; Kaetsu, I.

1979-01-01

The effect of cooling rate of a monomeric system on the porosity and activity of an immobilized enzyme prepared by radiation-induced polymerization of 2-hydroxyethyl methacrylate at low temperatures has been studied. Slow cooling gave the same effect on porosity of the polymer as decreasing the monomer concentration. A glass-forming solvent such as diethylene glycol was added to water to study the effect of the supercooling tendency of the solvent. Addition of diethylene glycol decreased porosity and also enzymic activity. Water was replaced by the miscible solvent p-dioxane and the immiscible solvent n-decane in order to clarify the effect of solvent. p-Dioxane had a similar effect to water on the relation between the monomer concentration, porosity and activity. On the other hand, polymer prepared from the system containing n-decane showed different immobilization properties owing to the presence of independent pores in the matrix. (author)

Evaluation of the Seismic Characterision of Select Engineered Nanoparticles in Saturated Glass Beads

Science.gov (United States)

A laboratory testing apparatus was developed for the study of seismic body wave propagation through nanoparticles dispersed in pore fluid that is essentially saturating glass beads. First, the responses of water-saturated glass bead specimens were studied to establish baseline si...

Isolated ecosystems on supercooled scree slopes in subalpine environments - interaction between permafrost, soil and vegetation

Science.gov (United States)

Schwindt, Daniel; Kozák, Johanna-Luise; Kohlpaintner, Michael

2017-04-01

In the central European Alps, permafrost can be expected in altitudes above 2300 m a.s.l., where mean annual air temperatures are below -1°C. However, attributed to the thermally induced "chimney effect", isolated permafrost lenses can be found in scree slopes far below the timberline where mean annual air temperature is positive. Usually the supercooled subsurface appears as lenses at the foot of talus slopes, covered by a thick layer of organic material and a unique vegetation composition most obviously characterized by dwarf grown trees ("Hexenwäldli") and azonal plant species. The fact that mean annual air temperature is positive and therefore can be excluded as a driving factor makes these sites unique for studying interdependencies between a supercooled subsurface, plant adaptation and vegetation sociology as well as the soil development. Three study sites in the Swiss Alps, differing in altitude and substrate (granite, dolomite, limestone) were investigated. Studies covered the permafrost-affected central parts of the slope as well as the surrounding areas. For characterizing distribution and temporal variability of ground ice geophysical methods were applied (electrical resistivity- and seismic refraction tomography). Temperature data loggers were used for monitoring the thermal regime (air-, surface- and soil temperatures). Chemical parameters (pH, C/N ratio) and nutrient contents (N, P, Ca, Mg, Mn, K) were analyzed in different depth levels. Plant communities were analyzed with the Braun-Blanquet method. To characterize physiognomic adaptation of trees, transects have been determined parallel to slope, measuring tree height, diameter and age. Results show a strong spatial correlation between frozen ground, formation of a thick organic layer (Tangelhumus), azonal plant species distribution and pronounced dwarfing of trees. Surrounding areas with unfrozen subsurface show an - for the particular altitude - expected species and soil composition and normal

The Thermal Collector With Varied Glass Covers

International Nuclear Information System (INIS)

Luminosu, I.; Pop, N.

2010-01-01

The thermal collector with varied glass covers represents an innovation realized in order to build a collector able to reach the desired temperature by collecting the solar radiation from the smallest surface, with the highest efficiency. In the case of the thermal collector with variable cover glasses, the number of the glass plates covering the absorber increases together with the length of the circulation pipe for the working fluid. The thermal collector with varied glass covers compared to the conventional collector better meet user requirements because: for the same temperature increase, has the collecting area smaller; for the same collection area, realizes the highest temperature increase and has the highest efficiency. This works is addressed to researchers in the solar energy and to engineers responsible with air-conditioning systems design or industrial and agricultural products drying.

Glass forming ability and magnetic properties of Co{sub (40.2−x)}Fe{sub (20.1+x)}Ni{sub 6.7}B{sub 22.7}Si{sub 5.3}Nb{sub 5} (x=0–10) bulk metallic glasses produced by suction casting

Energy Technology Data Exchange (ETDEWEB)

Sarlar, Kagan [Physics Department, Faculty of Arts and Sciences, Uludag University, Gorukle Campus, 16059 Bursa (Turkey); Physics Department, Kamil Ozdag Faculty of Sciences, Karamanoglu Mehmetbey University, YunusEmre Campus, 70100 Karaman (Turkey); Kucuk, Ilker, E-mail: ikucuk@uludag.edu.tr [Physics Department, Faculty of Arts and Sciences, Uludag University, Gorukle Campus, 16059 Bursa (Turkey)

2015-01-15

The effect of Fe concentration on the glass forming ability (GFA) and magnetic properties in Co{sub (40.2−x)}Fe{sub (20.1+x)}Ni{sub 6.7}B{sub 22.7}Si{sub 5.3}Nb{sub 5} (x=0–10) bulk metallic glasses were investigated. By suction casting method, the bulk metallic glasses with diameters up to 2 mm were produced. We try to find out which Fe concentration makes an influence on Co based system's magnetic properties and glass forming ability. The curves of thermal analysis, obtained using differential scanning calorimetry (DSC), show that the Co{sub (40.2−x)}Fe{sub (20.1+x)}Ni{sub 6.7}B{sub 22.7}Si{sub 5.3}Nb{sub 5} (x=0–10) have a supercooled liquid region (∆T{sub x}) of about 44 K. The saturation magnetizations (J{sub s}) for as-cast BMG alloys were in the range of 0.62 T−0.81 T. - Highlights: • The effect of Fe concentration on the glass forming ability. • The substitution of an appropriate amount of Fe can enhance the GFA. • The substitution of Fe for Co also improves soft magnetic properties of the BMGs. • The high of J{sub s} 0.62−0.81 T with a low H{sub c} of 2−289 A/m of the alloys.

Simultaneous Synchrotron WAXD and Fast Scanning (Chip) Calorimetry: On the (Isothermal) Crystallization of HDPE and PA11 at High Supercoolings and Cooling Rates up to 200 °C s(-1).

Science.gov (United States)

Baeten, Dorien; Mathot, Vincent B F; Pijpers, Thijs F J; Verkinderen, Olivier; Portale, Giuseppe; Van Puyvelde, Peter; Goderis, Bart

2015-06-01

An experimental setup, making use of a Flash DSC 1 prototype, is presented in which materials can be studied simultaneously by fast scanning calorimetry (FSC) and synchrotron wide angle X-ray diffraction (WAXD). Accumulation of multiple, identical measurements results in high quality, millisecond WAXD patterns. Patterns at every degree during the crystallization and melting of high density polyethylene at FSC typical scanning rates from 20 up to 200 °C s(-1) are discussed in terms of the temperature and scanning rate dependent material crystallinities and crystal densities. Interestingly, the combined approach reveals FSC thermal lag issues, for which can be corrected. For polyamide 11, isothermal solidification at high supercooling yields a mesomorphic phase in less than a second, whereas at very low supercooling crystals are obtained. At intermediate supercooling, mixtures of mesomorphic and crystalline material are generated at a ratio proportional to the supercooling. This ratio is constant over the isothermal solidification time. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An overview on the conventional and nonconventional methods for manufacturing the metallic glasses

Directory of Open Access Journals (Sweden)

Axinte Eugen

2017-01-01

Full Text Available Metallic glasses (MGs, first discovered in 1959 at Caltech are currently among the most studied metallic materials. MGs called also glassy metals, amorphous metals, liquid metals, are considered to be among the materials of the future. The “classic” methods for industrialization of MGs are : end-casting in copper molds and protected environment, die forging , atomization for obtaining MG powder ,selective laser melting , imprinting in molds, thermoplastic shaping in the super-cooled temperature region. These methods are suitable for producing high value-added precision components but the problems still exists: expensive tools, limited lifetime of tools and the occurring of crystallization. Actually methods (thermoplastic shaping, casting and die forging are limited by the low flexibility of production and by higher costs of tools and accessories. More suitable methods are greatly desired to machine MGs for their wider applications.

Phosphate glass fibre scaffolds: Tailoring of the properties and enhancement of the bioactivity through mesoporous glass particles.

Science.gov (United States)

Novajra, G; Boetti, N G; Lousteau, J; Fiorilli, S; Milanese, D; Vitale-Brovarone, C

2016-10-01

Novel bone glass fibre scaffolds were developed by thermally bonding phosphate glass fibres belonging to the P2O5-CaO-Na2O-SiO2-MgO-K2O-TiO2 system (TiPS2.5 glass). Scaffolds with fibres of 85 or 110μm diameter were fabricated, showing compressive strength in the range of 2-3.5MPa, comparable to that of the trabecular bone. The effect of different thermal treatments and fibre diameters and length on the final scaffold structure was investigated by means of micro-CT analysis. The change of the sintering time from 30 to 60min led to a decrease in the scaffold overall porosity from 58 to 21vol.% for the 85μm fibre scaffold and from 50 to 40vol.% when increasing the sintering temperature from 490 to 500°C for the 110μm fibre scaffold. The 85μm fibres resulted in an increase of the scaffold overall porosity, increased pore size and lower trabecular thickness; the use of different fibre diameters allowed the fabrication of a scaffold showing a porosity gradient. In order to impart bioactive properties to the scaffold, for the first time in the literature the introduction in these fibre scaffolds of a bioactive phase, a melt-derived bioactive glass (CEL2) powder or spray-dried mesoporous bioactive glass particles (SD-MBG) was investigated. The scaffold bioactivity was assessed through soaking in simulated body fluid. CEL2/glass fibre scaffold did not show promising results due to particle detachment from the fibres during soaking in simulated body fluid. Instead the use of mesoporous bioactive powders showed to be an effective way to impart bioactivity to the scaffold and could be further exploited in the future through the ability of mesoporous particles to act as systems for the controlled release of drugs. Copyright © 2016 Elsevier B.V. All rights reserved.

Vesicles in Apollo 15 Green Glasses: The Nature of Ancient Lunar Gases

Science.gov (United States)

Thomas-Keprta, K. L.; Clemett, S. J.; Berger, E. L.; Rahman, Z.; McKay, D. S.; Gibson, E. K.; Wentworth, S. J.

2014-01-01

Detailed studies of Apollo 15 green glass and related beads have shown they were formed in gas-rich fire fountains.. As the magmatic fluid became super-saturated in volatile gas, bubbles or vesicles formed within the magma. These exsolved gases became trapped within vesicles as the glasses were ejected from the fire-fountain and subsequently quenched. One of the keys to understanding formation processes on the ancient moon includes determining the composition of volatile species and elements, including metals, dissolved in magmatic gases. Here we report the nature of mineral phases spatially associated with vesicles in a green glass bead from Apollo sample 15411,42. The phases reflect the composition of the cooling/degassing magmatic vapors and fluids present at the time of bead formation approx, 3 Ga ago

Turbulent heat transfer as a control of platelet ice growth in supercooled under-ice ocean boundary layers

Science.gov (United States)

McPhee, Miles G.; Stevens, Craig L.; Smith, Inga J.; Robinson, Natalie J.

2016-04-01

Late winter measurements of turbulent quantities in tidally modulated flow under land-fast sea ice near the Erebus Glacier Tongue, McMurdo Sound, Antarctica, identified processes that influence growth at the interface of an ice surface in contact with supercooled seawater. The data show that turbulent heat exchange at the ocean-ice boundary is characterized by the product of friction velocity and (negative) water temperature departure from freezing, analogous to similar results for moderate melting rates in seawater above freezing. Platelet ice growth appears to increase the hydraulic roughness (drag) of fast ice compared with undeformed fast ice without platelets. Platelet growth in supercooled water under thick ice appears to be rate-limited by turbulent heat transfer and that this is a significant factor to be considered in mass transfer at the underside of ice shelves and sea ice in the vicinity of ice shelves.

Recent Evidence on Bioactive Glass Antimicrobial and Antibiofilm Activity: A Mini-Review

Directory of Open Access Journals (Sweden)

Lorenzo Drago

2018-02-01

Full Text Available Bone defects caused by trauma or pathological events are major clinical and socioeconomic burdens. Thus, the efforts of regenerative medicine have been focused on the development of non-biodegradable materials resembling bone features. Consequently, the use of bioactive glass as a promising alternative to inert graft materials has been proposed. Bioactive glass is a synthetic silica-based material with excellent mechanical properties able to bond to the host bone tissue. Indeed, when immersed in physiological fluids, bioactive glass reacts, developing an apatite layer on the granule’s surface, playing a key role in the osteogenesis process. Moreover, the contact of bioactive glass with biological fluids results in the increase of osmotic pressure and pH due to the leaching of ions from granules’ surface, thus making the surrounding environment hostile to microbial growth. The bioactive glass antimicrobial activity is effective against a wide selection of aerobic and anaerobic bacteria, either in planktonic or sessile forms. Furthermore, bioglass is able to reduce pathogens’ biofilm production. For the aforementioned reasons, the use of bioactive glass might be a promising solution for the reconstruction of bone defects, as well as for the treatment and eradication of bone infections, characterized by bone necrosis and destruction of the bone structure.

Toward an understanding of surface layer formation, growth, and transformation at the glass-fluid interface

Science.gov (United States)

Hopf, J.; Eskelsen, J. R.; Chiu, M.; Ievlev, A. V.; Ovchinnikova, O. S.; Leonard, D.; Pierce, E. M.

2018-05-01

Silicate glass is a metastable and durable solid that has application to a number of energy and environmental challenges (e.g., microelectronics, fiber optics, and nuclear waste storage). If allowed to react with water over time silicate glass develops an altered layer at the solid-fluid interface. In this study, we used borosilicate glass (LAWB45) as a model material to develop a robust understanding of altered layer formation (i.e., amorphous hydrated surface layer and crystalline reaction products). Experiments were conducted at high surface area-to-volume ratio (∼200,000 m-1) and 90 °C in the pressurized unsaturated flow (PUF) apparatus for 1.5-years to facilitate the formation of thick altered layers and allow for the effluent solution chemistry to be monitored continuously. A variety of microscopy techniques were used to characterize reacted grains and suggest the average altered layer thickness is 13.2 ± 8.3 μm with the hydrated and clay layer representing 74.8% and 25.2% of the total altered layer, respectively. The estimate of hydrated layer thickness is within the experimental error of the value estimated from the B release rate data (∼10 ± 1 μm/yr) over the 1.5-year duration. PeakForce® quantitative nanomechanical mapping results suggest the hydrated layer has a modulus that ranges between ∼20 and 40 GPa, which is in the range of porous silica that contains from ∼20 to ∼50% porosity, yet significantly lower than dense silica (∼70-80 GPa). Scanning transmission electron microscopy (STEM) images confirm the presence of pores and an analysis of a higher resolution image provides a qualitative estimate of ≥22% porosity in the hydrated layer with variations in void volume with increasing distance from the unaltered glass. Chemical composition analyses, based on a combination of time-of-flight secondary-ion mass spectrometry (ToF-SIMS), scanning electron microscopy with X-ray energy dispersive spectroscopy (EDS), and STEM-EDS, clearly show

Fluid flow analysis of E-glass fiber reinforced pipe joints in oil and gas industry

Science.gov (United States)

Bobba, Sujith; Leman, Z.; Zainuddin, E. S.; Sapuan, S. M.

2018-04-01

Glass Fiber reinforced composites have become increasingly important over the past few years and now they are the first choice materials for fabricating pipes with low weight in combination with high strength and stiffness. In Oil And Gas Industry, The Pipelines transporting heavy crude oil are subjected to variable pressure waves causing fluctuating stress levels in the pipes. Computational Fluid Dynamics (CFD) analysis was performed using solid works flow stimulation software to study the effects of these pressure waves on some specified joints in the pipes. Depending on the type of heavy crude oil being used, the flow behavior indicated a considerable degree of stress levels in certain connecting joints, causing the joints to become weak over a prolonged period of use. This research proposes a new perspective that is still required to be developed regarding the change of the pipe material, fiber winding angle in those specified joints and finally implementing cad wind technology to check the output result of the stress levels so that the life of the pipes can be optimized.

Volcanic glasses, their origins and alteration processes

Science.gov (United States)

Friedman, I.; Long, W.

1984-01-01

Natural glass can be formed by volcanic processes, lightning (fulgarites) burning coal, and by meteorite impact. By far the most common process is volcanic - basically the glass is rapidly chilled molten rock. All natural glasses are thermodynamically unstable and tend to alter chemically or to crystallize. The rate of these processes is determined by the chemical composition of the magma. The hot and fluid basaltic melts have a structure that allows for rapid crystal growth, and seldom forms glass selvages greater than a few centimeters thick, even when the melt is rapidly cooled by extrusion in the deep sea. In contrast the cooler and very viscous rhyolitic magmas can yield bodies of glass that are tens of meters thick. These highly polymerized magmas have a high silica content - often 71-77% SiO2. Their high viscosity inhibits diffusive crystal growth. Basalt glass in sea water forms an alteration zone called palagonite whose thickness increases linearly with time. The rate of diffusion of water into rhyolitic glass, which follows the relationship - thickness = k (time) 1 2, has been determined as a function of the glass composition and temperature. Increased SiO2 increases the rate, whereas increased CaO, MgO and H2O decrease the rate. The activation energy of water diffusion varies from about 19 to 22 kcal/mol. for the glasses studied. The diffusion of alkali out of rhyolite glass occurs simultaneously with water diffusion into the glass. The rate of devitrification of rhyolitic glass is a function of the glass viscosity, which in turn is a function of water content and temperature. Although all of the aforementioned processes tend to destroy natural glasses, the slow rates of these processes, particularly for rhyolitic glass, has allowed samples of glass to persist for 60 million years. ?? 1984.

Natural glass analogues to alteration of nuclear waste glass: A review and recommendations for further study

International Nuclear Information System (INIS)

McKenzie, W.F.

1990-01-01

The purpose of this report is to review previous work on the weathering of natural glasses; and to make recommendations for further work with respect to studying the alteration of natural glasses as it relates quantifying rates of dissolution. the first task was greatly simplified by the published papers of Jercinovic and Ewing (1987) and Byers, Jercinovic, and Ewing (1987). The second task is obviously the more difficult of the two and the author makes no claim of completeness in this regard. Glasses weather in the natural environment by reacting with aqueous solutions producing a rind of secondary solid phases. It had been proposed by some workers that the thickness of this rind is a function of the age of the glass and thus could be used to estimate glass dissolution rates. However, Jercinovic and Ewing (1987) point out that in general the rind thickness does not correlate with the age of the glass owing to the differences in time of contact with the solution compared to the actual age of the sample. It should be noted that the rate of glass dissolution is also a function of the composition of both the glass and the solution, and the temperature. Quantification of the effects of these parameters (as well as time of contact with the aqueous phase and flow rates) would thus permit a prediction of the consequences of glass-fluid interactions under varying environmental conditions. Defense high- level nuclear waste (DHLW), consisting primarily of liquid and sludge, will be encapsulated by and dispersed in a borosilicate glass before permanent storage in a HLW repository. This glass containing the DHLW serves to dilute the radionuclides and to retard their dispersion into the environment. 318 refs

Natural glass analogues to alteration of nuclear waste glass: A review and recommendations for further study

Energy Technology Data Exchange (ETDEWEB)

McKenzie, W.F.

1990-01-01

The purpose of this report is to review previous work on the weathering of natural glasses; and to make recommendations for further work with respect to studying the alteration of natural glasses as it relates quantifying rates of dissolution. the first task was greatly simplified by the published papers of Jercinovic and Ewing (1987) and Byers, Jercinovic, and Ewing (1987). The second task is obviously the more difficult of the two and the author makes no claim of completeness in this regard. Glasses weather in the natural environment by reacting with aqueous solutions producing a rind of secondary solid phases. It had been proposed by some workers that the thickness of this rind is a function of the age of the glass and thus could be used to estimate glass dissolution rates. However, Jercinovic and Ewing (1987) point out that in general the rind thickness does not correlate with the age of the glass owing to the differences in time of contact with the solution compared to the actual age of the sample. It should be noted that the rate of glass dissolution is also a function of the composition of both the glass and the solution, and the temperature. Quantification of the effects of these parameters (as well as time of contact with the aqueous phase and flow rates) would thus permit a prediction of the consequences of glass-fluid interactions under varying environmental conditions. Defense high- level nuclear waste (DHLW), consisting primarily of liquid and sludge, will be encapsulated by and dispersed in a borosilicate glass before permanent storage in a HLW repository. This glass containing the DHLW serves to dilute the radionuclides and to retard their dispersion into the environment. 318 refs.

Thermo-physical characterization of the Fe_6_7Mo_6Ni_3_._5Cr_3_._5P_1_2C_5_._5B_2_._5 bulk metallic glass forming alloy

International Nuclear Information System (INIS)

Bochtler, Benedikt; Gross, Oliver; Gallino, Isabella; Busch, Ralf

2016-01-01

The iron-phosphorus based bulk metallic glass forming alloy Fe_6_7Mo_6Ni_3_._5Cr_3_._5P_1_2C_5_._5B_2_._5 is characterized with respect to its thermophysical properties, crystallization and relaxation behavior, as well as its viscosity. The alloy provides a high critical casting thickness of 13 mm, thus allowing for the casting of amorphous parts with a considerable size. Calorimetric measurements reveal the characteristic transformation temperatures, transformation enthalpies, and the specific heat capacity. The analyses show that no stable supercooled liquid region exists upon heating. The specific heat capacity data are used to calculate the enthalpy, entropy, and Gibbs free energy differences between the crystalline and the supercooled liquid state. The crystallization behavior of amorphous samples upon heating is analyzed by differential scanning calorimetry and X-ray diffraction, and a time-temperature-transformation diagram is constructed. Dilatometry is used to determine the thermal expansion behavior. The equilibrium viscosity below the glass transition as well as volume relaxation behavior are measured by three-point beam bending and dilatometry, respectively, to assess the kinetic fragility. With a kinetic fragility parameter of D* = 21.3, the alloy displays a rather strong liquid behavior. Viscosity above the melting point is determined using electromagnetic levitation in microgravity on a reduced gravity aircraft in cooperation with the German Aerospace Center (DLR). These high-temperature viscosity data are compared with the low-temperature three-point beam bending measurements. The alloy displays a strong liquid behavior at low temperatures and a fragile behavior at high temperatures. These results are analogous to the ones observed in several Zr-based bulk metallic glass forming liquids, indicating a strong to fragile liquid-liquid transition in the undercooled liquid, which is obscured by crystallization.

Kinetic arrest and glass-glass transition in short-ranged attractive colloids

International Nuclear Information System (INIS)

Sztucki, M.; Narayanan, T.; Belina, G.; Moussaied, A.; Pignon, F.; Hoekstra, H.

2006-01-01

A thermally reversible repulsive hard-sphere to sticky-sphere transition was studied in a model colloidal system over a wide volume fraction range. The static microstructure was obtained from high resolution small angle x-ray scattering, the colloid dynamics was probed by dynamic x-ray and light scattering, and supplementary mechanical properties were derived from bulk rheology. At low concentration, the system shows features of gas-liquid type phase separation. The bulk phase separation is presumably interrupted by a gelation transition at the intermediate volume fraction range. At high volume fractions, fluid-attractive glass and repulsive glass-attractive glass transitions are observed. It is shown that the volume fraction of the particles can be reliably deduced from the absolute scattered intensity. The static structure factor is modeled in terms of an attractive square-well potential, using the leading order series expansion of Percus-Yevick approximation. The ensemble-averaged intermediate scattering function shows different levels of frozen components in the attractive and repulsive glassy states. The observed static and dynamic behavior are consistent with the predictions of a mode-coupling theory and numerical simulations for a square-well attractive system

FeNbB bulk metallic glass: the influence of fluxing technique

Energy Technology Data Exchange (ETDEWEB)

Stoica, Mihai; Eckert, Juergen [IFW Dresden, Institute for Complex Materials, P.O. Box 270116, D-01171 Dresden (Germany); Kumar, Santosh [IFW Dresden, Institute for Complex Materials, P.O. Box 270116, D-01171 Dresden (Germany); Materials Science Centre, Indian Institute of Technology, Kharagpur 721302 (India); Roth, Stefan [IFW Dresden, Institute for Metallic Materials, P.O. Box 270116, D-01171 Dresden (Germany); Ram, Shanker [Materials Science Centre, Indian Institute of Technology, Kharagpur 721302 (India); Yavari, Alain Reza [LTPCM-CNRS, Institut National Politechnique de Grenoble, 1130 Rue de la Piscine, BP 75, Saint Martin d' Heres Campus 38402 (France)

2008-07-01

Recently, a new Fe-based BMG containing only 3 elements and a very high boron (Fe{sub 66}Nb{sub 4}B{sub 30}) content was synthesized. The preparation of this BMG was done by employing the copper mould casting method and using the fluxing technique. This new BMG is ferromagnetic, with a Curie temperature around 550 K and a saturation magnetization of 105 emu/g. Differential scanning calorimetry (DSC) investigations revealed a reduced glass transition temperature of 0.58 and an extension of the supercooled liquid region of about 31 K, values which indicate a relatively good thermal stability. Fluxed and not-fluxed master alloys were used to cast samples. The present work aims to discuss, for both kinds of samples, the kinetics of the phase formation using the Kissinger analysis and Johnson-Mehl-Avrami plots, correlated with the results obtained from X-ray diffraction (XRD) of samples with different metastable structures. Additionally, the magnetic behaviour of different phase(s) is discussed.

Structure-solubility relationships in fluoride-containing phosphate based bioactive glasses

Science.gov (United States)

Shaharyar, Yaqoot

The dissolution of fluoride-containing bioactive glasses critically affects their biomedical applications. Most commercial fluoride-releasing bioactive glasses have been designed in the soda-lime-silica system. However, their relatively slow chemical dissolution and the adverse effect of fluoride on their bioactivity are stimulating the study of novel biodegradable materials with higher bioactivity, such as biodegradable phosphate-based bioactive glasses, which can be a viable alternative for applications where a fast release of active ions is sought. In order to design new biomaterials with controlled degradability and high bioactivity, it is essential to understand the connection between chemical composition, molecular structure, and solubility in physiological fluids.Accordingly, in this work we have combined the strengths of various experimental techniques with Molecular Dynamics (MD) simulations, to elucidate the impact of fluoride ions on the structure and chemical dissolution of bioactive phosphate glasses in the system: 10Na2O - (45-x) CaO - 45P2O5 - xCaF2, where x varies between 0 -- 10 mol.%. NMR and MD data reveal that the medium-range atomic-scale structure of thse glasses is dominated by Q2 phosphate units followed by Q1 units, and the MD simulations further show that fluoride tends to associate with network modifier cations to form alkali/alkaline-earth rich ionic aggregates. On a macroscopic scale, we find that incorporating fluoride in phosphate glasses does not affect the rate of apatite formation on the glass surface in simulated body fluid (SBF). However, fluoride has a marked favorable impact on the glass dissolution in deionized water. Similarly, fluoride incorporation in the glasses results in significant weight gain due to adsorption of water (in the form of OH ions). These macroscopic trends are discussed on the basis of the F effect on the atomistic structure of the glasses, such as the F-induced phosphate network re-polymerization, in a

Acoustic Streaming and Its Suppression in Inhomogeneous Fluids.

Science.gov (United States)

Karlsen, Jonas T; Qiu, Wei; Augustsson, Per; Bruus, Henrik

2018-02-02

We present a theoretical and experimental study of boundary-driven acoustic streaming in an inhomogeneous fluid with variations in density and compressibility. In a homogeneous fluid this streaming results from dissipation in the boundary layers (Rayleigh streaming). We show that in an inhomogeneous fluid, an additional nondissipative force density acts on the fluid to stabilize particular inhomogeneity configurations, which markedly alters and even suppresses the streaming flows. Our theoretical and numerical analysis of the phenomenon is supported by ultrasound experiments performed with inhomogeneous aqueous iodixanol solutions in a glass-silicon microchip.

Cooling rate and starvation affect supercooling point and cold tolerance of the Khapra beetle, Trogoderma granarium Everts fourth instar larvae (Coleoptera: Dermestidae).

Science.gov (United States)

Mohammadzadeh, M; Izadi, H

2018-01-01

Trogoderma granarium Everts (Coleoptera: Dermestidae) is an important insect pest of stored products. In this study, the survival strategies of T. granarium fourth instar larvae were investigated at different sub-zero temperatures following different cooling rates, acclimation to different relative humidity (RH) and different starvation times. Our results show that larvae of T. granarium are freeze-intolerant. There was a strong link between cooling rates and supercooling point, which means the slower the decrease in temperature, the lower the supercooling point. Trehalose content was greater in insects cooled at a rate of 0.5°C/min. According to results, the RH did not affect supercooling point. However, acclimation to an RH of 25% increased mortality following exposure to - 10°C/24h. The time necessary to reach 95% mortality was 1737h and 428h at - 5°C and - 10°C. The lowest lipid and trehalose content was detected in insects acclimated to 25% RH, although, the different RH treatments did not significantly affect glycogen content of T. granarium larvae. The supercooling point of larvae was gradually increased following starvation. By contrast, fed larvae had the greatest lipid, glycogen, and trehalose content, and insects starved for eight days had the lowest energy contents. There was a sharp decline in the survival of larvae between - 11 and - 18°C after 1h exposure. Our results indicate the effects of cooling rate and starvation on energy reserves and survival of T. granarium. We conclude that T. granarium may not survive under similar stress conditions of the stored products. Copyright © 2017 Elsevier Ltd. All rights reserved.

Two-phase quasi-equilibrium in β-type Ti-based bulk metallic glass composites

Science.gov (United States)

Zhang, L.; Pauly, S.; Tang, M. Q.; Eckert, J.; Zhang, H. F.

2016-01-01

The microstructural evolution of cast Ti/Zr-based bulk metallic glass composites (BMGCs) containing β-Ti still remains ambiguous. This is why to date the strategies and alloys suitable for producing such BMGCs with precisely controllable volume fractions and crystallite sizes are still rather limited. In this work, a Ti-based BMGC containing β-Ti was developed in the Ti-Zr-Cu-Co-Be system. The glassy matrix of this BMGC possesses an exceptional glass-forming ability and as a consequence, the volume fractions as well as the composition of the β-Ti dendrites remain constant over a wide range of cooling rates. This finding can be explained in terms of a two-phase quasi-equilibrium between the supercooled liquid and β-Ti, which the system attains on cooling. The two-phase quasi-equilibrium allows predicting the crystalline and glassy volume fractions by means of the lever rule and we succeeded in reproducing these values by slight variations in the alloy composition at a fixed cooling rate. The two-phase quasi-equilibrium could be of critical importance for understanding and designing the microstructures of BMGCs containing the β-phase. Its implications on the nucleation and growth of the crystalline phase are elaborated. PMID:26754315

Orientational ordering as a possible mechanism for viscosity-enhancement of supercooled liquids

International Nuclear Information System (INIS)

Dattagupta, S.

1990-07-01

A supercooled liquid is viewed to have regions of local orientational order which can be picturized in terms of cages that restrict single particle diffusion. The mismatch in the orientation of two locally ordered neighbouring regions causes an internal stress which is added to the stress that appears in the Maxwell model of viscoelasticity. This leads to a ''renormalized'' Maxwell time which is related to the susceptibility associated with the orientational order. Hence, when the latter becomes very large, one obtains a large enhancement of the viscosity. (author). 7 refs

Heterogeneous nucleation from a supercooled ionic liquid on a carbon surface.

Science.gov (United States)

He, Xiaoxia; Shen, Yan; Hung, Francisco R; Santiso, Erik E

2016-12-07

Classical molecular dynamics simulations were used to study the nucleation of the crystal phase of the ionic liquid [dmim + ][Cl - ] from its supercooled liquid phase, both in the bulk and in contact with a graphitic surface of D = 3 nm. By combining the string method in collective variables [Maragliano et al., J. Chem. Phys. 125, 024106 (2006)], with Markovian milestoning with Voronoi tessellations [Maragliano et al., J. Chem. Theory Comput. 5, 2589-2594 (2009)] and order parameters for molecular crystals [Santiso and Trout, J. Chem. Phys. 134, 064109 (2011)], we computed minimum free energy paths, the approximate size of the critical nucleus, the free energy barrier, and the rates involved in these nucleation processes. For homogeneous nucleation, the subcooled liquid phase has to overcome a free energy barrier of ∼85 kcal/mol to form a critical nucleus of size ∼3.6 nm, which then grows into the monoclinic crystal phase. This free energy barrier becomes about 42% smaller (∼49 kcal/mol) when the subcooled liquid phase is in contact with a graphitic disk, and the critical nucleus formed is about 17% smaller (∼3.0 nm) than the one observed for homogeneous nucleation. The crystal formed in the heterogeneous nucleation scenario has a structure that is similar to that of the bulk crystal, with the exception of the layers of ions next to the graphene surface, which have larger local density and the cations lie with their imidazolium rings parallel to the graphitic surface. The critical nucleus forms near the graphene surface separated only by these layers of ions. The heterogeneous nucleation rate (∼4.8 × 10 11 cm -3 s -1 ) is about one order of magnitude faster than the homogeneous rate (∼6.6 × 10 10 cm -3 s -1 ). The computed free energy barriers and nucleation rates are in reasonable agreement with experimental and simulation values obtained for the homogeneous and heterogeneous nucleation of other systems (ice, urea, Lennard-Jones spheres, and oxide

NASA/FAA/NCAR Supercooled Large Droplet Icing Flight Research: Summary of Winter 1996-1997 Flight Operations

Science.gov (United States)

Miller, Dean; Ratvasky, Thomas; Bernstein, Ben; McDonough, Frank; Strapp, J. Walter

1998-01-01

During the winter of 1996-1997, a flight research program was conducted at the NASA-Lewis Research Center to study the characteristics of Supercooled Large Droplets (SLD) within the Great Lakes region. This flight program was a joint effort between the National Aeronautics and Space Administration (NASA), the National Center for Atmospheric Research (NCAR), and the Federal Aviation Administration (FAA). Based on weather forecasts and real-time in-flight guidance provided by NCAR, the NASA-Lewis Icing Research Aircraft was flown to locations where conditions were believed to be conducive to the formation of Supercooled Large Droplets aloft. Onboard instrumentation was then used to record meteorological, ice accretion, and aero-performance characteristics encountered during the flight. A total of 29 icing research flights were conducted, during which "conventional" small droplet icing, SLD, and mixed phase conditions were encountered aloft. This paper will describe how flight operations were conducted, provide an operational summary of the flights, present selected experimental results from one typical research flight, and conclude with practical "lessons learned" from this first year of operation.

Electro-suppression of water nano-droplets' solidification in no man's land: Electromagnetic fields' entropic trapping of supercooled water

Science.gov (United States)

Nandi, Prithwish K.; Burnham, Christian J.; English, Niall J.

2018-01-01

Understanding water solidification, especially in "No Man's Land" (NML) (150 K < T < 235 K) is crucially important (e.g., upper-troposphere cloud processes) and challenging. A rather neglected aspect of tropospheric ice-crystallite formation is inevitably present electromagnetic fields' role. Here, we employ non-equilibrium molecular dynamics of aggressively quenched supercooled water nano-droplets in the gas phase under NML conditions, in externally applied electromagnetic (e/m) fields, elucidating significant differences between effects of static and oscillating fields: although static fields induce "electro-freezing," e/m fields exhibit the contrary - solidification inhibition. This anti-freeze action extends not only to crystal-ice formation but also restricts amorphisation, i.e., suppression of low-density amorphous ice which forms otherwise in zero-field NML environments. E/m-field applications maintain water in the deeply supercooled state in an "entropic trap," which is ripe for industrial impacts in cryo-freezing, etc.

Structural dynamics of supercooled water from quasielastic neutron scattering and molecular simulations.

Science.gov (United States)

Qvist, Johan; Schober, Helmut; Halle, Bertil

2011-04-14

One of the outstanding challenges presented by liquid water is to understand how molecules can move on a picosecond time scale despite being incorporated in a three-dimensional network of relatively strong H-bonds. This challenge is exacerbated in the supercooled state, where the dramatic slowing down of structural dynamics is reminiscent of the, equally poorly understood, generic behavior of liquids near the glass transition temperature. By probing single-molecule dynamics on a wide range of time and length scales, quasielastic neutron scattering (QENS) can potentially reveal the mechanistic details of water's structural dynamics, but because of interpretational ambiguities this potential has not been fully realized. To resolve these issues, we present here an extensive set of high-quality QENS data from water in the range 253-293 K and a corresponding set of molecular dynamics (MD) simulations to facilitate and validate the interpretation. Using a model-free approach, we analyze the QENS data in terms of two motional components. Based on the dynamical clustering observed in MD trajectories, we identify these components with two distinct types of structural dynamics: picosecond local (L) structural fluctuations within dynamical basins and slower interbasin jumps (J). The Q-dependence of the dominant QENS component, associated with J dynamics, can be quantitatively rationalized with a continuous-time random walk (CTRW) model with an apparent jump length that depends on low-order moments of the jump length and waiting time distributions. Using a simple coarse-graining algorithm to quantitatively identify dynamical basins, we map the newtonian MD trajectory on a CTRW trajectory, from which the jump length and waiting time distributions are computed. The jump length distribution is gaussian and the rms jump length increases from 1.5 to 1.9 Å as the temperature increases from 253 to 293 K. The rms basin radius increases from 0.71 to 0.75 Å over the same range. The

Surface Tension of Supercooled Water: No Inflection Point down to-25 degrees C

Czech Academy of Sciences Publication Activity Database

Hrubý, Jan; Vinš, Václav; Mareš, R.; Hykl, Jiří; Kalová, J.

2014-01-01

Roč. 5, č. 3 (2014), s. 425-428 ISSN 1948-7185 R&D Projects: GA AV ČR(CZ) IAA200760905; GA ČR(CZ) GPP101/11/P046; GA MŠk(CZ) LG13056 Grant - others:Rada Programu interní podpory projektů mezinárodní spolupráce AV ČR(CZ) M100761201 Institutional support: RVO:61388998 Keywords : liquid * metastable * supercooled Subject RIV: JE - Non-nuclear Energetics, Energy Consumption ; Use Impact factor: 7.458, year: 2014

Sol-gel synthesis and in vitro bioactivity of copper and zinc-doped silicate bioactive glasses and glass-ceramics.

Science.gov (United States)

Bejarano, Julian; Caviedes, Pablo; Palza, Humberto

2015-03-11

Metal doping of bioactive glasses based on ternary 60SiO2-36CaO-4P2O5 (58S) and quaternary 60SiO2-25CaO-11Na2O-4P2O5 (NaBG) mol% compositions synthesized using a sol-gel process was analyzed. In particular, the effect of incorporating 1, 5 and 10 mol% of CuO and ZnO (replacing equivalent quantities of CaO) on the texture, in vitro bioactivity, and cytocompatibility of these materials was evaluated. Our results showed that the addition of metal ions can modulate the textural property of the matrix and its crystal structure. Regarding the bioactivity, after soaking in simulated body fluid (SBF) undoped 58S and NaBG glasses developed an apatite surface layer that was reduced in the doped glasses depending on the type of metal and its concentration with Zn displaying the largest inhibitions. Both the ion release from samples and the ion adsorption from the medium depended on the type of matrix with 58S glasses showing the highest values. Pure NaBG glass was more cytocompatible to osteoblast-like cells (SaOS-2) than pure 58S glass as tested by 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) assay. The incorporation of metal ions decreased the cytocompatibility of the glasses depending on their concentration and on the glass matrix doped. Our results show that by changing the glass composition and by adding Cu or Zn, bioactive materials with different textures, bioactivity and cytocompatibility can be synthesized.

Air oxidation of Zr65Cu17.5Ni10Al7.5 in its amorphous and supercooled liquid states, studied by thermogravimetric analysis

International Nuclear Information System (INIS)

Dhawan, A.; Sharma, S.K.; Raetzke, K.; Faupel, F.

2003-01-01

The oxidation behaviour of the bulk amorphous alloy Zr 65 Cu 17.5 Ni 10 Al 7.5 was studied in air at various temperatures in the temperature range 591-732 K using a thermogravimetric analyser (TGA). The oxidation kinetics of the alloy obeys the parabolic rate law showing two different linear regions (in the plots of mass gain versus square root of oxidation time) which are attributed to the amorphous and the supercooled liquid states of the alloy. The value of the activation energy Q for the amorphous state as calculated from the temperature dependence of the rate constants is found to be 1.80±0.1 eV and the corresponding value obtained for the supercooled liquid state is 1.20±0.1 eV. It is suggested that the rate controlling process during oxidation of the amorphous state is the back-diffusion of Ni, and possibly Cu also, while the oxidation in the supercooled liquid state is dominated by the inward diffusion of oxygen. (copyright 2003 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Impulsive Stimulated Light Scattering Studies of the Liquid-Glass Transition: on the Experimental Verification of Mode-Coupling Theory Predictions.

Science.gov (United States)

Halalay, Ion C.

A study of the structural glass transition trough impulsive stimulated light scattering experiments has been carried out in concentrated aqueous lithium chloride solutions, at temperatures ranging from ambient to cryogenic. A specially designed sample cell made it possible to cover the whole temperature interval from simple liquid, to viscoelastic supercooled liquid, to glass. It is shown that a phenomenological description of the results of these experiments in terms of a spectrum of relaxation times through the use of a Kohlrausch-Williams-Watts relaxation function is inadequate. Based on predictions of mode-coupling theory of the liquid-glass transition, an alternative approach to data interpretation is proposed. It is shown that for an aqueous lithium chloride solution, the prediction of simple scaling and identical scaling for mechanical and electrical susceptibilities seems to be valid. However, another prediction of theory is called into question: instead of a power-law behavior on temperature difference, it is found experimentally that the behavior of the susceptibility spectrum minimum is exponential. Similar disagreements are found for other two materials, triphenyl phosphite and polypropylene oxide. The causes for these discrepancies are discussed and it is concluded that additional experimentation is necessary to verify theoretical claims. Experiments are proposed which can test these predictions and serve as guide for the construction of theoretical models for the glass transition in real systems. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617 -253-5668; Fax 617-253-1690.).

A model for radiative cooling of a semitransparent molten glass jet

International Nuclear Information System (INIS)

Song, M.; Ball, K.S.; Bergman, T.L.

1998-01-01

Transfer of molten glass from location to location typically involves a pouring process, during which a stream of glass is driven by gravity and cooled by combined convective and radiative heat transfer. This study of the thermal and fluid mechanics aspects of glass pouring is motivated by the glass casting of vitrified, surplus weapons-grade plutonium. Here, a mathematical model for the radiative cooling of a semitransparent molten glass jet with temperature-dependent viscosity has been developed and is implemented numerically. The axial velocity and jet diameter variations along the length of the jet, the axial bulk mean temperature distributions, and the centerline-to-surface glass temperature distributions are determined for different processing conditions. Comparisons are also made between the semitransparent predictions, which are based on a spectral discrete ordinates model, and predictions for an opaque medium

On turbulence structure in vertical pipe flow of fiber suspensions [refractivity, flow measurement, turbulent flow, glass fibers, fluid flow

International Nuclear Information System (INIS)

Steen, M.

1989-01-01

A suspension of glass fibers in alcohol has been used to investigate a upward vertical developing pipe flow. The refractive index of the alcohol was matched to that of the glass fibers, making the whole suspension transparent. Laser Doppler Anemometry (LDA) was applied, and fluid velocities could then be measured for consistencies up to c = 12 g/l. Radial profiles of axial U-velocity and turbulence spectra have been recorded at various positions (z/D = 2, 5, 36) downstream of an orifice (step) with 64% open area. Measurements were taken for different consistencies (c = 1.2, 12 g/l), fiber lengths (l = 1, 3 mm) and Reynolds numbers (R e = 8.5 ⋅ 10 3 , 6.5 ⋅ 10 4 ). The fiber crowding factor (n f ) has been used to discuss the observed effects of the present fibers on momentum transfer and turbulence structure. The results show both an increase (l= 1 mm, c= 1.2 g/l) and decrease (l=3 mm, c = 12 g/l) in turbulence levels in the presence of fibers. Suspensions with long fibers at the highest consistency show plug flow in parts of the core. This causes damping of the turbulence mainly at smaller length scales. For short fibers at low consistency, the increased turbulent energy was mainly observed at small length scales in the spectrum. (author)

Tuning the magnetocaloric response of Er-based metallic glasses by varying structural order in disorder

Energy Technology Data Exchange (ETDEWEB)

Luo, Qiang [School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China); Tang, Meibo [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Shen, Jun, E-mail: junshen@tongji.edu.cn [School of Materials Science and Engineering, Tongji University, Shanghai 201804 (China)

2016-03-01

The effects of structural order on magnetocaloric response have been explored in Er{sub 60}Al{sub 16}Co{sub 20}Ni{sub 4} metallic glass (MG). Compared with the fully amorphous structure of the as-spun ribbon (cooling rate ∼10{sup 6} K/s), the rod sample fabricated with a lower cooling rate (∼10{sup 3} K/s) contains a few crystalline phases embedded in the amorphous matrix. Annealing the ribbon in the supercooled liquid region results in formation of a large amount of nanocrystalline phase. Both the as-spun ribbon and rod samples show a single spin-glass-like transition behavior, while the annealed sample exhibits double-freezing processes. It is found that the sparsely distributed micro-sized crystalline phases (content fraction of 13%) exert a slight effect on the magnetic entropy change (MEC). However, densely distributed nanocrystallization phase (∼50%) in amorphous matrix leads to an obvious reduction of the MEC and refrigerant capacity (RC). The exponent n of field dependence of MEC is found to related to exchange frustration, random anisotropy, and structure ordering degrees. - Highlights: • We determined the significant role of the size and distribution of the crystalline phases on the magnetic structure and magnetic performance of metallic glass composite. • It is found that the sparsely distributed micro-sized crystalline phases (content fraction of 13%) exert a slight effect on the MEC. • Densely distributed nanocrystalline phase (~50%) leads to an obvious reduction of the MEC.

Laser cladding of bioactive glass coatings.

Science.gov (United States)

Comesaña, R; Quintero, F; Lusquiños, F; Pascual, M J; Boutinguiza, M; Durán, A; Pou, J

2010-03-01

Laser cladding by powder injection has been used to produce bioactive glass coatings on titanium alloy (Ti6Al4V) substrates. Bioactive glass compositions alternative to 45S5 Bioglass were demonstrated to exhibit a gradual wetting angle-temperature evolution and therefore a more homogeneous deposition of the coating over the substrate was achieved. Among the different compositions studied, the S520 bioactive glass showed smoother wetting angle-temperature behavior and was successfully used as precursor material to produce bioactive coatings. Coatings processed using a Nd:YAG laser presented calcium silicate crystallization at the surface, with a uniform composition along the coating cross-section, and no significant dilution of the titanium alloy was observed. These coatings maintain similar bioactivity to that of the precursor material as demonstrated by immersion in simulated body fluid. Copyright 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Elastic moduli of a Brownian colloidal glass former

Science.gov (United States)

Fritschi, S.; Fuchs, M.

2018-01-01

The static, dynamic and flow-dependent shear moduli of a binary mixture of Brownian hard disks are studied by an event-driven molecular dynamics simulation. Thereby, the emergence of rigidity close to the glass transition encoded in the static shear modulus G_∞ is accessed by three methods. Results from shear stress auto-correlation functions, elastic dispersion relations, and the elastic response to strain deformations upon the start-up of shear flow are compared. This enables one to sample the time-dependent shear modulus G(t) consistently over several decades in time. By that a very precise specification of the glass transition point and of G_∞ is feasible. Predictions by mode coupling theory of a finite shear modulus at the glass transition, of α-scaling in fluid states close to the transition, and of shear induced decay in yielding glass states are tested and broadly verified.

Preparation and bioactive properties of nano bioactive glass and segmented polyurethane composites.

Science.gov (United States)

Aguilar-Pérez, Fernando J; Vargas-Coronado, Rossana F; Cervantes-Uc, Jose M; Cauich-Rodríguez, Juan V; Covarrubias, Cristian; Pedram-Yazdani, Merhdad

2016-04-01

Composites of glutamine-based segmented polyurethanes with 5 to 25 wt.% bioactive glass nanoparticles were prepared, characterized, and their mineralization potential was evaluated in simulated body fluid. Biocompatibility with dental pulp stem cells was assessed by MTS to an extended range of compositions (1 to 25 wt.% of bioactive glass nanoparticles). Physicochemical characterization showed that composites retained many of the matrix properties, i.e. those corresponding to semicrystalline elastomeric polymers as they exhibited a glass transition temperature (Tg) between -41 and -36℃ and a melting temperature (Tm) between 46 and 49℃ in agreement with X-ray reflections at 23.6° and 21.3°. However, with bioactive glass nanoparticles addition, tensile strength and strain were reduced from 22.2 to 12.2 MPa and 667.2 to 457.8%, respectively with 25 wt.% of bioactive glass nanoparticles. Although Fourier transform infrared spectroscopy did not show evidence of mineralization after conditioning of these composites in simulated body fluid, X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray microanalysis showed the formation of an apatite layer on the surface which increased with higher bioactive glass concentrations and longer conditioning time. Dental pulp stem cells proliferation at day 5 was improved in bioactive glass nanoparticles composites containing lower amounts of the filler (1-2.5 wt.%) but it was compromised at day 9 in composites containing high contents of nBG (5, 15, 25 wt.%). However, Runx2 gene expression was particularly upregulated for the dental pulp stem cells cultured with composites loaded with 15 and 25 wt.% of bioactive glass nanoparticles. In conclusion, low content bioactive glass nanoparticles and segmented polyurethanes composites deserve further investigation for applications such as guided bone regeneration membranes, where osteoconductivity is desirable but not a demanding mechanical performance. © The

Influence of ejection temperature on structure and glass transition behavior for Zr-based rapidly quenched disordered alloys

International Nuclear Information System (INIS)

Wang, X.H.; Inoue, A.; Kong, F.L.; Zhu, S.L.; Stoica, M.; Kaban, I.; Chang, C.T.; Shalaan, E.; Al-Marzouki, F.; Eckert, J.

2016-01-01

We examined the influence of ejection liquid temperature (T el ) on the structure, thermal stability and crystallization of Zr−Al−Ni−Cu ribbons prepared by the melt-spinning technique. The increase in T el was found to cause the formation of an oxide phase on the ribbon surface, more loose atomic configurations, the absence of glass transition (GT) and supercooled liquid (SL) region, and the rise of crystallization temperature. The changes in the GT and SL region occur reversibly by controlling the T el . Neither the change in alloy composition except oxygen nor the difference in crystallized phases is seen. Their hardness increases significantly by the disappearance of GT and SL region. The reversible changes in the appearance and disappearance of GT and SL region was found for different Zr-based glassy ribbons, being independent of alloy compositions. The disappearance is presumably due to the change in atomic configurations from high-coordinated to less-coordinated atomic packing in the melt-spun ribbons by freezing high-temperature liquid. The observed phenomenon of the reversible changes provides a novel opportunity for deep understanding of mutual correlations among liquid structure, GT, stability of SL and bulk glass-forming ability for metallic alloys.

Molecular dynamics in supercooled liquid and glassy states of antibiotics: azithromycin, clarithromycin and roxithromycin studied by dielectric spectroscopy. Advantages given by the amorphous state.

Science.gov (United States)

Adrjanowicz, K; Zakowiecki, D; Kaminski, K; Hawelek, L; Grzybowska, K; Tarnacka, M; Paluch, M; Cal, K

2012-06-04

Antibiotics are chemical compounds of extremely important medical role. Their history can be traced back more than one hundred years. Despite the passing time and significant progress made in pharmacy and medicine, treatment of many bacterial infections without antibiotics would be completely impossible. This makes them particularly unique substances and explains the unflagging popularity of antibiotics within the medical community. Herein, using dielectric spectroscopy we have studied the molecular mobility in the supercooled liquid and glassy states of three well-known antibiotic agents: azithromycin, clarithromycin and roxithromycin. Dielectric studies revealed a number of relaxation processes of different molecular origin. Besides the primary α-relaxation, observed above the respective glass transition temperatures of antibiotics, two secondary relaxations in the glassy state were identified. Interestingly, the fragility index as well as activation energies of the secondary processes turned out to be practically the same for all three compounds, indicating probably much the same molecular dynamics. Long-term stability of amorphous antibiotics at room temperature was confirmed by X-ray diffraction technique, and calorimetric studies were performed to evaluate the basic thermodynamic parameters. Finally, we have also checked the experimental solubility advantages given by the amorphous form of the examined antibiotics.

Glass microspheres for medical applications

Science.gov (United States)

Conzone, Samuel David

Radioactive dysprosium lithium borate glass microspheres have been developed as biodegradable radiation delivery vehicles for the radiation synovectomy treatment of rheumatoid arthritis. Once injected into a diseased joint, the microspheres deliver a potent dose of radiation to the diseased tissue, while a non-uniform chemical reaction converts the glass into an amorphous, porous, hydrated dysprosium phosphate reaction product. The non-radioactive, lithium-borate component is dissolved from the glass (up to 94% weight loss), while the radioactive 165Dy reacts with phosphate anions in the body fluids, and becomes "chemically" trapped in a solid, dysprosium phosphate reaction product that has the same size as the un-reacted glass microsphere. Ethylene diamine tetraacetate (EDTA) chelation therapy can be used to dissolve the dysprosium phosphate reaction product after the radiation delivery has subsided. The dysprosium phosphate reaction product, which formed in vivo in the joint of a Sprague-Dawley rat, was dissolved by EDTA chelation therapy in 100 Gy) of localized beta radiation to a treatment site within the body, followed by complete biodegradability. The non-uniform reaction process is a desirable characteristic for a biodegradable radiation delivery vehicle, but it is also a novel material synthesis technique that can convert a glass to a highly porous materials with widely varying chemical composition by simple, low-temperature, glass/solution reaction. The reaction product formed by nonuniform reaction occupies the same volume as the un-reacted glass, and after drying for 1 h at 300°C, has a specific surface area of ≈200 m2/g, a pore size of ≈30 nm, and a nominal crushing strength of ≈10 MPa. Finally, rhenium glass microspheres, composed of micron-sized, metallic rhenium particles dispersed within a magnesium alumino borate glass matrix were produced by sintering ReO2 powder and glass frit at 1050°C. A 50 mg injection of radioactive rhenium glass

Thermoplastic deformation of ferromagnetic CoFe-based bulk metallic glasses

Science.gov (United States)

Wu, Chenguang; Hu, Renchao; Man, Qikui; Chang, Chuntao; Wang, Xinmin

2017-12-01

The superplastic deformation behavior of the ferromagnetic Co31Fe31Nb8B30 bulk metallic glass (BMG) in the supercooled liquid region was investigated. At a given temperature, the BMG exhibits a Newtonian behavior at low strain rates but a non-Newtonian behavior at high strain rates. The high thermal stability of this glassy alloy system offers an enough processing window to thermoplastic forming (TPF), and the strong processing ability was examined by simple micro-replication experiments. It is demonstrated that the TPF formability on length scales ranging down to nanometers can be achieved in the selected experimental condition. Based on the analysis of deformation behavior, the nearly full density sample (i.e. nearly 100%), was produced from water-atomized glassy powders and consolidated by the hot-pressing technique. The sample exhibits good soft-magnetic and mechanical properties, i.e., low coercive force of 0.43 Oe, high initial permeability of 4100 and high Vickers hardness 1398. These results suggest that the hot-pressing process opens up possibilities for the commercial exploitation of BMGs in engineering applications.

Development of Cu-Hf-Al ternary systems and tungsten wire/particle reinforced Cu48Hf43Al9 bulk metallic glass composites for strengthening

International Nuclear Information System (INIS)

Park, Joyoung; An, Jihye; Choi-Yim, Haein

2010-01-01

Stable bulk glass forming alloys can be developed over a wide range of compositions in Cu-Hf-Al ternary systems starting from the Cu 49 Hf 42 Al 9 bulk metallic glass. Ternary Cu-Hf-Al alloys can be cast directly from the melt into copper molds to form fully amorphous strips with thicknesses of 1 to 6 mm. The maximum critical diameter of the new Cu-Hf-Al ternary alloy was 6 mm. X-ray diffraction patterns were used to confirm the amorphous nature of the ternary Cu-Hf-Al alloys. To increase the toughness of these metallic glasses, we reinforced the Cu 48 Hf 43 Al 9 bulk metallic glass-forming liquid with a 50% volume fraction of tungsten particles and an 80% volume fraction of tungsten wires with diameters of 242.4 μm. Composites with a critical diameter of 7 mm and length 70 mm were synthesized. The structure of the composites was confirmed by using X-ray diffraction (XRD), and the scanning electron microscopy (SEM). The mechanical properties of the composites were studied in compression tests. The thermal stability and the crystallization processes of the Cu-Hf-Al alloys and composites were investigated by using differential scanning calorimetry (DSC). Values of the glass transition temperature (T g ), the crystallization temperature (T x ), and the supercooled liquid region (ΔT = T x - T g ) are given in this paper.

Modeling of glass fusion furnaces; Modelisation des fours de fusion de verre

Energy Technology Data Exchange (ETDEWEB)

Mechitoua, N. [Electricite de France (EDF), 78 - Chatou (France). Direction des Etudes et Recherches; Plard, C. [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches

1997-12-31

The furnaces used for glass melting are industrial installations inside which complex and coupled physical and chemical phenomena occur. Thermal engineering plays a major role and numerical simulation is a precious tool for the analysis of the different coupling, of their interaction and of the influence of the different parameters. In order to optimize the functioning of glass furnaces and to improve the quality of the glass produced, Electricite de France (EdF) has developed a specialized version of the ESTET fluid mechanics code, called `Joule`. This paper describes the functioning principle of glass furnaces, the interactions between heat transfers and flows inside the melted glass, the interactions between heat transfers and the thermal regulation of the furnace, the interactions between heat transfers and glass quality and the heat transfer interactions between the melted glass, the furnace walls and the combustion area. (J.S.)

Substrate and surfactant effects on the glass-liquid transition of thin water films.

Science.gov (United States)

Souda, Ryutaro

2006-09-07

Temperature-programmed time-of-flight secondary ion mass spectrometry (TP-TOF-SIMS) and temperature-programmed desorption (TPD) have been used to perform a detailed investigation of the adsorption, desorption, and glass-liquid transition of water on the graphite and Ni(111) surfaces in the temperature range 13-200 K. Water wets the graphite surface at 100-120 K, and the hydrogen-bonded network is formed preferentially in the first monolayer to reduce the number of nonbonding hydrogens. The strongly chemisorbed water molecules at the Ni(111) surface do not form such a network and play a role in stabilizing the film morphology up to 160 K, where dewetting occurs abruptly irrespective of the film thickness. The surface structure of the water film formed on graphite is fluctuated considerably, resulting in deweting at 150-160 K depending on the film thickness. The dewetted patches of graphite are molecularly clean, whereas the chemisorbed water remains on the Ni(111) surface even after evaporation of the film. The abrupt drop in the desorption rate of water molecules at 160 K, which has been attributed to crystallization in the previous TPD studies, is found to disappear completely when a monolayer of methanol is present on the surface. This is because the morphology of supercooled liquid water is changed by the surface tension, and it is quenched by termination of the free OH groups on the surface. The surfactant methanol desorbs above 160 K since the hydrogen bonds of the water molecules are reconstructed. The drastic change in the properties of supercooled liquid water at 160 K should be ascribed to the liquid-liquid phase transition.

Antibacterial effects and dissolution behavior of six bioactive glasses.

Science.gov (United States)

Zhang, Di; Leppäranta, Outi; Munukka, Eveliina; Ylänen, Heimo; Viljanen, Matti K; Eerola, Erkki; Hupa, Mikko; Hupa, Leena

2010-05-01

Dissolution behavior of six bioactive glasses was correlated with the antibacterial effects of the same glasses against sixteen clinically important bacterial species. Powdered glasses (<45 microm) were immersed in simulated body fluid (SBF) for 48 h. The pH in the solution inside the glass powder was measured in situ with a microelectrode. After 2, 4, 27, and 48 h, the pH and concentration of ions after removing the particles and mixing the SBF were measured with a normal glass pH electrode and ICP-OES. The bacteria were cultured in broth with the glass powder for up to 4 days, after which the viability of the bacteria was determined. The antibacterial effect of the glasses increased with increasing pH and concentration of alkali ions and thus with increased dissolution tendency of the glasses, but it also depended on the bacterium type. The changes in the concentrations of Si, Ca, Mg, P, and B ions in SBF did not show statistically significant influence on the antibacterial property. Bioactive glasses showed strong antibacterial effects for a wide selection of aerobic bacteria at a high sample concentration (100 mg/mL). The antibacterial effects increased with glass concentration and a concentration of 50 mg/mL (SA/V 185 cm(-1)) was required to generate the bactericidal effects. Understanding the dissolution mechanisms of bioactive glasses is essential when assessing their antibacterial effects. Copyright 2009 Wiley Periodicals, Inc.

Inflorescences of alpine cushion plants freeze autonomously and may survive subzero temperatures by supercooling

Science.gov (United States)

Hacker, Jürgen; Ladinig, Ursula; Wagner, Johanna; Neuner, Gilbert

2011-01-01

Freezing patterns in the high alpine cushion plants Saxifraga bryoides, Saxifraga caesia, Saxifraga moschata and Silene acaulis were studied by infrared thermography at three reproductive stages (bud, anthesis, fruit development). The single reproductive shoots of a cushion froze independently in all four species at every reproductive stage. Ice formation caused lethal damage to the respective inflorescence. After ice nucleation, which occurred mainly in the stalk or the base of the reproductive shoot, ice propagated throughout that entire shoot, but not into neighboring shoots. However, anatomical ice barriers within cushions were not detected. The naturally occurring temperature gradient within the cushion appeared to interrupt ice propagation thermally. Consequently, every reproductive shoot needed an autonomous ice nucleation event to initiate freezing. Ice nucleation was not only influenced by minimum temperatures but also by the duration of exposure. At moderate subzero exposure temperatures (−4.3 to −7.7 °C) the number of frozen inflorescences increased exponentially. Due to efficient supercooling, single reproductive shoots remained unfrozen down to −17.4 °C (cooling rate 6 K h−1). Hence, the observed freezing pattern may be advantageous for frost survival of individual inflorescences and reproductive success of high alpine cushion plants, when during episodic summer frosts damage can be avoided by supercooling. PMID:21151351

Traction and lubricant film temperature as related to the glass transition temperature and solidification. [using infrared spectroscopy on EHD contacts

Science.gov (United States)

Lauer, J. L.; Peterkin, M. E.

1978-01-01

Does a traction fluid have to be a glass or solid under operating conditions. Infrared spectra on dynamic EHD contacts of several types of fluid were used to determine the surface and oil-film temperatures. Polarized spectral runs were made to study molecular alignment. Static glass transition pressures at appropriate temperatures were between 0.1 and 2.0 GPa, with the traction fluid showing the highest. In the EHD contact region, the traction fluid showed both the highest film temperatures as well as the greatest degree of molecular alignment. A plot of the difference between the film and surface temperatures vs shear rate resulted in a master plot valid for all the fluids. From this work, the authors propose a model of 'fluid' traction, where friction between parallel rough molecules provides the traction.

Influence of Mo on the structure of borosilicate glass for the immobilization of high level waste

International Nuclear Information System (INIS)

Petrov, I.; Dimitriev, Y.; Kashchieva, E.

2015-01-01

It has been shown that the classic multi-borosilicate glass with concentration of MoO 3 has a low melting in the range of 1300 to 1400 ° C, but for achieving of complete homogenization and vitrification it is required temperature above 1400 ° C. Under this temperature in all tested samples areas of crystallization were observed, due to incomplete vitrification processes. It is understood that in all multicomponent borosilicate glass featuring MoO 3 , occur micro vitrification processes, and at a concentration of MoO 3 above 20% - macro segregation; It has been shown that the introduction of Nd in compound borosilicate glass featuring MoO 3 is observed crystallization of the phase Na 0.5 Nd 0.5 Mo, and it has been also found that the phase Na 0.5 Nd 0.5 Mo 4 can be synthesized either by solid phase reaction or supercooled melt. The results of surveys show that It is possible to prevent the occurrence of liquid phase separation in the studied multicomponent glass. From a structural point of view, the cause of liquid phase separation is the result of structural incompatibility of molybdenum units with structural units borosilicate network since not been established links Mo-O-B-O and Mo-Si. From a thermodynamic point of view in the lamination multi windows may be due to overlapping areas of delamination in component binary and triple systems. From the kinetic point of view of course the liquid phase by settling, and crystallization may be due to imbalances conditions the cooling process, in the course of which flow various processes of imbalances metastable settling, followed by crystallization of molybdate phases

Statistical mechanics and the physics of fluids

CERN Document Server

Tosi, Mario

This volume collects the lecture notes of a course on statistical mechanics, held at Scuola Normale Superiore di Pisa for third-to-fifth year students in physics and chemistry. Three main themes are covered in the book. The first part gives a compact presentation of the foundations of statistical mechanics and their connections with thermodynamics. Applications to ideal gases of material particles and of excitation quanta are followed by a brief introduction to a real classical gas and to a weakly coupled classical plasma, and by a broad overview on the three states of matter.The second part is devoted to fluctuations around equilibrium and their correlations. Coverage of liquid structure and critical phenomena is followed by a discussion of irreversible processes as exemplified by diffusive motions and by the dynamics of density and heat fluctuations. Finally, the third part is an introduction to some advanced themes: supercooling and the glassy state, non-Newtonian fluids including polymers and liquid cryst...

Laser Machining and In Vitro Assessment of Wollastonite-Tricalcium Phosphate Eutectic Glasses and Glass-Ceramics

Directory of Open Access Journals (Sweden)

Daniel Sola

2018-01-01

Full Text Available Bioactivity and ingrowth of ceramic implants is commonly enhanced by a suitable interconnected porous network. In this work, the laser machining of CaSiO3‒Ca3(PO42 biocompatible eutectic glass-ceramics and glasses was studied. For this purpose, 300 µm diameter craters were machined by using pulsed laser radiation at 532 nm with a pulsewidth in the nanosecond range. Machined samples were soaked in simulated body fluid for 2 months to assess the formation of a hydroxyapatite layer on the surface of the laser machined areas. The samples were manufactured by the laser floating zone technique using a CO2 laser. Morphology, composition and microstructure of the machined samples were described by Field Emission Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy and micro-Raman Spectroscopy.

A Peristaltic Pump Integrated on a 100% Glass Microchip Using Computer Controlled Piezoelectric Actuators

Directory of Open Access Journals (Sweden)

Yo Tanaka

2014-05-01

Full Text Available Lab-on-a-chip technology is promising for the miniaturization of chemistry, biochemistry, and/or biology researchers looking to exploit the advantages of a microspace. To manipulate fluid on a microchip, on-chip pumps are indispensable. To date, there have been several types of on-chip pumps including pneumatic, electroactive, and magnetically driven. However these pumps introduce polymers, metals, and/or silicon to the microchip, and these materials have several disadvantages, including chemical or physical instability, or an inherent optical detection limit. To overcome/avoid these issues, glass has been one of the most commonly utilized materials for the production of multi-purpose integrated chemical systems. However, glass is very rigid, and it is difficult to incorporate pumps onto glass microchips. This paper reports the use of a very flexible, ultra-thin glass sheet (minimum thickness of a few micrometers to realize a pump installed on an entirely glass-based microchip. The pump is a peristaltic-type, composed of four serial valves sealing a cavity with two penetrate holes using ultra-thin glass sheet. By this pump, an on-chip circulating flow was demonstrated by directly observing fluid flow, visualized via polystyrene tracking particles. The flow rate was proportional to the pumping frequency, with a maximum flow rate of approximately 0.80 μL/min. This on-chip pump could likely be utilized in a wide range of applications which require the stability of a glass microchip.

Packaged integrated opto-fluidic solution for harmful fluid analysis

Science.gov (United States)

Allenet, T.; Bucci, D.; Geoffray, F.; Canto, F.; Couston, L.; Jardinier, E.; Broquin, J.-E.

2016-02-01

Advances in nuclear fuel reprocessing have led to a surging need for novel chemical analysis tools. In this paper, we present a packaged lab-on-chip approach with co-integration of optical and micro-fluidic functions on a glass substrate as a solution. A chip was built and packaged to obtain light/fluid interaction in order for the entire device to make spectral measurements using the photo spectroscopy absorption principle. The interaction between the analyte solution and light takes place at the boundary between a waveguide and a fluid micro-channel thanks to the evanescent part of the waveguide's guided mode that propagates into the fluid. The waveguide was obtained via ion exchange on a glass wafer. The input and the output of the waveguides were pigtailed with standard single mode optical fibers. The micro-scale fluid channel was elaborated with a lithography procedure and hydrofluoric acid wet etching resulting in a 150+/-8 μm deep channel. The channel was designed with fluidic accesses, in order for the chip to be compatible with commercial fluidic interfaces/chip mounts. This allows for analyte fluid in external capillaries to be pumped into the device through micro-pipes, hence resulting in a fully packaged chip. In order to produce this co-integrated structure, two substrates were bonded. A study of direct glass wafer-to-wafer molecular bonding was carried-out to improve detector sturdiness and durability and put forward a bonding protocol with a bonding surface energy of γ>2.0 J.m-2. Detector viability was shown by obtaining optical mode measurements and detecting traces of 1.2 M neodymium (Nd) solute in 12+/-1 μL of 0.01 M and pH 2 nitric acid (HNO3) solvent by obtaining an absorption peak specific to neodymium at 795 nm.

Slow Dynamics and Structure of Supercooled Water in Confinement

Directory of Open Access Journals (Sweden)

Gaia Camisasca

2017-04-01

Full Text Available We review our simulation results on properties of supercooled confined water. We consider two situations: water confined in a hydrophilic pore that mimics an MCM-41 environment and water at interface with a protein. The behavior upon cooling of the α relaxation of water in both environments is well interpreted in terms of the Mode Coupling Theory of glassy dynamics. Moreover, we find a crossover from a fragile to a strong regime. We relate this crossover to the crossing of the Widom line emanating from the liquid-liquid critical point, and in confinement we connect this crossover also to a crossover of the two body excess entropy of water upon cooling. Hydration water exhibits a second, distinctly slower relaxation caused by its dynamical coupling with the protein. The crossover upon cooling of this long relaxation is related to the protein dynamics.

Synthesis, characterization of CaF2 doped silicate glass-ceramics.

Science.gov (United States)

Riaz, Madeeha; Zia, Rehana; Mirza, Ambreen; Hussain, Tousif; Bashir, Farooq; Anjum, Safia

2017-06-01

This paper reports the fabrication and characterization of silicate glass-ceramics doped with (0-12mol%) CaF 2 . TGA-DSC analysis was carried out to determine the crystallization temperature and stability of glass measured by two glass parameters; Hruby parameter K H =(T x -T g )/(T L -T x ) and Weinberg parameter K W =(T c -T g )/T L . It was found that with CaF 2 doping improved sinterability at low temperature and provided stability to the glass. The XRD pattern exhibits a single phase of combeite and doping of CaF 2 cause increase in crystallite size. Microstructure of samples was also improved with CaF 2 addition, pores were significantly reduced. After 15days immersion in simulated body fluid all samples developed apatite layer onto its surface. Hence, the addition of CaF 2 provided bioactive glass-ceramic material having a low processing temperature. Copyright © 2017 Elsevier B.V. All rights reserved.

In vitro behaviour of three biocompatible glasses in composite implants.

Science.gov (United States)

Varila, Leena; Lehtonen, Timo; Tuominen, Jukka; Hupa, Mikko; Hupa, Leena

2012-10-01

Poly(L,DL-lactide) composites containing filler particles of bioactive glasses 45S5 and S53P4 were compared with a composite containing a slowly dissolving glass S68. The in vitro reactivity of the composites was studied in simulated body fluid, Tris-buffered solution, and phosphate buffered saline. The high processing temperature induced thermal degradation giving cavities in the composites containing 45S5 and S53P4, while good adhesion of S68 to the polymer was observed. The cavities partly affected the in vitro reactivity of the composites. The degradation of the composites containing the bioactive glasses was faster in phosphate buffered saline than in the two other solutions. Hydroxyapatite precipitation suggesting bone tissue bonding capability was observed on these two composites in all three solutions. The slower dissolution of S68 glass particles and the limited hydroxyapatite precipitation suggested that this glass has potential as a reinforcing composition with the capability to guide bone tissue growth in biodegradable polymer composites.

Glass transition in soft-sphere dispersions

International Nuclear Information System (INIS)

RamIrez-Gonzalez, P E; Medina-Noyola, M

2009-01-01

The concept of dynamic equivalence among mono-disperse soft-sphere fluids is employed in the framework of the self-consistent generalized Langevin equation (SCGLE) theory of colloid dynamics to calculate the ideal glass transition phase diagram of model soft-sphere colloidal dispersions in the softness-concentration state space. The slow dynamics predicted by this theory near the glass transition is compared with available experimental data for the decay of the intermediate scattering function of colloidal dispersions of soft-microgel particles. Increasing deviations from this simple scheme occur for increasingly softer potentials, and this is studied here using the Rogers-Young static structure factor of the soft-sphere systems as the input of the SCGLE theory, without assuming a priori the validity of the equivalence principle above.

PREFACE: Complex dynamics of fluids in disordered and crowded environments Complex dynamics of fluids in disordered and crowded environments

Science.gov (United States)

Coslovich, Daniele; Kahl, Gerhard; Krakoviack, Vincent

2011-06-01

. In fact, theory and simulations were recently able to predict new and surprising dynamical features, such as the occurrence of sub-diffusive laws, which result from the trapping due to the geometric and topological constraints and/or quenched disorder, the presence of both continuous and discontinuous glass transitions, and diffusion-localization transitions. Together, theory and simulations are thus able to contribute to a deeper insight into the complex dynamical behaviour of fluids in disordered confinement. Still, many yet unsolved problems remain. The fact that theoretical and simulation approaches have caught up with experimental investigations, has motivated us to organize a workshop on the dynamics of fluids confined in disordered environments, so as to bring together the different communities working in this field: theory and simulations, with their recent developments based on the mode-coupling theory of the glass transition, and experiments, with particular emphasis on colloidal systems and novel techniques. In an effort to give credit to recent developments in related problems of biophysical relevance, an entire session of the programme was dedicated to anomalous diffusion in crowded environments. The workshop was thus aimed at providing a deeper understanding of the complex dynamics of fluids in confinement as well as up-to-date perspectives on the interdisciplinary applications of this field of research. We are proud to say that all 32 contacted speakers accepted our invitation. Additional participants were attracted by our scientific programme, contributing poster presentations to the workshop. In total, close to 50 participants were registered, arriving from 11 different countries (including the US, Japan, and Mexico). Thus we conclude that the workshop indeed addressed a highly topical scientific field. From the scientific point of view a broad range of problems was covered, ranging from biophysics over soft matter to fermion systems. From the vivid

Numerical simulation of travelling wave induced electrothermal fluid flow

International Nuclear Information System (INIS)

Perch-Nielsen, Ivan R; Green, Nicolas G; Wolff, Anders

2004-01-01

Many microdevices for manipulating particles and cells use electric fields to produce a motive force on the particles. The movement of particles in non-uniform electric fields is called dielectrophoresis, and the usual method of applying this effect is to pass the particle suspension over a microelectrode structure. If the suspension has a noticeable conductivity, one important side effect is that the electric field drives a substantial conduction current through the fluid, causing localized Joule-heating. The resulting thermal gradient produces local conductivity and permittivity changes in the fluid. Dielectrophoretic forces acting upon these pockets of fluid will then produce motion of both the fluid and the particles. This paper presents a numerical solution of the electrical force and the resulting electrothermal driven fluid flow on a travelling wave structure. This common electrode geometry consists of interdigitated electrodes laid down in a long array, with the phase of the applied potential shifted by 90 0 on each subsequent electrode. The resulting travelling electric field was simulated and the thermal field and electrical body force on the fluid calculated, for devices constructed from two typical materials: silicon and glass. The electrothermal fluid flow in the electrolyte over the electrode array was then numerically simulated. The model predicts that the thermal field depends on the conductivity and applied voltage, but more importantly on the geometry of the system and the material used in the construction of the device. The velocity of the fluid flow depends critically on the same parameters, with slight differences in the thermal field for glass and silicon leading to diametrically opposite flow direction with respect to the travelling field for the two materials. In addition, the imposition of slight external temperature gradients is shown to have a large effect on the fluid flow in the device, under certain conditions leading to a reversal of

Role of glass structure in defining the chemical dissolution behavior, bioactivity and antioxidant properties of zinc and strontium co-doped alkali-free phosphosilicate glasses.

Science.gov (United States)

Kapoor, Saurabh; Goel, Ashutosh; Tilocca, Antonio; Dhuna, Vikram; Bhatia, Gaurav; Dhuna, Kshitija; Ferreira, José M F

2014-07-01

We investigated the structure-property relationships in a series of alkali-free phosphosilicate glass compositions co-doped with Zn(2+) and Sr(2+). The emphasis was laid on understanding the structural role of Sr(2+) and Zn(2+) co-doping on the chemical dissolution behavior of glasses and its impact on their in vitro bioactivity. The structure of glasses was studied using molecular dynamics simulations in combination with solid state nuclear magnetic resonance spectroscopy. The relevant structural properties are then linked to the observed degradation behavior, in vitro bioactivity, osteoblast proliferation and oxidative stress levels. The apatite-forming ability of glasses has been investigated by X-ray diffraction, infrared spectroscopy and scanning electron microscopy-energy-dispersive spectroscopy after immersion of glass powders/bulk in simulated body fluid (SBF) for time durations varying between 1h and 14 days, while their chemical degradation has been studied in Tris-HCl in accordance with ISO 10993-14. All the glasses exhibit hydroxyapatite formation on their surface within 1-3h of their immersion in SBF. The cellular responses were observed in vitro on bulk glass samples using human osteosarcoma MG63 cell line. The dose-dependent cytoprotective effect of glasses with respect to the concentration of zinc and strontium released from the glasses is also discussed. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Molecular dynamics beyonds the limits: Massive scaling on 72 racks of a BlueGene/P and supercooled glass dynamics of a 1 billion particles system

KAUST Repository

Allsopp, Nicholas

2012-04-01

We report scaling results on the world\\'s largest supercomputer of our recently developed Billions-Body Molecular Dynamics (BBMD) package, which was especially designed for massively parallel simulations of the short-range atomic dynamics in structural glasses and amorphous materials. The code was able to scale up to 72 racks of an IBM BlueGene/P, with a measured 89% efficiency for a system with 100 billion particles. The code speed, with 0.13. s per iteration in the case of 1 billion particles, paves the way to the study of billion-body structural glasses with a resolution increase of two orders of magnitude with respect to the largest simulation ever reported. We demonstrate the effectiveness of our code by studying the liquid-glass transition of an exceptionally large system made by a binary mixture of 1 billion particles. © 2012.

Simulation of the solidification in a channel of a water-cooled glass flow

Directory of Open Access Journals (Sweden)

G. E. Ovando Chacon

2014-12-01

Full Text Available A computer simulation study of a laminar steady-state glass flow that exits from a channel cooled with water is reported. The simulations are carried out in a two-dimensional, Cartesian channel with a backward-facing step for three different angles of the step and different glass outflow velocities. We studied the interaction of the fluid dynamics, phase change and thermal behavior of the glass flow due to the heat that transfers to the cooling water through the wall of the channel. The temperature, streamline, phase change and pressure fields are obtained and analyzed for the glass flow. Moreover, the temperature increments of the cooling water are characterized. It is shown that, by reducing the glass outflow velocity, the solidification is enhanced; meanwhile, an increase of the step angle also improves the solidification of the glass flow.

Glass–water interaction: Effect of high-valence cations on glass structure and chemical durability

Energy Technology Data Exchange (ETDEWEB)

Hopf, J.; Kerisit, Sebastien N.; Angeli, F.; Charpentier, Thibault M.; Icenhower, Jonathan P.; McGrail, Bernard P.; Windisch, Charles F.; Burton, Sarah D.; Pierce, Eric M.

2016-05-15

Borosilicate glass is a durable solid, but it dissolves when in contact with aqueous fluids. The dissolution mechanism, which involves a variety of sequential reactions that occur at the solid-fluid interface, has important implications for the corrosion resistance of industrial and nuclear waste glasses. In this study, spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high–valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na2O–Al2O3–B2O3–HfO2–SiO2 system (e.g., Na/[Al+B] = 1.0 and HfO2/SiO2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N4 (tetrahedral boron/total boron) and increases the amount of Si—O—Hf moieties in the glass. Results from flow–through experiments conducted under dilute and near–saturated conditions show a decrease of approximately 100× or more in the dissolution rate over the series from 0 to 20 mol% HfO2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveals a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the stronger binding of Si sites that deposit on the surface from the influent when Hf is present in the glass. As a result, the residence time at the glass surface of these newly-formed Si sites is longer in the presence of Hf, which increases the density of anchor sites from which altered layers

Carbon dioxide and ethanol release from champagne glasses, under standard tasting conditions.

Science.gov (United States)

Liger-Belair, Gérard; Beaumont, Fabien; Bourget, Marielle; Pron, Hervé; Parvitte, Bertrand; Zéninari, Virginie; Polidori, Guillaume; Cilindre, Clara

2012-01-01

A simple glass of champagne or sparkling wine may seem like the acme of frivolity to most people, but in fact, it may rather be considered as a fantastic playground for any fluid physicist or physicochemist. In this chapter, results obtained concerning various steps where the CO₂ molecule plays a role (from its ingestion in the liquid phase during the fermentation process to its progressive release in the headspace above the tasting glass) are gathered and synthesized to propose a self-consistent and global overview of how gaseous and dissolved CO₂ impact champagne and sparkling wine science. Some recent investigations, conducted through laser tomography techniques, on ascending bubbles and ascending-bubble-driven flow patterns found in champagne glasses are reported, which illustrate the fine interplay between ascending bubbles and the fluid around under standard tasting conditions. The simultaneous monitoring of gaseous CO₂ and ethanol in the headspace of both a flute and a coupe filled with champagne was reported, depending on whether or not the glass shows effervescence. Both gaseous CO₂ and ethanol were found to be enhanced by the presence of ascending bubbles, thus confirming the close link between ascending bubbles, ascending-bubble-driven flow patterns, and the release of gaseous CO₂ and volatile organic compounds. Copyright © 2012 Elsevier Inc. All rights reserved.

Using Peltier cells to study solid-liquid-vapour transitions and supercooling

International Nuclear Information System (INIS)

Torzo, Giacomo; Soletta, Isabella; Branca, Mario

2007-01-01

We propose an apparatus for teaching experimental thermodynamics in undergraduate introductory courses, using thermoelectric modules and a real-time data acquisition system. The device may be made at low cost, still providing an easy approach to the investigation of liquid-solid and liquid-vapour phase transitions and of metastable states (supercooling). The thermoelectric module (a technological evolution of the thermocouple) is by itself an interesting subject that offers a clear example of both thermo-electric (Seebeck effect) and electro-thermal (Peltier effect) energy transformation. We report here some cooling/heating measurements for several liquids and mixtures, including water, salt/water, ethanol/water and sodium acetate, showing how to evaluate the phenomena of freezing point depression and elevation, and how to evaluate the water latent heat

Vibrating-Wire, Supercooled Liquid Water Content Sensor Calibration and Characterization Progress

Science.gov (United States)

King, Michael C.; Bognar, John A.; Guest, Daniel; Bunt, Fred

2016-01-01

NASA conducted a winter 2015 field campaign using weather balloons at the NASA Glenn Research Center to generate a validation database for the NASA Icing Remote Sensing System. The weather balloons carried a specialized, disposable, vibrating-wire sensor to determine supercooled liquid water content aloft. Significant progress has been made to calibrate and characterize these sensors. Calibration testing of the vibrating-wire sensors was carried out in a specially developed, low-speed, icing wind tunnel, and the results were analyzed. The sensor ice accretion behavior was also documented and analyzed. Finally, post-campaign evaluation of the balloon soundings revealed a gradual drift in the sensor data with increasing altitude. This behavior was analyzed and a method to correct for the drift in the data was developed.

Study of magnetoresistance in the supercooled state of Dy-Y alloys

Science.gov (United States)

Jena, Rudra Prasad; Lakhani, Archana

2018-02-01

We report the magnetoresistance studies on Dy1-xYx (x ≤ 0.05) alloys across the first order helimagnetic to ferromagnetic phase transition. These alloys exhibit multiple magnetic phases on varying the temperature and magnetic field. The magnetoresistance studies in the hysteresis region shows irreversibility in forward and reverse field cycles. The resistivity values at zero field for these alloys after zero field cooling to the measurement temperatures, are different in both forward and reverse field cycles. The path dependence of magnetoresistance suggests the presence of helimagnetic phase as the supercooled metastable state which transforms to the stable ferromagnetic state on increasing the field. At high magnetic fields negative magnetoresistance following a linear dependence with field is observed which is attributed to the magnon scattering.

Heat Transfer Model of a Small-Scale Waste Glass Melter with Cold Cap Layer

Energy Technology Data Exchange (ETDEWEB)

Abboud, Alexander; Guillen, Donna Post; Pokorny, Richard

2016-09-01

At the Hanford site in the state of Washington, more than 56 million gallons of radioactive waste is stored in underground tanks. The cleanup plan for this waste is vitrification at the Waste Treatment Plant (WTP), currently under construction. At the WTP, the waste will be blended with glass-forming materials and heated to 1423K, then poured into stainless steel canisters to cool and solidify. A fundamental understanding of the glass batch melting process is needed to optimize the process to reduce cost and decrease the life cycle of the cleanup effort. The cold cap layer that floats on the surface of the glass melt is the primary reaction zone for the feed-to-glass conversion. The conversion reactions include water release, melting of salts, evolution of batch gases, dissolution of quartz and the formation of molten glass. Obtaining efficient heat transfer to this region is crucial to achieving high rates of glass conversion. Computational fluid dynamics (CFD) modeling is being used to understand the heat transfer dynamics of the system and provide insight to optimize the process. A CFD model was developed to simulate the DM1200, a pilot-scale melter that has been extensively tested by the Vitreous State Laboratory (VSL). Electrodes are built into the melter to provide Joule heating to the molten glass. To promote heat transfer from the molten glass into the reactive cold cap layer, bubbling of the molten glass is used to stimulate forced convection within the melt pool. A three-phase volume of fluid approach is utilized to model the system, wherein the molten glass and cold cap regions are modeled as separate liquid phases, and the bubbling gas and plenum regions are modeled as one lumped gas phase. The modeling of the entire system with a volume of fluid model allows for the prescription of physical properties on a per-phase basis. The molten glass phase and the gas phase physical properties are obtained from previous experimental work. Finding representative

Nature of the anomalies in the supercooled liquid state of the mW model of water

Science.gov (United States)

Holten, Vincent; Limmer, David T.; Molinero, Valeria; Anisimov, Mikhail A.

2013-05-01

The thermodynamic properties of the supercooled liquid state of the mW model of water show anomalous behavior. Like in real water, the heat capacity and compressibility sharply increase upon supercooling. One of the possible explanations of these anomalies, the existence of a second (liquid-liquid) critical point, is not supported by simulations for this model. In this work, we reproduce the anomalies of the mW model with two thermodynamic scenarios: one based on a non-ideal "mixture" with two different types of local order of the water molecules, and one based on weak crystallization theory. We show that both descriptions accurately reproduce the model's basic thermodynamic properties. However, the coupling constant required for the power laws implied by weak crystallization theory is too large relative to the regular backgrounds, contradicting assumptions of weak crystallization theory. Fluctuation corrections outside the scope of this work would be necessary to fit the forms predicted by weak crystallization theory. For the two-state approach, the direct computation of the low-density fraction of molecules in the mW model is in agreement with the prediction of the phenomenological equation of state. The non-ideality of the "mixture" of the two states never becomes strong enough to cause liquid-liquid phase separation, also in agreement with simulation results.

Nature of the anomalies in the supercooled liquid state of the mW model of water.

Science.gov (United States)

Holten, Vincent; Limmer, David T; Molinero, Valeria; Anisimov, Mikhail A

2013-05-07

The thermodynamic properties of the supercooled liquid state of the mW model of water show anomalous behavior. Like in real water, the heat capacity and compressibility sharply increase upon supercooling. One of the possible explanations of these anomalies, the existence of a second (liquid-liquid) critical point, is not supported by simulations for this model. In this work, we reproduce the anomalies of the mW model with two thermodynamic scenarios: one based on a non-ideal "mixture" with two different types of local order of the water molecules, and one based on weak crystallization theory. We show that both descriptions accurately reproduce the model's basic thermodynamic properties. However, the coupling constant required for the power laws implied by weak crystallization theory is too large relative to the regular backgrounds, contradicting assumptions of weak crystallization theory. Fluctuation corrections outside the scope of this work would be necessary to fit the forms predicted by weak crystallization theory. For the two-state approach, the direct computation of the low-density fraction of molecules in the mW model is in agreement with the prediction of the phenomenological equation of state. The non-ideality of the "mixture" of the two states never becomes strong enough to cause liquid-liquid phase separation, also in agreement with simulation results.

Fluid flow behaviour of gas-condensate and near-miscible fluids at the pore scale

Energy Technology Data Exchange (ETDEWEB)

Dawe, Richard A. [Department of Chemical Engineering, University of West Indies, St. Augustine (Trinidad and Tobago); Grattoni, Carlos A. [Department of Earth Science and Engineering, Imperial College, London, SW7 2BP (United Kingdom)

2007-02-15

Retrograde condensate reservoir behaviour is complex with much of the detailed mechanisms of the multiphase fluid transport and mass transfer between the phases within the porous matrix still speculative. Visual modelling of selected processes occurring at the pore level under known and controlled boundary conditions can give an insight to fluid displacements at the core scale and help the interpretation of production behaviour at reservoir scale. Visualisation of the pore scale two-phase flow mechanisms has been studied experimentally at low interfacial tensions, < 0.5 mN/m, using a partially miscible fluid system in glass visual micro models. As the interfacial tension decreases the balance between fluid-fluid forces (interfacial, spreading and viscous) and fluid-solid interactions (wettability and viscous interactions) changes. Data measurements in the laboratory, particularly relative permeability, will therefore always be difficult especially for condensate fluids just below their dew point. What is certain is that gas production from a gas-condensate leads to condensate dropout when pressure falls below the dew point, either within the wellbore or, more importantly, in the reservoir. This paper illustrates some pore scale physics, particularly interfacial phenomena at low interfacial tension, which has relevance to appreciating the flow of condensate fluids close to their dew point either near the wellbore (which affects well productivity) or deep inside the reservoir (which affects condensate recovery). (author)

Understanding the structural drivers governing glass-water interactions in borosilicate based model bioactive glasses.

Science.gov (United States)

Stone-Weiss, Nicholas; Pierce, Eric M; Youngman, Randall E; Gulbiten, Ozgur; Smith, Nicholas J; Du, Jincheng; Goel, Ashutosh

2018-01-01

borosilicate based model melt-quenched bioactive glass system has been studied to depict the impact of thermal history on its molecular structure and dissolution behavior in water. It has been shown that the methodology of quenching of the glass melt impacts the dissolution rate of the studied glasses by 1.5×-3× depending on the changes induced in their molecular structure due to variation in thermal history. Further, a recommendation has been made to study dissolution behavior of bioactive glasses using surface area of the sample - to - volume of solution (SA/V) approach instead of the currently followed mass of sample - to - volume of solution approach. The structural and chemical dissolution data obtained from bioactive glasses following the approach presented in this paper can be used to develop the structural descriptors and potential energy functions over a broad range of bioactive glass compositions. Realizing the goal of designing third generation bioactive glasses requires a thorough understanding of the complex sequence of reactions that control their rate of degradation (in physiological fluids) and the structural drivers that control them. In this article, we have highlighted some major experimental challenges and choices that need to be carefully navigated in order to unearth the mechanisms governing the chemical dissolution behavior of borosilicate based bioactive glasses. The proposed experimental approach allows us to gain a new level of conceptual understanding about the composition-structure-property relationships in these glass systems, which can be applied to attain a significant leap in designing borosilicate based bioactive glasses with controlled dissolution rates tailored for specific patient and disease states. Copyright © 2017 Acta Materialia Inc. All rights reserved.

Recycle Glass in Foam Glass Production

DEFF Research Database (Denmark)

Petersen, Rasmus Rosenlund; König, Jakob; Yue, Yuanzheng

The foam glass industry turn recycle glass into heat insulating building materials. The foaming process is relative insensitive to impurities in the recycle glass. It is therefore considered to play an important role in future glass recycling. We show and discuss trends of use of recycled glasses...... in foam glass industry and the supply sources and capacity of recycle glass....

Rotational dynamics in supercooled water from nuclear spin relaxation and molecular simulations.

Science.gov (United States)

Qvist, Johan; Mattea, Carlos; Sunde, Erik P; Halle, Bertil

2012-05-28

Structural dynamics in liquid water slow down dramatically in the supercooled regime. To shed further light on the origin of this super-Arrhenius temperature dependence, we report high-precision (17)O and (2)H NMR relaxation data for H(2)O and D(2)O, respectively, down to 37 K below the equilibrium freezing point. With the aid of molecular dynamics (MD) simulations, we provide a detailed analysis of the rotational motions probed by the NMR experiments. The NMR-derived rotational correlation time τ(R) is the integral of a time correlation function (TCF) that, after a subpicosecond librational decay, can be described as a sum of two exponentials. Using a coarse-graining algorithm to map the MD trajectory on a continuous-time random walk (CTRW) in angular space, we show that the slowest TCF component can be attributed to large-angle molecular jumps. The mean jump angle is ∼48° at all temperatures and the waiting time distribution is non-exponential, implying dynamical heterogeneity. We have previously used an analogous CTRW model to analyze quasielastic neutron scattering data from supercooled water. Although the translational and rotational waiting times are of similar magnitude, most translational jumps are not synchronized with a rotational jump of the same molecule. The rotational waiting time has a stronger temperature dependence than the translation one, consistent with the strong increase of the experimentally derived product τ(R) D(T) at low temperatures. The present CTRW jump model is related to, but differs in essential ways from the extended jump model proposed by Laage and co-workers. Our analysis traces the super-Arrhenius temperature dependence of τ(R) to the rotational waiting time. We present arguments against interpreting this temperature dependence in terms of mode-coupling theory or in terms of mixture models of water structure.

Ice-lens formation and geometrical supercooling in soils and other colloidal materials

KAUST Repository

Style, Robert W.

2011-10-14

We present a physically intuitive model of ice-lens formation and growth during the freezing of soils and other dense, particulate suspensions. Motivated by experimental evidence, we consider the growth of an ice-filled crack in a freezing soil. At low temperatures, ice in the crack exerts large pressures on the crack walls that will eventually cause the crack to split open. We show that the crack will then propagate across the soil to form a new lens. The process is controlled by two factors: the cohesion of the soil and the geometrical supercooling of the water in the soil, a new concept introduced to measure the energy available to form a new ice lens. When the supercooling exceeds a critical amount (proportional to the cohesive strength of the soil) a new ice lens forms. This condition for ice-lens formation and growth does not appeal to any ad hoc, empirical assumptions, and explains how periodic ice lenses can form with or without the presence of a frozen fringe. The proposed mechanism is in good agreement with experiments, in particular explaining ice-lens pattern formation and surges in heave rate associated with the growth of new lenses. Importantly for systems with no frozen fringe, ice-lens formation and frost heave can be predicted given only the unfrozen properties of the soil. We use our theory to estimate ice-lens growth temperatures obtaining quantitative agreement with the limited experimental data that are currently available. Finally we suggest experiments that might be performed in order to verify this theory in more detail. The theory is generalizable to complex natural-soil scenarios and should therefore be useful in the prediction of macroscopic frost-heave rates. © 2011 American Physical Society.

Theoretical flow investigations of an all glass evacuated tubular collector

DEFF Research Database (Denmark)

Shah, Louise Jivan; Furbo, Simon

2007-01-01

Heat transfer and flow structures inside all glass evacuated tubular collectors for different operating conditions are investigated by means of computational fluid dynamics. The investigations are based on a collector design with horizontal tubes connected to a vertical 14 manifold channel. Three...... the highest efficiency, the optimal inlet flow rate was around 0.4-1 kg/min, the flow structures in the glass tubes were relatively uninfluenced by the inlet flow rate, Generally, the results showed only small variations in the efficiencies. This indicates that the collector design is well working for most...

Laser bioengineering of glass-titanium implants surface

Science.gov (United States)

Lusquiños, F.; Arias-González, F.; Penide, J.; del Val, J.; Comesaña, R.; Quintero, F.; Riveiro, A.; Boutinguiza, M.; Pascual, M. J.; Durán, A.; Pou, J.

2013-11-01

Osseointegration is the mean challenge when surgical treatments fight against load-bearing bone diseases. Absolute bone replacement by a synthetic implant has to be completed not only from the mechanics point of view, but also from a biological approach. Suitable strength, resilience and stress distribution of titanium alloy implants are spoiled by the lack of optimal biological characteristics. The inert quality of extra low interstitial titanium alloy, which make it the most attractive metallic alloy for biomedical applications, oppose to an ideal surface with bone cell affinity, and capable to stimulate bone attachment bone growth. Diverse laser treatments have been proven as effective tools to modify surface properties, such as wettability in contact to physiological fluids, or osteoblast guided and slightly enhanced attachment. The laser surface cladding can go beyond by providing titanium alloy surfaces with osteoconduction and osteoinduction properties. In this research work, the laser radiation is used to produce bioactive glass coatings on Ti6Al4V alloy substrates. Specific silicate bioactive glass compositions has been investigated to achieve suitable surface tension and viscosity temperature behavior during processing, and to provide with the required release of bone growth gene up regulation agents in the course of resorption mediated by physiological fluids. The produced coatings and interfaces, the surface osteoconduction properties, and the chemical species release in simulated physiological fluid were characterized by scanning electron microscopy (SEM), hot stage microscopy (HSM), X-ray diffraction (XRD), X ray fluorescence (XRF), and Fourier transform infrared spectroscopy (FTIR).

EFFECTS OF INCORPORATING NATURAL MINERALS ON PRODUCTION AND BIOACTIVITY OF BIOACTIVE GLASS CERAMICS

Directory of Open Access Journals (Sweden)

Franco Matias Stabile

2016-07-01

Full Text Available Two glass-ceramics composition were produced from natural minerals. Quartzes and feldspars were pre-selected on the basis of their purities studied by X-ray diffraction (XRD and chemical analysis. Prepared compositions of glasses precursors were two different theoretical leucite (KAlSi₂O₆ /Bioglass 45S5 (L/Bg ratios. Transformations of raw materials mixtures and glass precursors were studied by differential thermal analyses. On the basis of thermal analysis results, glass ceramics were produced and characterized by XRD. Glass-ceramics were composed of two major crystalline phases, leucite and sodium calcium silicate. Bioactivity tests were performed submerging the glass-ceramics into simulated body fluid (SBF for different periods (1, 5 and 10 days. Bioactive behavior was monitored by XRD and scanning electron microscopy (SEM. Studied samples were found to be bioactive, in which hydroxyapatite layer was developed within 5 days of contact with SBF.

Hierarchical Structures and Shaped Particles of Bioactive Glass and Its In Vitro Bioactivity

Directory of Open Access Journals (Sweden)

U. Boonyang

2013-01-01

Full Text Available In this study, bioactive glass particles with controllable structure and porosity were prepared using dual-templating methods. Block copolymers used as one template component produced mesopores in the calcined samples. Polymer colloidal crystals as the other template component yielded either three-dimensionally ordered macroporous (3DOM products or shaped bioactive glass nanoparticles. The in vitro bioactivity of these bioactive glasses was studied by soaking the samples in simulated body fluid (SBF at body temperature (37°C for varying lengths of time and monitoring the formation of bone-like apatite on the surface of the bioactive glass. A considerable bioactivity was found that all of bioactive glass samples have the ability to induce the formation of an apatite layer on its surface when in contact with SBF. The development of bone-like apatite is faster for 3DOM bioactive glasses than for nanoparticles.

Asymptotic solutions of glass temperature profiles during steady optical fibre drawing

KAUST Repository

Taroni, M.; Breward, C. J. W.; Cummings, L. J.; Griffiths, I. M.

2013-01-01

In this paper we derive realistic simplified models for the high-speed drawing of glass optical fibres via the downdraw method that capture the fluid dynamics and heat transport in the fibre via conduction, convection and radiative heating. We

Role of the Short Distance Order in Glass Reactivity

Directory of Open Access Journals (Sweden)

María Vallet-Regi

2018-03-01

Full Text Available In 2005, our group described for the first time the structural characterization at the atomic scale of bioactive glasses and the influence of the glasses’ nanostructure in their reactivity in simulated body fluids. In that study, two bioactive sol-gel glasses with composition 80%SiO2–20%CaO and 80%SiO2–17%CaO–3%P2O5 (in mol-% were characterized by High-Resolution Transmission Electron Microscopy (HRTEM. Such characterization revealed unknown features of the glasses’ structure at the local scale that allowed the understanding of their different in vitro behaviors as a consequence of the presence or absence of P2O5. Since then, the nanostructure of numerous bioactive glasses, including melt-prepared, sol-gel derived, and mesoporous glasses, was investigated by HRTEM, Nuclear Magnetic Resonance (NMR spectroscopy, Molecular Dynamics (MD simulations, and other experimental techniques. These studies have shown that although glasses are amorphous solids, a certain type of short distance order, which greatly influences the in vitro and in vivo reactivity, is always present. This paper reviews the most significant advances in the understanding of bioactive glasses that took place in the last years as a result of the growing knowledge of the glasses’ nanostructure.

Role of the Short Distance Order in Glass Reactivity

Science.gov (United States)

2018-01-01

In 2005, our group described for the first time the structural characterization at the atomic scale of bioactive glasses and the influence of the glasses’ nanostructure in their reactivity in simulated body fluids. In that study, two bioactive sol-gel glasses with composition 80%SiO2–20%CaO and 80%SiO2–17%CaO–3%P2O5 (in mol-%) were characterized by High-Resolution Transmission Electron Microscopy (HRTEM). Such characterization revealed unknown features of the glasses’ structure at the local scale that allowed the understanding of their different in vitro behaviors as a consequence of the presence or absence of P2O5. Since then, the nanostructure of numerous bioactive glasses, including melt-prepared, sol-gel derived, and mesoporous glasses, was investigated by HRTEM, Nuclear Magnetic Resonance (NMR) spectroscopy, Molecular Dynamics (MD) simulations, and other experimental techniques. These studies have shown that although glasses are amorphous solids, a certain type of short distance order, which greatly influences the in vitro and in vivo reactivity, is always present. This paper reviews the most significant advances in the understanding of bioactive glasses that took place in the last years as a result of the growing knowledge of the glasses’ nanostructure. PMID:29534481

Novel resorbable glass-ceramic scaffolds for hard tissue engineering: from the parent phosphate glass to its bone-like macroporous derivatives.

Science.gov (United States)

Bretcanu, Oana; Baino, Francesco; Verné, Enrica; Vitale-Brovarone, Chiara

2014-05-01

One of the major challenges of hard tissue engineering research focuses on the development of scaffolds that can match the mechanical properties of the host bone and resorb at the same rate as the bone is repaired. The aim of this work was the synthesis and characterization of a resorbable phosphate glass, as well as its application for the fabrication of three dimensional (3-D) scaffolds for bone regeneration. The glass microstructure and behaviour upon heating were analysed by X-ray diffraction, differential scanning calorimetry and hot stage microscopy. The glass solubility was investigated according to relevant ISO standards using distilled water, simulated body fluid (SBF) and Tris-HCl as testing media. The glass underwent progressive dissolution over time in all three media but the formation of a hydroxyapatite-like layer was also observed on the samples soaked in SBF and Tris-HCl, which demonstrated the bioactivity of the material. The glass powder was used to fabricate 3-D macroporous bone-like glass-ceramic scaffolds by adopting polyethylene particles as pore formers: during thermal treatment, the polymer additive was removed and the sintering of glass particles was allowed. The obtained scaffolds exhibited high porosity (87 vol.%) and compressive strength around 1.5 MPa. After soaking for 4 months in SBF, the scaffolds mass loss was 76 wt.% and the pH of the solution did not exceed the 7.55 value, thereby remaining in a physiological range. The produced scaffolds, being resorbable, bioactive, architecturally similar to trabecular bone and exhibiting interesting mechanical properties, can be proposed as promising candidates for bone repair applications.

Computational Analysis of Effect of Transient Fluid Force on Composite Structures

Science.gov (United States)

2013-12-01

as they well represent an E-glass fiber reinforced composite frequently used in research and industrial applications. The fluid domain was sized...provide unique perspectives on peak stress ratios . The two models both share increased structural rigidity. The cylinder is reinforced by... Poisson ratio of 0.3 and Young’s modulus of 20 GPa were added to the transient structural engineering data cell (Figure 69). 78 Figure 69. E-Glass

Design of a day tank glass furnace using a transient model and steady-state computation fluid dynamics

International Nuclear Information System (INIS)

Díaz-Ibarra, Oscar; Abad, Pablo; Molina, Alejandro

2013-01-01

To design day tanks with energy efficiency and good operation standards, a detailed transient model that considers the melting, refining, cooling and working stages of the glass production process was developed. With the model, the required power input was determined, with glass coverage with batch (β) as parameter, for a furnace with a daily production of 1130 kg of soda-lime glass and 14 h for melting/refining. A detailed analysis of the energy balance with the model showed that during the daily cycle about 70% of the energy input is released with the flue gas. During the working stage most of the energy escapes through the doors. As the peak of energy consumption is during the refining process, the power requirement for this stage defines the global power requirement. Calculated energy efficiencies vary between 13% and 16% for β = 70% and 30% respectively. A steady state CFD simulation of the combustion chamber and glass tank shows that a side-fired burner configuration allows for lower gas velocities and temperatures close to the glass and the furnace walls while guaranteeing the same heat transfer characteristics to the glass than the more traditional end-fired (U-type) furnaces. -- Highlights: ► A transient model of a day tank glass furnace captures main process characteristics. ► Heat loss through doors during working stage impacts thermal efficiency. ► A side-fired burner configuration should be preferred to an end-fired approach

Surface Tension of Supercooled Water: Inflection Point-Free Course down to 250 K Confirmed Using a Horizontal Capillary Tube

Czech Academy of Sciences Publication Activity Database

Vinš, Václav; Hošek, Jan; Hykl, Jiří; Hrubý, Jan

2017-01-01

Roč. 62, č. 11 (2017), s. 3823-3832 ISSN 0021-9568 R&D Projects: GA ČR(CZ) GJ15-07129Y Institutional support: RVO:61388998 Keywords : horizontal technique * metastable liquid * supercooled Subject RIV: BJ - Thermodynamics OBOR OECD: Thermodynamics Impact factor: 2.323, year: 2016 http://pubs.acs.org/doi/pdf/10.1021/acs.jced.7b00519

In situ study at high pressure and temperature of the environment of water in hydrous Na and Ca aluminosilicate melts and coexisting aqueous fluids

Science.gov (United States)

Le Losq, Charles; Dalou, Célia; Mysen, Bjorn O.

2017-07-01

The bonding and speciation of water dissolved in Na silicate and Na and Ca aluminosilicate melts were inferred from in situ Raman spectroscopy of the samples, in hydrothermal diamond anvil cells, while at crustal temperature and pressure conditions. Raman data were also acquired on Na silicate and Na and Ca aluminosilicate glasses, quenched from hydrous melts equilibrated at high temperature and pressure in a piston cylinder apparatus. In the hydrous melts, temperature strongly influences O-H stretching ν(O-H) signals, reflecting its control on the bonding of protons between different molecular complexes. Pressure and melt composition effects are much smaller and difficult to discriminate with the present data. However, the chemical composition of the melt + fluid system influences the differences between the ν(O-H) signals from the melts and the fluids and, hence, between their hydrogen partition functions. Quenching modifies the O-H stretching signals: strong hydrogen bonds form in the glasses below the glass transition temperature Tg, and this phenomenon depends on glass composition. Therefore, glasses do not necessarily record the O-H stretching signal shape in melts near Tg. The melt hydrogen partition function thus cannot be assessed with certainty using O-H stretching vibration data from glasses. From the present results, the ratio of the hydrogen partition functions of hydrous silicate melts and aqueous fluids mostly depends on temperature and the bulk melt + fluid system chemical composition. This implies that the fractionation of hydrogen isotopes between magmas and aqueous fluids in water-saturated magmatic systems with differences in temperature and bulk chemical composition will be different.

Glass consistency and glass performance

International Nuclear Information System (INIS)

Plodinec, M.J.; Ramsey, W.G.

1994-01-01

Glass produced by the Defense Waste Processing Facility (DWPF) will have to consistently be more durable than a benchmark glass (evaluated using a short-term leach test), with high confidence. The DWPF has developed a Glass Product Control Program to comply with this specification. However, it is not clear what relevance product consistency has on long-term glass performance. In this report, the authors show that DWPF glass, produced in compliance with this specification, can be expected to effectively limit the release of soluble radionuclides to natural environments. However, the release of insoluble radionuclides to the environment will be limited by their solubility, and not glass durability

Means and Method for Measurement of Drilling Fluid Properties

Science.gov (United States)

Lysyannikov, A.; Kondrashov, P.; Pavlova, P.

2016-06-01

The paper addresses the problem on creation of a new design of the device for determining rheological parameters of drilling fluids and the basic requirements which it must meet. The key quantitative parameters that define the developed device are provided. The algorithm of determining the coefficient of the yield point from the rheological Shvedov- Bingam model at a relative speed of rotation of glasses from the investigated drilling fluid of 300 and 600 rpm is presented.

Effect of Mo-Fe substitution on glass forming ability, thermal stability, and hardness of Fe-C-B-Mo-Cr-W bulk amorphous alloys

Energy Technology Data Exchange (ETDEWEB)

Khalifa, Hesham E.; Cheney, Justin L. [University of California, San Diego Materials Science and Engineering Program, 9500 Gilman Drive, La Jolla, CA 92093-0411 (United States); Vecchio, Kenneth S. [University of California, San Diego Department of NanoEngineering, 9500 Gilman Drive, La Jolla, CA 92093-0411 (United States)], E-mail: kvecchio@ucsd.edu

2008-08-25

Amorphous Fe{sub 67-x}C{sub 10}B{sub 9}Mo{sub 7+x}Cr{sub 4}W{sub 3} (x = 1-7 at.%) plates with 640 {mu}m thickness were prepared by copper mold casting. The thermal properties and microstructural development during heat treatments were investigated by a combination of differential scanning calorimetry (DSC), differential thermal analysis, and X-ray diffractometry (XRD). The glass forming ability (GFA) and activation energy for crystallization have a distinct dependence on Mo content. Fe{sub 62}C{sub 10}B{sub 9}Mo{sub 12}Cr{sub 4}W{sub 3} is the best glass former in this study, demonstrating a supercooled liquid region, {delta}T{sub x} = 51 K, and an activation energy for crystallization, Q = 453 kJ/mol. The GFA of alloys in this system was governed by elastic strain optimization resulting directly from the variation in Mo content. Heat treatments were performed to demonstrate resistance to crystallization under typical processing conditions. Alloys in this system exhibited a three-phase evolution during crystallization. A second set of heat treatments was performed to identify each phase. Hardness data was collected at each of the heat treatment conditions, and a bulk metallic glasses (BMG)-derived composite containing a Mo-rich phase exhibited Vickers Hardness in excess of 2000. The fully amorphous alloys had an average hardness approaching 1500.

Removal of unwanted fluid

Science.gov (United States)

Subudhi, Sudhakar; Sreenivas, K. R.; Arakeri, Jaywant H.

2013-01-01

This work is concerned with the removal of unwanted fluid through the source-sink pair. The source consists of fluid issuing out of a nozzle in the form of a jet and the sink is a pipe that is kept some distance from the source pipe. Of concern is the percentage of source fluid sucked through the sink. The experiments have been carried in a large glass water tank. The source nozzle diameter is 6 mm and the sink pipe diameter is either 10 or 20 mm. The horizontal and vertical separations and angles between these source and sink pipes are adjustable. The flow was visualized using KMnO4 dye, planer laser induced fluorescence and particle streak photographs. To obtain the effectiveness (that is percentage of source fluid entering the sink pipe), titration method is used. The velocity profiles with and without the sink were obtained using particle image velocimetry. The sink flow rate to obtain a certain effectiveness increase dramatically with lateral separation. The sink diameter and the angle between source and the sink axes don't influence effectiveness as much as the lateral separation.

Design and Fabrication of Automatic Glass Cutting Machine

Science.gov (United States)

Veena, T. R.; Kadadevaramath, R. S.; Nagaraj, P. M.; Madhusudhan, S. V.

2016-09-01

This paper deals with the design and fabrication of the automatic glass or mirror cutting machine. In order to increase the accuracy of cut and production rate; and decrease the production time and accidents caused due to manual cutting of mirror or glass, this project aims at development of an automatic machine which uses a programmable logic controller (PLC) for controlling the movement of the conveyer and also to control the pneumatic circuit. In this machine, the work of the operator is to load and unload the mirror. The cutter used in this machine is carbide wheel with its cutting edge ground to a V-shaped profile. The PLC controls the pneumatic cylinder and intern actuates the cutter along the glass, a fracture layer is formed causing a mark to be formed below the fracture layer and a crack to be formed below the rib mark. The machine elements are designed using CATIA V5R20 and pneumatic circuit are designed using FESTO FLUID SIM software.

Bioactivity evolution of the surface functionalized bioactive glasses.

Science.gov (United States)

Magyari, Klára; Baia, Lucian; Vulpoi, Adriana; Simon, Simion; Popescu, Octavian; Simon, Viorica

2015-02-01

The formation of a calcium phosphate layer on the surface of the SiO2 -CaO-P2 O5 glasses after immersion in simulated body fluid (SBF) generally demonstrates the bioactivity of these materials. Grafting of the surface by chemical bonding can minimize the structural changes in protein adsorbed on the surface. Therefore, in this study our interest was to evaluate the bioactivity and blood biocompatibility of the SiO2 -CaO-P2 O5 glasses after their surface modification by functionalization with aminopropyl-triethoxysilane and/or by fibrinogen. It is shown that the fibrinogen adsorbed on the glass surfaces induces a growing of the apatite-like layer. It is also evidenced that the protein content from SBF influences the growth of the apatite-like layer. Furthermore, the good blood compatibility of the materials after fibrinogen and bovine serum albumin adsorption is proved from the assessment of the β-sheet-β-turn ratio. © 2014 Wiley Periodicals, Inc.

Calcium phosphate glass-ceramics for bioactive coating on a β-titanium alloy

International Nuclear Information System (INIS)

Kasuga, T.; Nogami, M.; Niinomi, M.

2003-01-01

The formation of a porous coating is the decisive feature for the bio-compatibility of silica-free calcium phosphate glass ceramics on alloy surfaces like the β-Ti structured Ti-29Nb-13Ta-4.6Zr used in this work. The ceramic composition is highly important: 50CaO-40P 2 O 5 -7Na 2 O-3TiO 2 glass powder produces a pore-free coating unable to bind hydroxyapatite, whereas 60CaO-30P 2 O 5 -7Na 2 O-3TiO 2 glass incorporates pores from which a crystalline hydroxyapatite phase can grow over the surface from simulated body fluid (see Figure). (Abstract Copyright [2003], Wiley Periodicals, Inc.)

Bioactivity and cytotoxicity of glass and glass-ceramics based on the 3CaO·P₂O₅--SiO₂--MgO system.

Science.gov (United States)

Daguano, Juliana K M F; Rogero, Sizue O; Crovace, Murilo C; Peitl, Oscar; Strecker, Kurt; Dos Santos, Claudinei

2013-09-01

The mechanical strength of bioactive glasses can be improved by controlled crystallization, turning its use as bulk bone implants viable. However, crystallization may affect the bioactivity of the material. The aim of this study was to develop glass-ceramics of the nominal composition (wt%) 52.75(3CaO·P₂O₅)-30SiO₂-17.25MgO, with different crystallized fractions and to evaluate their in vitro cytotoxicity and bioactivity. Specimens were heat-treated at 700, 775 and 975 °C, for 4 h. The major crystalline phase identified was whitlockite, an Mg-substituted tricalcium phosphate. The evaluation of the cytotoxicity was carried out by the neutral red uptake methodology. Ionic exchanges with the simulated body fluid SBF-K9 acellular solution during the in vitro bioactivity tests highlight the differences in terms of chemical reactivity between the glass and the glass-ceramics. The effect of crystallinity on the rates of hydroxycarbonate apatite (HCA) formation was followed by Fourier transformed infrared spectroscopy. Although all glass-ceramics can be considered bioactive, the glass-ceramic heat-treated at 775 °C (V775-4) presented the most interesting result, because the onset for HCA formation is at about 24 h and after 7 days the HCA layer dominates completely the spectrum. This occurs probably due to the presence of the whitlockite phase (3(Ca,Mg)O·P₂O₅). All samples were considered not cytotoxic.

PIXE characterization of tissues surrounding metallic prostheses coated with biological glasses

International Nuclear Information System (INIS)

Barbotteau, Y.; Irigaray, J.L.; Moretto, Ph.

2004-01-01

Biological glasses can be used as coatings for metallic prostheses in order to prevent corrosion. According to their composition, these glasses have different properties. We studied, in vivo, two glasses referred to as BVA and BVH. They are used as coatings of Ti6Al4V metallic implant. BVA glass disappears after 3 months of implantation and is replaced by bone. Prostheses initially coated by this glass have a larger osseous contact perimeter compared to the uncoated prostheses. This ensures a better anchoring of the implant and limits the micro-motions which cause wear debris. BVH glass keeps a constant composition during implantation and it is used like a layer which isolates metal implant from biological environment. In order to characterize the bony environment surrounding implants, we have used PIXE and RBS methods. This paper shows results of the behavior of bony tissue under micro-beam, the quality tests of new bone which replaces the BVA glass coating and the evaluation of corrosion effects. Titanium release in bony tissues begins when the metal surface of the prosthesis is exposed to biological fluids. After a few months of implantation, the titanium contamination is stabilized and remains localized within the first tens of micrometers of surrounding bone

In vitro study of manganese-doped bioactive glasses for bone regeneration

International Nuclear Information System (INIS)

Miola, Marta; Brovarone, Chiara Vitale; Maina, Giovanni; Rossi, Federica; Bergandi, Loredana; Ghigo, Dario; Saracino, Silvia; Maggiora, Marina; Canuto, Rosa Angela; Muzio, Giuliana; Vernè, Enrica

2014-01-01

A glass belonging to the system SiO 2 –P 2 O 5 –CaO–MgO–Na 2 O–K 2 O was modified by introducing two different amounts of manganese oxide (MnO). Mn-doped glasses were prepared by melt and quenching technique and characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) observation and energy dispersion spectrometry (EDS) analysis. In vitro bioactivity test in simulated body fluid (SBF) showed a slight decrease in the reactivity kinetics of Mn-doped glasses compared to the glass used as control; however the glasses maintained a good degree of bioactivity. Mn-leaching test in SBF and minimum essential medium (MEM) revealed fluctuating trends probably due to a re-precipitation of Mn compounds during the bioactivity process. Cellular tests showed that all the Mn-doped glasses, up to a concentration of 50 μg/cm 2 (μg of glass powders/cm 2 of cell monolayer), did not produce cytotoxic effects on human MG-63 osteoblasts cultured for up to 5 days. Finally, biocompatibility tests demonstrated a good osteoblast proliferation and spreading on Mn-doped glasses and most of all that the Mn-doping can promote the expression of alkaline phosphatase (ALP) and some bone morphogenetic proteins (BMPs). - Highlights: • Novel bioactive glasses doped with manganese were prepared. • Mn-doped bioactive glasses were not cytotoxic towards human MG-63 osteoblasts. • The Mn introduction promotes the expression of ALP and bone morphogenetic proteins. • Mn-doped glass may be a promising material for bone regeneration procedures

Electrophoretic deposition of mesoporous bioactive glass on glass-ceramic foam scaffolds for bone tissue engineering.

Science.gov (United States)

Fiorilli, Sonia; Baino, Francesco; Cauda, Valentina; Crepaldi, Marco; Vitale-Brovarone, Chiara; Demarchi, Danilo; Onida, Barbara

2015-01-01

In this work, the coating of 3-D foam-like glass-ceramic scaffolds with a bioactive mesoporous glass (MBG) was investigated. The starting scaffolds, based on a non-commercial silicate glass, were fabricated by the polymer sponge replica technique followed by sintering; then, electrophoretic deposition (EPD) was applied to deposit a MBG layer on the scaffold struts. EPD was also compared with other techniques (dipping and direct in situ gelation) and it was shown to lead to the most promising results. The scaffold pore structure was maintained after the MBG coating by EPD, as assessed by SEM and micro-CT. In vitro bioactivity of the scaffolds was assessed by immersion in simulated body fluid and subsequent evaluation of hydroxyapatite (HA) formation. The deposition of a MBG coating can be a smart strategy to impart bioactive properties to the scaffold, allowing the formation of nano-structured HA agglomerates within 48 h from immersion, which does not occur on uncoated scaffold surfaces. The mechanical properties of the scaffold do not vary after the EPD (compressive strength ~19 MPa, fracture energy ~1.2 × 10(6) J m(-3)) and suggest the suitability of the prepared highly bioactive constructs as bone tissue engineering implants for load-bearing applications.

Effects of radionuclide decay on waste glass behavior: A critical review

International Nuclear Information System (INIS)

Wronkiewicz, D.J.

1993-12-01

This paper is an extension of a chapter in an earlier report [1] that provides an updated review on the status of radiation damage problems in nuclear waste glasses. This report will focus on radiation effects on vitrified borosilicate nuclear waste glasses under conditions expected in the proposed Yucca mountain repository. Radiation effects on high-level waste glasses and their surrounding repository environment are important considerations for radionuclide immobilization because of the potential to alter the glass stability and thereby influence the radionuclide retentive properties of this waste form. The influence of radionuclide decay on vitrified nuclear waste may be manifested by several changes, including volume, stored energy, structure, microstructure, mechanical properties, and phase separation. Radiation may also affect the composition of aqueous fluids and atmospheric gases in relatively close proximity to the waste form. What is important to the radionuclide retentive properties of the repository is how these radiation effects collectively or individually influence the durability and radionuclide release from the glass in the event of liquid water contact

In vitro study of manganese-doped bioactive glasses for bone regeneration.

Science.gov (United States)

Miola, Marta; Brovarone, Chiara Vitale; Maina, Giovanni; Rossi, Federica; Bergandi, Loredana; Ghigo, Dario; Saracino, Silvia; Maggiora, Marina; Canuto, Rosa Angela; Muzio, Giuliana; Vernè, Enrica

2014-05-01

A glass belonging to the system SiO2-P2O5-CaO-MgO-Na2O-K2O was modified by introducing two different amounts of manganese oxide (MnO). Mn-doped glasses were prepared by melt and quenching technique and characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) observation and energy dispersion spectrometry (EDS) analysis. In vitro bioactivity test in simulated body fluid (SBF) showed a slight decrease in the reactivity kinetics of Mn-doped glasses compared to the glass used as control; however the glasses maintained a good degree of bioactivity. Mn-leaching test in SBF and minimum essential medium (MEM) revealed fluctuating trends probably due to a re-precipitation of Mn compounds during the bioactivity process. Cellular tests showed that all the Mn-doped glasses, up to a concentration of 50 μg/cm(2) (μg of glass powders/cm(2) of cell monolayer), did not produce cytotoxic effects on human MG-63 osteoblasts cultured for up to 5 days. Finally, biocompatibility tests demonstrated a good osteoblast proliferation and spreading on Mn-doped glasses and most of all that the Mn-doping can promote the expression of alkaline phosphatase (ALP) and some bone morphogenetic proteins (BMPs). Copyright © 2014 Elsevier B.V. All rights reserved.

Ice barriers promote supercooling and prevent frost injury in reproductive buds, flowers and fruits of alpine dwarf shrubs throughout the summer.

Science.gov (United States)

Kuprian, Edith; Briceño, Verónica F; Wagner, Johanna; Neuner, Gilbert

2014-10-01

Over-wintering reproductive buds of many woody plants survive frost by supercooling. The bud tissues are isolated from acropetally advancing ice by the presence of ice barriers that restrict ice growth. Plants living in alpine environments also face the risk of ice formation in summer months. Little knowledge exists, how reproductive structures of woody alpine plants are protected from frost injury during episodic summer frosts. In order to address this question, frost resistance of three common dwarf shrubs, Calluna vulgaris , Empetrum hermaphroditum and Loiseleuria procumbens was measured and ice formation and propagation were monitored in twigs bearing reproductive shoots during various stages of reproductive development (bud, anthesis, and fruit) throughout the alpine summer. Results indicated that, in the investigated species, ice barriers were present at all reproductive stages, isolating the reproductive shoots from ice advancing from the subtending vegetative shoot. Additionally, in the reproductive stems ice nucleating agents that are active at warm, sub-zero temperatures, were absent. The ice barriers were 100% effective, with the exception of L. procumbens , where in 13% of the total observations, the ice barrier failed. The ice barriers were localized at the base of the pedicel, at the anatomical junction of the vegetative and reproductive shoot. There, structural aspects of the tissue impede or prevent ice from advancing from the frozen stem into the pedicel of the reproductive shoot. Under the experimental conditions used in this study, ice nucleation initially occurred in the stem of the vegetative shoot at species-specific mean temperatures in the range of -4.7 to -5.8 °C. Reproductive shoots, however, remained supercooled and ice free down to a range of -7.2 to -18.2 °C or even below -22 °C, the lowest temperature applied in the study. This level of supercooling is sufficient to prevent freezing of reproductive structures at the lowest air

Micro-ion beam analysis of physico-chemical reactions in vitro induced by nano-structured sol-gel derived bioactive glasses

International Nuclear Information System (INIS)

Lao, J.

2007-07-01

The study of bioactive glasses is a multi-field area of research aiming at a major goal: the development of new generation biomaterials that would be able to bond with host tissues through the formation of a strong interfacial bond, together with helping the body heal itself through the stimulation of specific cellular responses. Thus clinical applications of bioactive glasses mainly concern dental surgery and orthopedics, for filling osseous defects. For this purpose, we have elaborated bioactive glasses in the binary SiO 2 -CaO system, ternary SiO 2 -CaO-P 2 O 5 system, and for the first time, to our knowledge, strontium-doped SiO 2 -CaO-SrO and SiO 2 -CaO-P 2 O 5 -SrO glasses. The materials were elaborated using the sol-gel process, which allowed the synthesis of nano-porous materials with great purity and homogeneity. The bio-activity of the glasses was clearly demonstrated in vitro: in contact with biological fluids, the whole lot of mate-rials were able to induce the formation of a Ca-P-Mg layer a few microns thick at their surface. Our work is characterized by the use of PIXE-RBS nuclear microprobes to study the bioactive glass/biological fluids interface. Thanks to these methods we obtained chemical maps that made possible the analysis of major and trace elements concentrations at the interface. Moreover, quantitative information regarding the local reactivity of glasses were acquired. These data are important to evaluate the kinetics and amplitude of the physico-chemical reactions involved in the bio-activity process. Thus, we highlighted that the binary glass is the highest reactive regarding the dissolution of the glassy matrix as well as the first appearance of the Ca-P rich layer. However the Ca/P atomic ratio calculated at the glass/biological fluids interface decreases slowly, indicating that the Ca-P-Mg layer encounters difficulties to be changed into a more stable apatitic phase. For the P-containing glasses, the de-alkalinization of the matrix and

Memory phenomenon in a lanthanum based bulk metallic glass

Energy Technology Data Exchange (ETDEWEB)

Zhou, Ye [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Huang, Wei Min, E-mail: mwmhuang@ntu.edu.sg [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Zhao, Yong [School of Chemistry and Chemical Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013 (China); Ding, Zhen [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Li, Yan [School of Materials Science and Engineering, Beihang University, Beijing 100191 (China); Tor, Shu Beng; Liu, Erjia [School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore)

2016-07-05

In this paper, we experimentally investigate two memory phenomena in a lanthanum based bulk metallic glass (BMG). While the temperature memory effect (TME) is not found by differential scanning calorimeter (DSC) test, shape recovery is observed in samples indented at both low and high temperatures. In terms of shape memory related characteristics, this BMG shares some features of shape memory alloys (SMAs) due to its metal nature, and some other features of shape memory polymers (SMPs) owing to its glassy–rubbery transition. The formation of protrusion in the polished sample after heating to super-cooled liquid region (SCLR) indicates that surface tension is not a necessarily positive contributor for shape recovery. Release of internal elastic stress is concluded as the major player. Although the amorphous nature of BMGs enables for storing appreciable amount of internal elastic stress upon deformation, without the presence of cross-linker as in typical SMPs, the shape recovery in BMGs is rather limited. - Highlights: • Experimental investigation of shape recovery in BMG. • Surface tension is not the major reason for shape recovery in BMG. • Release of internal stress is the major contributor for shape recovery. • Comparison of shape memory features of BMG with other shape memory materials.

Memory phenomenon in a lanthanum based bulk metallic glass

International Nuclear Information System (INIS)

Zhou, Ye; Huang, Wei Min; Zhao, Yong; Ding, Zhen; Li, Yan; Tor, Shu Beng; Liu, Erjia

2016-01-01

In this paper, we experimentally investigate two memory phenomena in a lanthanum based bulk metallic glass (BMG). While the temperature memory effect (TME) is not found by differential scanning calorimeter (DSC) test, shape recovery is observed in samples indented at both low and high temperatures. In terms of shape memory related characteristics, this BMG shares some features of shape memory alloys (SMAs) due to its metal nature, and some other features of shape memory polymers (SMPs) owing to its glassy–rubbery transition. The formation of protrusion in the polished sample after heating to super-cooled liquid region (SCLR) indicates that surface tension is not a necessarily positive contributor for shape recovery. Release of internal elastic stress is concluded as the major player. Although the amorphous nature of BMGs enables for storing appreciable amount of internal elastic stress upon deformation, without the presence of cross-linker as in typical SMPs, the shape recovery in BMGs is rather limited. - Highlights: • Experimental investigation of shape recovery in BMG. • Surface tension is not the major reason for shape recovery in BMG. • Release of internal stress is the major contributor for shape recovery. • Comparison of shape memory features of BMG with other shape memory materials.

Tailoring properties of porous Poly (vinylidene fluoride) scaffold through nano-sized 58s bioactive glass.

Science.gov (United States)

Shuai, Cijun; Huang, Wei; Feng, Pei; Gao, Chengde; Shuai, Xiong; Xiao, Tao; Deng, Youwen; Peng, Shuping; Wu, Ping

2016-01-01

The biological properties of porous poly (vinylidene fluoride) (PVDF) scaffolds fabricated by selective laser sintering were tailored through nano-sized 58s bioactive glass. The results showed that 58s bioactive glass distributed evenly in the PVDF matrix. There were some exposed particles on the surface which provided attachment sites for biological response. It was confirmed that the scaffolds had highly bioactivity by the formation of bone-like apatite in simulated body fluid. And the bone-like apatite became dense with the increase in 58s bioactive glass and culture time. Moreover, the scaffolds were suitable for cell adhesion and proliferation compared with the PVDF scaffolds without 58s bioactive glass. The research showed that the PVDF/58s bioactive glass scaffolds had latent application in bone tissue engineering.

Thermal conductivity enhancement of sodium acetate trihydrate by adding graphite powder and the effect on stability of supercooling

DEFF Research Database (Denmark)

Johansen, Jakob Berg; Dannemand, Mark; Kong, Weiqiang

2015-01-01

. The graphite powder was stabilized using carboxymetyl cellulose and successfully tested in heating and supercooling cycles with no loss of performance. Thermal conductivity enhancing properties of graphite powder was shown in samples. Since the experiments were conducted in small scale, at 200 g per sample......, large scale experiments are required to validate graphite as a thermo conductivity enhancing agent, suitable for use in seasonal heat storage applications utilizing SAT....

Size and pressure effects on glass transition temperature of poly (methyl methacrylate) thin films

International Nuclear Information System (INIS)

Lang, X.Y.; Zhang, G.H.; Lian, J.S.; Jiang, Q.

2006-01-01

A simple and unified model, without any adjustable parameter, is developed for size and pressure effects on glass transition temperatures of nanopolymers. The model is based on a model for size dependent glass transition temperature of nanopolymer glasses under ambient pressure, and a pressure-dependent function of the root of mean-square displacement of atom vibration. It is found that the size- and pressure-dependent glass transition temperatures of free-standing films or supported films having weak interaction with substrates decreases with decreasing of pressure and size. However, the glass transition temperature of supported films having strong interaction with substrates increases with the increase of pressure and the decrease of size. The predicted results correspond with available experimental evidences for atactic-Poly (methyl methacrylate) thin films under hydrostatic pressure or under the pressure induced by supercritical fluid CO 2 . In addition, the predicted glass transition temperature of isotactic-Poly (methyl methacrylate) thin films under ambient pressure is consistent with available experimental evidences

Modeling surface area to volume effects on borosilicate glass dissolution

International Nuclear Information System (INIS)

Bourcier, W.L.; Ebert, W.L.; Feng, X.

1992-11-01

We simulated the reaction of SRL-131 glass with equilibrated J-13 water in order to investigate the effects of surface area to volume ratio (SA/V) on glass dissolution. We show that glass-fluid ion exchange causes solution pH to rise to progressively higher values as SA/V increases. Because the ion exchange is rapid relative to the duration of the glass dissolution experiment, the pH effect does not scale with (SA/V)*time. Experiments compared at the same (SA/V)*time value therefore have different pHs, with higher pHs at higher SA/V ratios. Both experimental data and our simulation results show similar trends of increasing reaction rate as a function of SA/V ratio when scaled to (SA/V)*time. Glasses which react in systems of differing SA/V ratio therefore follow different reaction paths and high SA/V ratios cannot be used to generate data which accurately scales to long time periods unless the ion exchange effect is taken into account. We suggest some simple test designs which enable more reliable high. SA/V accelerated tests

Silver-containing mesoporous bioactive glass with improved antibacterial properties.

Science.gov (United States)

Gargiulo, Nicola; Cusano, Angela Maria; Causa, Filippo; Caputo, Domenico; Netti, Paolo Antonio

2013-09-01

The aim of the present work is the study of the bacteriostatic/bactericidal effect of a silver-containing mesoporous bioactive glass obtained by evaporation-induced self-assembly and successive thermal stabilization. Samples of the manufactured mesophase were characterized by means of transmission electron microscopy and N₂ adsorption/desorption at 77 K, revealing structural and textural properties similar to SBA-15 mesoporous silica. Glass samples used for bioactivity experiments were put in contact with a standardized, commercially available cell culture medium instead of lab-produced simulated body fluid, and were then characterized by means of X-ray diffraction, field emission scanning electron microscopy and Fourier transform infrared spectroscopy. All these analyses confirmed the development of a hydroxyl carbonate apatite layer on glass particles. Moreover, the investigated mesostructure showed a very good antibacterial effect against S. aureus strain, with a strong evidence of bactericidal activity already registered at 0.5 mg/mL of glass concentration. A hypothesis about the mechanism by which Ag affects the bacterial viability, based on the intermediate formation of crystalline AgCl, was also taken into account. With respect to what already reported in the literature, these findings claim a deeper insight into the possible use of silver-containing bioactive glasses as multifunctional ceramic coatings for orthopedic devices.

The Effect of Ag Addition on the Enhancement of the Thermal and Mechanical Properties of CuZrAl Bulk Metallic Glasses

Directory of Open Access Journals (Sweden)

Tsan-Man Chung

2016-09-01

Full Text Available In this study, the thermal and mechanical properties of Cu50−xZr43Al7Agx (x = 0, 3, 4, 5, 6 bulk metallic glasses (BMGs are investigated by using an X-ray diffractometer (XRD, a differential scanning calorimeter (DSC, differential thermal analysis (DTA, a Vickers hardness tester, a material test system (MTS, scanning electron microscopy (SEM, and transmission electron microscopy (TEM. Cu50−xZr43Al7Agx (x = 0, 3, 4, 5, 6 BMGs were made by arc-melting and an injection casting process. The results revealed that the glass transition temperature (Tg and the crystallization temperature (Tx of CuZrAl alloy decreased with the Ag addition. Hence, the supercooled liquid region and γ of Cu45Zr43Al7Ag5 alloy increased to 76 K and 0.42, respectively. The thermal stability and glass forming ability of CuZrAlAg BMG alloys were enhanced by the microalloyed Ag content. The room temperature compressive fracture strength and strain measured of Cu47Zr43Al7Ag3 were about 2200 MPa and 2.1%, respectively. The distribution of vein patterns and the formation of nanocrystalline phases on the fracture surface of Cu47Zr43Al7Ag3 alloy can be observed by SEM and TEM to be significant, indicating a typical ductile fracture behavior and an improved plasticity of alloys with the addition of microalloyed Ag from 0 to 6 atom %.

Investigation of bioactivity and cell effects of nano-porous sol–gel derived bioactive glass film

Energy Technology Data Exchange (ETDEWEB)

Ma, Zhijun, E-mail: mokuu@zju.edu.cn [State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640 (China); Ji, Huijiao [College of Life Science, Zhejiang University, Hangzhou, 310028 (China); Hu, Xiaomeng [School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510640 (China); Teng, Yu [State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640 (China); Zhao, Guiyun; Mo, Lijuan; Zhao, Xiaoli [College of Life Science, Zhejiang University, Hangzhou, 310028 (China); Chen, Weibo [School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510640 (China); Qiu, Jianrong, E-mail: qjr@scut.edu.cn [State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou, 510640 (China); Zhang, Ming, E-mail: zhangming201201@126.com [College of Life Science, Zhejiang University, Hangzhou, 310028 (China)

2013-11-01

In orthopedic surgery, bioactive glass film coating is extensively studied to improve the synthetic performance of orthopedic implants. A lot of investigations have confirmed that nano-porous structure in bioactive glasses can remarkably improve their bioactivity. Nevertheless, researches on preparation of nano-porous bioactive glasses in the form of film coating and their cell response activities are scarce. Herein, we report the preparation of nano-porous bioactive glass film on commercial glass slide based on a sol–gel technique, together with the evaluation of its in vitro bioactivity through immersion in simulated body fluid and monitoring the precipitation of apatite-like layer. Cell responses of the samples, including attachment, proliferation and osteogenic differentiation, were also investigated using BMSCS (bone marrow derived mesenchymal stem cells) as a model. The results presented here provide some basic information on structural influence of bioactive glass film on the improvement of bioactivity and cellular effects.

Investigation of bioactivity and cell effects of nano-porous sol-gel derived bioactive glass film

Science.gov (United States)

Ma, Zhijun; Ji, Huijiao; Hu, Xiaomeng; Teng, Yu; Zhao, Guiyun; Mo, Lijuan; Zhao, Xiaoli; Chen, Weibo; Qiu, Jianrong; Zhang, Ming

2013-11-01

In orthopedic surgery, bioactive glass film coating is extensively studied to improve the synthetic performance of orthopedic implants. A lot of investigations have confirmed that nano-porous structure in bioactive glasses can remarkably improve their bioactivity. Nevertheless, researches on preparation of nano-porous bioactive glasses in the form of film coating and their cell response activities are scarce. Herein, we report the preparation of nano-porous bioactive glass film on commercial glass slide based on a sol-gel technique, together with the evaluation of its in vitro bioactivity through immersion in simulated body fluid and monitoring the precipitation of apatite-like layer. Cell responses of the samples, including attachment, proliferation and osteogenic differentiation, were also investigated using BMSCS (bone marrow derived mesenchymal stem cells) as a model. The results presented here provide some basic information on structural influence of bioactive glass film on the improvement of bioactivity and cellular effects.

Experimental investigations on heat content of supercooled sodium acetate trihydrate by a simple heat loss method

DEFF Research Database (Denmark)

Kong, Weiqiang; Dannemand, Mark; Johansen, Jakob Berg

2016-01-01

Sodium acetate trihydrate is a phase change material that can be used for long term heat storage in solar heating systems because of its relatively high heat of fusion, a melting temperature of 58 °C and its ability to supercool stable. In practical applications sodium acetate trihydrate tend to ......, 0.3–0.5 % (wt.%) Xanthan Gum or 1–2% (wt.%) of some solid or liquid polymers as additives had significantly higher heat contents compared to samples of sodium acetate trihydrate suffering from phase separation....

Elaboration, caractérisation structurale et mise en forme d'alliages de magnésium vitreux

OpenAIRE

Puech , Sylvain

2008-01-01

The amorphous structure of metallic glasses results in high mechanical properties at room temperature, high hardness and strength, large elastic deformation domain, but also interesting forming capacity in their supercooled liquid region. Because of their out of equilibrium state, a crystallisation can develop during a heat treatment and lead to the formation of a glass/crystallites composite, for which properties are changed. We investigate in this thesis the Mg based bulk metallic glasses f...

Aging of a hard-sphere glass: effect of the microscopic dynamics

International Nuclear Information System (INIS)

Puertas, Antonio M

2010-01-01

We present simulations of the aging of a quasi-hard-sphere glass, with Newtonian and Brownian microscopic dynamics. The system is equilibrated at the desired density (above the glass transition in hard spheres) with short-range attractions, which are removed at t = 0. The structural part of the decay of the density correlation function can be time rescaled to collapse onto a master function independent of the waiting time, t w , and the timescale follows a power law with t w , with exponent z ∼ 0.89; the non-ergodicity parameter is larger than that of the glass transition point (the localization length is smaller) and oscillates in harmony with S q . The aging with both microscopic dynamics is identical, except for a scale factor from the age in Newtonian to the age in Brownian dynamics. This factor is approximately the same as that which scales the α-decay of the correlation function in fluids close to the glass transition.

DWPF GLASS BEADS AND GLASS FRIT TRANSPORT DEMONSTRATION

Energy Technology Data Exchange (ETDEWEB)

Adamson, D; Bradley Pickenheim, B

2008-11-24

DWPF is considering replacing irregularly shaped glass frit with spherical glass beads in the Slurry Mix Evaporator (SME) process to decrease the yield stress of the melter feed (a non-Newtonian Bingham Plastic). Pilot-scale testing was conducted on spherical glass beads and glass frit to determine how well the glass beads would transfer when compared to the glass frit. Process Engineering Development designed and constructed the test apparatus to aid in the understanding and impacts that spherical glass beads may have on the existing DWPF Frit Transfer System. Testing was conducted to determine if the lines would plug with the glass beads and the glass frit slurry and what is required to unplug the lines. The flow loop consisted of vertical and horizontal runs of clear PVC piping, similar in geometry to the existing system. Two different batches of glass slurry were tested: a batch of 50 wt% spherical glass beads and a batch of 50 wt% glass frit in process water. No chemicals such as formic acid was used in slurry, only water and glass formers. The glass beads used for this testing were commercially available borosilicate glass of mesh size -100+200. The glass frit was Frit 418 obtained from DWPF and is nominally -45+200 mesh. The spherical glass beads did not have a negative impact on the frit transfer system. The transferring of the spherical glass beads was much easier than the glass frit. It was difficult to create a plug with glass bead slurry in the pilot transfer system. When a small plug occurred from setting overnight with the spherical glass beads, the plug was easy to displace using only the pump. In the case of creating a man made plug in a vertical line, by filling the line with spherical glass beads and allowing the slurry to settle for days, the plug was easy to remove by using flush water. The glass frit proved to be much more difficult to transfer when compared to the spherical glass beads. The glass frit impacted the transfer system to the point

DWPF GLASS BEADS AND GLASS FRIT TRANSPORT DEMONSTRATION

International Nuclear Information System (INIS)

Adamson, D.; Pickenheim, Bradley

2008-01-01

DWPF is considering replacing irregularly shaped glass frit with spherical glass beads in the Slurry Mix Evaporator (SME) process to decrease the yield stress of the melter feed (a non-Newtonian Bingham Plastic). Pilot-scale testing was conducted on spherical glass beads and glass frit to determine how well the glass beads would transfer when compared to the glass frit. Process Engineering Development designed and constructed the test apparatus to aid in the understanding and impacts that spherical glass beads may have on the existing DWPF Frit Transfer System. Testing was conducted to determine if the lines would plug with the glass beads and the glass frit slurry and what is required to unplug the lines. The flow loop consisted of vertical and horizontal runs of clear PVC piping, similar in geometry to the existing system. Two different batches of glass slurry were tested: a batch of 50 wt% spherical glass beads and a batch of 50 wt% glass frit in process water. No chemicals such as formic acid was used in slurry, only water and glass formers. The glass beads used for this testing were commercially available borosilicate glass of mesh size -100+200. The glass frit was Frit 418 obtained from DWPF and is nominally -45+200 mesh. The spherical glass beads did not have a negative impact on the frit transfer system. The transferring of the spherical glass beads was much easier than the glass frit. It was difficult to create a plug with glass bead slurry in the pilot transfer system. When a small plug occurred from setting overnight with the spherical glass beads, the plug was easy to displace using only the pump. In the case of creating a man made plug in a vertical line, by filling the line with spherical glass beads and allowing the slurry to settle for days, the plug was easy to remove by using flush water. The glass frit proved to be much more difficult to transfer when compared to the spherical glass beads. The glass frit impacted the transfer system to the point

Effect of different glasses in glass bonded zeolite

International Nuclear Information System (INIS)

Lewis, M.A.; Ackerman, J.P.; Verma, S.

1995-01-01

A mineral waste form has been developed for chloride waste salt generated during the pyrochemical treatment of spent nuclear fuel. The waste form consists of salt-occluded zeolite powders bound within a glass matrix. The zeolite contains the salt and immobilizes the fission products. The zeolite powders are hot pressed to form a mechanically stable, durable glass bonded zeolite. Further development of glass bonded zeolite as a waste form requires an understanding of the interaction between the glass and the zeolite. Properties of the glass that enhance binding and durability of the glass bonded zeolite need to be identified. Three types of glass, boroaluminosilicate, soda-lime silicate, and high silica glasses, have a range of properties and are now being investigated. Each glass was hot pressed by itself and with an equal amount of zeolite. MCC-1 leach tests were run on both. Soda-lime silicate and high silica glasses did not give a durable glass bonded zeolite. Boroaluminosilicate glasses rich in alkaline earths did bind the zeolite and gave a durable glass bonded zeolite. Scanning electron micrographs suggest that the boroaluminosilicate glasses wetted the zeolite powders better than the other glasses. Development of the glass bonded zeolite as a waste form for chloride waste salt is continuing

Phosphate-based glass fiber vs. bulk glass: Change in fiber optical response to probe in vitro glass reactivity.

Science.gov (United States)

Massera, J; Ahmed, I; Petit, L; Aallos, V; Hupa, L

2014-04-01

This paper investigates the effect of fiber drawing on the thermal and structural properties as well as on the glass reactivity of a phosphate glass in tris(hydroxymethyl)aminomethane-buffered (TRIS) solution and simulated body fluid (SBF). The changes induced in the thermal properties suggest that the fiber drawing process leads to a weakening and probable re-orientation of the POP bonds. Whereas the fiber drawing did not significantly impact the release of P and Ca, an increase in the release of Na into the solution was noticed. This was probably due to small structural reorientations occurring during the fiber drawing process and to a slight diffusion of Na to the fiber surface. Both the powders from the bulk and the glass fibers formed a Ca-P surface layer when immersed in SBF and TRIS. The layer thickness was higher in the calcium and phosphate supersaturated SBF than in TRIS. This paper for the first time presents the in vitro reactivity and optical response of a phosphate-based bioactive glass (PBG) fiber when immersed in SBF. The light intensity remained constant for the first 48h after which a decrease with three distinct slopes was observed: the first decrease between 48 and 200h of immersion could be correlated to the formation of the Ca-P layer at the fiber surface. After this a faster decrease in light transmission was observed from 200 to ~425h in SBF. SEM analysis suggested that after 200h, the surface of the fiber was fully covered by a thin Ca-P layer which is likely to scatter light. For immersion times longer than ~425h, the thickness of the Ca-P layer increased and thus acted as a barrier to the dissolution process limiting further reduction in light transmission. The tracking of light transmission through the PBG fiber allowed monitoring of the fiber dissolution in vitro. These results are essential in developing new bioactive fiber sensors that can be used to monitor bioresponse in situ. Copyright © 2014 Elsevier B.V. All rights reserved.

Microfluidics with fluid walls.

Science.gov (United States)

Walsh, Edmond J; Feuerborn, Alexander; Wheeler, James H R; Tan, Ann Na; Durham, William M; Foster, Kevin R; Cook, Peter R

2017-10-10

Microfluidics has great potential, but the complexity of fabricating and operating devices has limited its use. Here we describe a method - Freestyle Fluidics - that overcomes many key limitations. In this method, liquids are confined by fluid (not solid) walls. Aqueous circuits with any 2D shape are printed in seconds on plastic or glass Petri dishes; then, interfacial forces pin liquids to substrates, and overlaying an immiscible liquid prevents evaporation. Confining fluid walls are pliant and resilient; they self-heal when liquids are pipetted through them. We drive flow through a wide range of circuits passively by manipulating surface tension and hydrostatic pressure, and actively using external pumps. Finally, we validate the technology with two challenging applications - triggering an inflammatory response in human cells and chemotaxis in bacterial biofilms. This approach provides a powerful and versatile alternative to traditional microfluidics.The complexity of fabricating and operating microfluidic devices limits their use. Walsh et al. describe a method in which circuits are printed as quickly and simply as writing with a pen, and liquids in them are confined by fluid instead of solid walls.

Structure, biodegradation behavior and cytotoxicity of alkali-containing alkaline-earth phosphosilicate glasses.

Science.gov (United States)

Kansal, Ishu; Reddy, AlluAmarnath; Muñoz, Francisco; Choi, Seong-Jun; Kim, Hae-Won; Tulyaganov, Dilshat U; Ferreira, José M F

2014-11-01

We report on the effect of sodium on the structure, chemical degradation and bioactivity of glasses in the CaO-MgO-SiO2-P2O5-CaF2 system. The (29)Si and (31)P magic angle spinning-nuclear magnetic resonance spectroscopy of melt-quenched glasses with varying Na2O/MgO ratios exhibit a silicate glass network with the dominance of Q(2)(Si) units and phosphorus mainly forming orthophosphate species. Sodium incorporation in the glasses did not induce a significant structural change in the silicate network, while it did influence the phosphate environment due to its lower ionic field strength in comparison with that of magnesium. The apatite forming ability of glasses has been investigated by immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1h and 7 days while their chemical degradation has been studied in Tris-HCl in accordance with ISO-10993-14. Increasing Na(+)/Mg(2+) ratio caused a decrease in the chemical durability of glasses and in the apatite forming ability especially during initial steps of interaction between glass and SBF solution. The cellular responses were observed in vitro on bulk glass samples using mouse-derived pre-osteoblastic MC3T3-E1 cell line. The preliminary study suggested that the increasing alkali-concentration in glasses led to cytotoxicity in the cell culture medium. Copyright © 2014 Elsevier B.V. All rights reserved.

More accurate X-ray scattering data of deeply supercooled bulk liquid water

Energy Technology Data Exchange (ETDEWEB)

Neuefeind, Joerg C [ORNL; Benmore, Chris J [Argonne National Laboratory (ANL); Weber, Richard [Argonne National Laboratory (ANL); Paschek, Dietmar [Rostock University, Rostock, Germany

2011-01-01

Deeply supercooled water droplets held container-less in an acoustic levitator are investigated with high energy X-ray scattering. The temperature dependence X-ray structure function is found to be non-linear. Comparison with two popular computer models reveals that structural changes are predicted too abrupt by the TIP5P model, while the rate of change predicted by TIP4P is in much better agreement with experiment. The abrupt structural changes predicted by the TIP5P model to occur in the temperature range between 260-240K as water approaches the homogeneous nucleation limit are unrealistic. Both models underestimate the distance between neighbouring oxygen atoms and overestimate the sharpness of the OO distance distribution, indicating that the strength of the H-bond is overestimated in these models.

Carbon and its isotopes in mid-oceanic basaltic glasses

International Nuclear Information System (INIS)

Des Marais, D.J.

1984-01-01

Three carbon components are evident in eleven analyzed mid-oceanic basalts: carbon on sample surfaces (resembling adsorbed gases, organic matter, or other non-magmatic carbon species acquired by the glasses subsequent to their eruption), mantle carbon dioxide in vesicles, and mantle carbon dissolved in the glasses. The combustion technique employed recovered only reduced sulfur, all of which appears to be indigenous to the glasses. The dissolved carbon concentration (measured in vesicle-free glass) increases with the eruption depth of the spreading ridge, and is consistent with earlier data which show that magma carbon solubility increases with pressure. The total glass carbon content (dissolved plus vesicular carbon) may be controlled by the depth of the shallowest ridge magma chamber. Carbon isotopic fractionation accompanies magma degassing; vesicle CO 2 is about 3.8per mille enriched in 13 C, relative to dissolved carbon. Despite this fractionation, delta 13 Csub(PDB) values for all spreading ridge glasses lie within the range -5.6 and -7.5, and the delta 13 Csub(PDB) of mantle carbon likely lies between -5 and -7. The carbon abundances and delta 13 Csub(PDB) values of Kilauea East Rift glasses apparently are influences by the differentiation and movement of magma within that Hawaiian volcano. Using 3 He and carbon data for submarine hydrothermal fluids, the present-day mid-oceanic ridge mantle carbon flux is estimated very roughly to be about 1.0 x 10 13 g C/yr. Such a flux requires 8 Gyr to accumulate the earth's present crustal carbon inventory. (orig.)

Fluids and the evolution of rock mechanical properties

International Nuclear Information System (INIS)

Reuschle, Thierry

1989-01-01

This research thesis reports the study of the various phenomena of fluid-solid interaction (mechanical or chemical interaction with fracturing by fluid overpressure, slow crack propagation, and pore deformation by transfer in solution) which may occur in the interaction of fluids with rocks. The author first presents the formalism of slow crack propagation based on the generalisation of the Griffith criterion. The model results are compared with experimental results obtained on four materials (glass, quartz, sandstone, and micrite) by using the double-torsion test. In the second part, the author addresses the issue of pore deformation by transfer in solution: dissolution and crystallisation under stress. The Gibbs chemical potential equation is firstly generalised to the case of a circular pore, and a formalism combining mechanics and thermodynamics is then proposed. A set of simulations highlights important parameters. In the third part, the author addresses the problem of fluid-rock mechanical interaction by studying the mechanical role of fluid pressure in crack initiation and propagation [fr

Calcium phosphate glass-ceramics for bioactive coating on a {beta}-titanium alloy

Energy Technology Data Exchange (ETDEWEB)

Kasuga, T.; Nogami, M. [Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Niinomi, M. [Department of Production Systems Engineering, Toyohashi University of Technology, Tenpaku-cho, Toyohashi 441-8580 (Japan)

2003-07-01

The formation of a porous coating is the decisive feature for the bio-compatibility of silica-free calcium phosphate glass ceramics on alloy surfaces like the {beta}-Ti structured Ti-29Nb-13Ta-4.6Zr used in this work. The ceramic composition is highly important: 50CaO-40P{sub 2}O{sub 5}-7Na{sub 2}O-3TiO{sub 2} glass powder produces a pore-free coating unable to bind hydroxyapatite, whereas 60CaO-30P{sub 2}O{sub 5}-7Na{sub 2}O-3TiO{sub 2} glass incorporates pores from which a crystalline hydroxyapatite phase can grow over the surface from simulated body fluid (see Figure). (Abstract Copyright [2003], Wiley Periodicals, Inc.)

In Vitro Evaluation of Some Types of Ferrimagnetic Glass Ceramics

Directory of Open Access Journals (Sweden)

S. A. M. Abdel-Hameed

2014-01-01

Full Text Available The present study aimed at studying the acceleration of the bioactive layer on the surface of ferrimagnetic glass ceramic with a basic composition 40Fe2O3–15P2O5–20SiO2–5TiO2 through the addition of 20% of different types of metal oxides like MgO or CaO or MnO or CuO or ZnO or CeO2. SEM, EDAX, and ICP were applied to present the results of the study. SEM and EDAX measurements indicated the presence of apatite layer formed on the surface of the prepared glass ceramics after immersion in SBF within 7 to 30 days. The investigation of the results clarified that the addition of CaO or ZnO accelerated the formation of apatite on the surfaces of the samples in the simulated body fluid faster than other metal oxides. Inductive coupled plasma (ICP analysis shows the evolution of ion extraction by the simulated body fluid solution (SBF with time in relation to the elemental composition.

fluid and electrolyte balance during the comrades marathon

African Journals Online (AJOL)

340 ml (all one type); Coca Cola (one size) = 300 ml; and a glass or cup of fluid = 200 m!. Blood was taken immediately after the race. Particular importance was attached to analysing all blood samples on the same afternoon and evening that the race was run. Sodium, chloride, potassium, urea and packed cell volumes.

In vitro bioactivity of polymer matrices reinforced with a bioactive glass phase

Directory of Open Access Journals (Sweden)

Oréfice Rodrigo L.

2000-01-01

Full Text Available Composites that can mimic the in vitro bioactive behavior of bioactive glasses were designed to fulfill two main features of bioactive glasses that are responsible for their high bond-to-bone rates: (1 capability of providing ions such as calcium and phosphate to the nearby environment and (2 ideal surface structure that allows fast heterogeneous precipitation of hydroxy-carbonate-apatite (HCA. The novel composites were prepared by incorporating bioactive glass particles into polymer matrices. The in vitro bioactivity test was performed by introducing samples into a buffered solution as well as into a simulated body fluid solution. FTIR was used to evaluate the kinetics of HCA (hydroxy-carbonate-apatite precipitation. The results showed that the obtained composites can supply ions, such as silicates and phosphates in rates and concentrations comparable or superior than bulk bioactive glasses. Moreover, the surface chemistry of the composites was altered to mimic the surface of bioactive glasses. It was demonstrated that the in vitro bioactivity of the composites was enhanced by chemically modifying polymer surfaces through the introduction of special alkoxysilane groups.

Phytic acid derived bioactive CaO-P2O5-SiO2 gel-glasses.

Science.gov (United States)

Li, Ailing; Qiu, Dong

2011-12-01

The possibility of using phytic acid as a precursor to synthesize CaO-P(2)O(5)-SiO(2) glasses by sol-gel method has been explored and the pseudo ternary phase diagram has been established. It was shown that gel-glasses over a broader range of compositions could be prepared compared to other phosphorus precursors or melt-quenching method. Furthermore, phytic acid was found to assist calcium being incorporated into glass networks. In vitro tests in simulated body fluid (SBF) were performed on the above gel-glasses and it was found that they were bioactive over a much broader compositional range especially at high phosphate content, thus enabling one to design bioactive materials with various degradation rates by adjusting the phosphate content.

Thermal stability of the French nuclear waste glass - long term behavior modeling; Etude de la stabilite thermique du verre nucleaire. Modelisation de son evolution a long terme

Energy Technology Data Exchange (ETDEWEB)

Orlhac, X

2000-07-01

The thermal stability of the French nuclear waste glass was investigated experimentally and by modeling to predict its long-term evolution at low temperature. The crystallization mechanisms were analyzed by studying devitrification in the supercooled liquid. Three main crystalline phases were characterized (CaMoO{sub 4}, CeCO{sub 2}, ZnCr{sub 2}O{sub 4}). Their crystallisation was TO 4.24 wt%, due to the low concentration of the constituent elements. The nucleation and growth curves showed that platinoid elements catalysed nucleation but did not affect growth, which was governed by volume diffusion. The criteria of classic nucleation theory were applied to determine the thermodynamic and diffusional activation energies. Viscosity measurements illustrate the analogy between the activation energy of viscous flow and diffusion, indicating control of crystallization by viscous flow phenomena. The combined action of nucleation and growth was assessed by TTT plots, revealing a crystallization equilibrium line that enables the crystallized fractions to be predicted over the long term. The authors show that hetero-genetics catalyze the transformation without modifying the maximum crystallized fraction. A kinetic model was developed to describe devitrification in the glass based on the nucleation and growth curves alone. The authors show that the low-temperature growth exhibits scale behavior (between time and temperature) similar to thermo-rheological simplicity. The analogy between the resulting activation energy and that of the viscosity was used to model growth on the basis of viscosity. After validation with a simplified (BaO{sub 2}SiO{sub 2}) glass, the model was applied to the containment glass. The result indicated that the glass remained completely vitreous after a cooling scenario with the one measured at the glass core. Under isothermal conditions, several million years would be required to reach the maximum theoretical crystallization fraction. (author)

Observation of a new surface mode on a fluid-saturated permeable solid

International Nuclear Information System (INIS)

Nagy, P.B.

1992-01-01

Almost ten years ago, S. Feng and D. L. Johnson predicted the presence of a new surface mode on a fluid/fluid-saturated porous solid interface with closed surface pores [J. Acoust. Soc. Am. 74, 906 (1983)]. We found that, due to surface tension, practically closed-pore boundary conditions can prevail at an interface between a nonwetting fluid (e.g., air) and a porous solid saturated with a wetting fluid (e.g., water or alcohol). Surface wave velocity and attenuation measurements were made on alcohol-saturated porous sintered glass at 100 kHz. The experimental results show clear evidence of the new ''slow'' surface mode predicted by Feng and Johnson

Synthesis and In Vitro Activity Assessment of Novel Silicon Oxycarbide-Based Bioactive Glasses

Directory of Open Access Journals (Sweden)

Isabel Gonzalo-Juan

2016-11-01

Full Text Available Novel bioactive glasses based on a Ca- and Mg-modified silicon oxycarbide (SiCaMgOC were prepared from a polymeric single-source precursor, and their in vitro activity towards hydroxyapatite mineralization was investigated upon incubating the samples in simulated body fluid (SBF at 37 °C. The as-prepared materials exhibit an outstanding resistance against devitrification processes and maintain their amorphous nature even after exposure to 1300 °C. The X-ray diffraction (XRD analysis of the SiCaMgOC samples after the SBF test showed characteristic reflections of apatite after only three days, indicating a promising bioactivity. The release kinetics of the Ca2+ and Mg2+ and the adsorption of H+ after immersion of SiCaMgOC in simulated body fluid for different soaking times were analyzed via optical emission spectroscopy. The results show that the mechanism of formation of apatite on the surface of the SiCaMgOC powders is similar to that observed for standard (silicate bioactive glasses. A preliminary cytotoxicity investigation of the SiOC-based bioactive glasses was performed in the presence of mouse embryonic fibroblasts (MEF as well as human embryonic kidney cells (HEK-293. Due to their excellent high-temperature crystallization resistance in addition to bioactivity, the Ca- and Mg-modified SiOC glasses presented here might have high potential in applications related to bone repair and regeneration.

A metastable liquid melted from a crystalline solid under decompression

Science.gov (United States)

Lin, Chuanlong; Smith, Jesse S.; Sinogeikin, Stanislav V.; Kono, Yoshio; Park, Changyong; Kenney-Benson, Curtis; Shen, Guoyin

2017-01-01

A metastable liquid may exist under supercooling, sustaining the liquid below the melting point such as supercooled water and silicon. It may also exist as a transient state in solid-solid transitions, as demonstrated in recent studies of colloidal particles and glass-forming metallic systems. One important question is whether a crystalline solid may directly melt into a sustainable metastable liquid. By thermal heating, a crystalline solid will always melt into a liquid above the melting point. Here we report that a high-pressure crystalline phase of bismuth can melt into a metastable liquid below the melting line through a decompression process. The decompression-induced metastable liquid can be maintained for hours in static conditions, and transform to crystalline phases when external perturbations, such as heating and cooling, are applied. It occurs in the pressure-temperature region similar to where the supercooled liquid Bi is observed. Akin to supercooled liquid, the pressure-induced metastable liquid may be more ubiquitous than we thought.

Plastic deformation behavior of Fe–Co–B–Si–Nb–Cr bulk metallic glasses under nanoindentation

Energy Technology Data Exchange (ETDEWEB)

Kim, J.T.; Hong, S.H.; Lee, C.H. [HMC, Faculty of Nanotechnology and Advanced Materials Engineering, Sejong University, 98 Gunja-dong, Gwangjin-gu, Seoul 143-747 (Korea, Republic of); Park, J.M., E-mail: jinman_park@hotmail.com [Materials Research Center, Samsung Advanced Institute of Technology (SAIT), San 14-1, Nongseo-dong, Giheung-gu, Yongin-si, Gyeonggi-do 446-712 (Korea, Republic of); Kim, T.W.; Lee, W.H. [HMC, Faculty of Nanotechnology and Advanced Materials Engineering, Sejong University, 98 Gunja-dong, Gwangjin-gu, Seoul 143-747 (Korea, Republic of); Yim, H.I. [Department of Physics, Sookmyung Women’s University, Hyochangwongil 52, Yongsan-ku, Seoul 140-742 (Korea, Republic of); Kim, K.B., E-mail: kbkim@sejong.ac.kr [HMC, Faculty of Nanotechnology and Advanced Materials Engineering, Sejong University, 98 Gunja-dong, Gwangjin-gu, Seoul 143-747 (Korea, Republic of)

2014-02-25

Highlights: • Additional Cr modulation of atomic structure of Fe-Co-B-Si-Nb BMGs. • An amount of free volume characterized by a combination of nanoindentation and AFM. • Free volume determined by height measurement of AFM after nanoindentation. -- Abstract: In this work, we investigate the effect of Cr addition on thermal properties and indentation behavior of Fe{sub 52}Co{sub 20−x}B{sub 20}Si{sub 4}Nb{sub 4}Cr{sub x} alloys with x = 0, 1, 3 and 5 at.%, respectively. Among all studied alloys, the Fe{sub 52}Co{sub 17}B{sub 20}Si{sub 4}Nb{sub 4}Cr{sub 3} bulk metallic glass (BMG) exhibits the highest thermal stability with large supercooled liquid region of 40 K and the pronounced plastic deformation features which is serrated flow (pop-in event) and significant pile-up of materials around indents. This demonstrates that the appropriate addition of Cr in Fe-based BMG can induce the internal atomic structure modulation and promote the mechanical softening, which are discussed in terms of free volume concept.

Plastic deformation behavior of Fe–Co–B–Si–Nb–Cr bulk metallic glasses under nanoindentation

International Nuclear Information System (INIS)

Kim, J.T.; Hong, S.H.; Lee, C.H.; Park, J.M.; Kim, T.W.; Lee, W.H.; Yim, H.I.; Kim, K.B.

2014-01-01

Highlights: • Additional Cr modulation of atomic structure of Fe-Co-B-Si-Nb BMGs. • An amount of free volume characterized by a combination of nanoindentation and AFM. • Free volume determined by height measurement of AFM after nanoindentation. -- Abstract: In this work, we investigate the effect of Cr addition on thermal properties and indentation behavior of Fe 52 Co 20−x B 20 Si 4 Nb 4 Cr x alloys with x = 0, 1, 3 and 5 at.%, respectively. Among all studied alloys, the Fe 52 Co 17 B 20 Si 4 Nb 4 Cr 3 bulk metallic glass (BMG) exhibits the highest thermal stability with large supercooled liquid region of 40 K and the pronounced plastic deformation features which is serrated flow (pop-in event) and significant pile-up of materials around indents. This demonstrates that the appropriate addition of Cr in Fe-based BMG can induce the internal atomic structure modulation and promote the mechanical softening, which are discussed in terms of free volume concept

An integrated process analytical technology (PAT) approach to monitoring the effect of supercooling on lyophilization product and process parameters of model monoclonal antibody formulations.

Science.gov (United States)

Awotwe Otoo, David; Agarabi, Cyrus; Khan, Mansoor A

2014-07-01

The aim of the present study was to apply an integrated process analytical technology (PAT) approach to control and monitor the effect of the degree of supercooling on critical process and product parameters of a lyophilization cycle. Two concentrations of a mAb formulation were used as models for lyophilization. ControLyo™ technology was applied to control the onset of ice nucleation, whereas tunable diode laser absorption spectroscopy (TDLAS) was utilized as a noninvasive tool for the inline monitoring of the water vapor concentration and vapor flow velocity in the spool during primary drying. The instantaneous measurements were then used to determine the effect of the degree of supercooling on critical process and product parameters. Controlled nucleation resulted in uniform nucleation at lower degrees of supercooling for both formulations, higher sublimation rates, lower mass transfer resistance, lower product temperatures at the sublimation interface, and shorter primary drying times compared with the conventional shelf-ramped freezing. Controlled nucleation also resulted in lyophilized cakes with more elegant and porous structure with no visible collapse or shrinkage, lower specific surface area, and shorter reconstitution times compared with the uncontrolled nucleation. Uncontrolled nucleation however resulted in lyophilized cakes with relatively lower residual moisture contents compared with controlled nucleation. TDLAS proved to be an efficient tool to determine the endpoint of primary drying. There was good agreement between data obtained from TDLAS-based measurements and SMART™ technology. ControLyo™ technology and TDLAS showed great potential as PAT tools to achieve enhanced process monitoring and control during lyophilization cycles. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Ground-glass opacity in lung metastasis from adenocarcinoma of the stomach: a case report

International Nuclear Information System (INIS)

Jung, Mi Ran; Kim, Jeong Kon; Lee, Jin Seong; Song, Koun Sik; Lim, Tae Hwan

2000-01-01

Ground-glass opacity is a frequent but nonspecific finding seen on high-resolution CT scans of lung parenchyma. Histologically, this appearance is observed when thickening of the alveolar wall and septal interstitium is minimal or the alveolar lumen is partially filled with fluid, macrophage, neutrophils, or amorphous material. It has been shown that ground-glass opacity may be caused not only by an active inflammatory process but also by fibrotic processes. When a focal area of ground-glass opacity persists or increases in size, the possibility of neoplasm-bronchioloalveolar carcinoma or adenoma, or lymphoma, for example, should be considered. Diffuse nonsegmental ground-glass opacity in both lung fields was incidentally found on follow up abdominal CT in a stomach cancer patient and signet-ring cell-type metastatic lung cancer was confirmed by transbronchial lung biopsy. We report a case of diffuse ground-glass opacity seen in metastatic lung cancer from adenocarcinoma of the stomach. (author)

Characterization of glass and glass ceramic nuclear waste forms

International Nuclear Information System (INIS)

Lutze, W.; Borchardt, J.; De, A.K.

1979-01-01

Characteristics of solidified nuclear waste forms, glass and glass ceramic compositions and the properties (composition, thermal stability, crystallization, phase behavior, chemical stability, mechanical stability, and radiation effects) of glasses and glass ceramics are discussed. The preparation of glass ceramics may be an optional step for proposed vitrification plants if tailored glasses are used. Glass ceramics exhibit some improved properties with respect to glasses. The overall leach resistance is similar to that of glasses. An increased leach resistance may become effective for single radionuclides being hosted in highly insoluble crystal phases mainly when higher melting temperatures are applicable in order to get more leach resistant residual glass phases. The development of glass ceramic is going on. The technological feasibility is still to be demonstrated. The potential gain of stability when using glass ceramics qualifies the material as an alternative nuclear waste form

Hydrophobic Surfaces: Topography Effects on Wetting by Supercooled Water and Freezing Delay

DEFF Research Database (Denmark)

Heydari, Golrokh; Thormann, Esben; Järn, Mikael

2013-01-01

Hydrophobicity, and in particular superhydrophobicity, has been extensively considered to promote ice-phobicity. Dynamic contact angle measurements above 0 °C have been widely used to evaluate the water repellency. However, it is the wetting properties of supercooled water at subzero temperatures...... and the derived work of adhesion that are important for applications dealing with icing. In this work we address this issue by determining the temperature-dependent dynamic contact angle of microliter-sized water droplets on a smooth hydrophobic and a superhydrophobic surface with similar surface chemistry....... The data highlight how the work of adhesion of water in the temperature interval from about 25 °C to below −10 °C is affected by surface topography. A marked decrease in contact angle on the superhydrophobic surface is observed with decreasing temperature, and we attribute this to condensation below...

In vitro study of nano-sized zinc doped bioactive glass

Energy Technology Data Exchange (ETDEWEB)

Goh, Yi-Fan; Alshemary, Ammar Z.; Akram, Muhammad [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM skudai, Johor Darul Ta' zim (Malaysia); Abdul Kadir, Mohammed Rafiq [Medical Implant Technology Group, Faculty of Biomedical Engineering and Health Science, Universiti Teknologi Malaysia, 81310 UTMJohor Bahru (Malaysia); Hussain, Rafaqat, E-mail: rafaqat@kimia.fs.utm.my [IbnuSina Institute for Fundamental Science Studies, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor DarulTa' zim (Malaysia)

2013-01-15

Surface reactivity in physiological fluid has been linked to bioactivity of a material. Past research has shown that bioactive glass containing zinc has the potential in bone regeneration field due to its enhanced bioactivity. However, results from literature are always contradictory. Therefore, in this study, surface reactivity of bioactive glass containing zinc was evaluated through the study of morphology and composition of apatite layer formed after immersion in simulated body fluid (SBF). Nano-sized bioactive glass with 5 and 10 mol% zinc were synthesized through quick alkali sol-gel method. The synthesized Zn-bioglass was characterized using field emission scanning electron microscope (FESEM), energy dispersive X-ray spectrometer (EDX), X-ray diffractometer (XRD) and Fourier transform infrared spectrometer (FTIR). Samples after SBF immersion were characterized using scanning electron microscope (SEM) and EDX. Morphological study through SEM showed the formation of spherical apatite particles with Ca/P ratio closer to 1.67 on the surface of 5 mol% Zn-bioglass. Whereas, the 10 mol% Zn-bioglass samples induced the formation of flake-like structure of calcite in addition to the spherical apatite particles with much higher Ca/P ratio. Our results suggest that the higher Zn content increases the bioactivity through the formation of bone-bonding calcite as well as the spherical apatite particles. -- Highlights: Black-Right-Pointing-Pointer Nano-sized bioactive glasses were synthesized through quick alkali sol-gel method. Black-Right-Pointing-Pointer 5 and 10 mol% Zn-bioglass induced the formation of spherical particles in SBF test. Black-Right-Pointing-Pointer 10 mol% Zn-bioglass also induced the formation of flake-like structure. Black-Right-Pointing-Pointer The flake-like structure is calcium carbonate; spherical particles are apatite. Black-Right-Pointing-Pointer High Zn contents negatively influence the chemical composition of the apatite layer.

Using 20-million-year-old amber to test the super-Arrhenius behaviour of glass-forming systems

Science.gov (United States)

Zhao, Jing; Simon, Sindee L.; McKenna, Gregory B.

2013-04-01

Fossil amber offers the opportunity to investigate the dynamics of glass-forming materials far below the nominal glass transition temperature. This is important in the context of classical theory, as well as some new theories that challenge the idea of an ‘ideal’ glass transition. Here we report results from calorimetric and stress relaxation experiments using a 20-million-year-old Dominican amber. By performing the stress relaxation experiments in a step-wise fashion, we measured the relaxation time at each temperature and, above the fictive temperature of this 20-million-year-old glass, this is an upper bound to the equilibrium relaxation time. The results deviate dramatically from the expectation of classical theory and are consistent with some modern ideas, in which the diverging timescale signature of complex fluids disappears below the glass transition temperature.

Atomic-level structure and structure-property relationship in metallic glass

Science.gov (United States)

Cheng, Yongqiang

One of the key tasks in material science is to understand the structure and structure-property relationship. The recently emerging bulk metallic glasses (BMGs) have demonstrated unique properties, especially intriguing mechanical properties such as their high strength and high propensity to localize deformation in shear bands. However, a comprehensive understanding of the structure of BMGs has been hindered by the complexity of these amorphous materials. Even more challenging is the structure-property correlation, which has been well established in crystals but has been seriously lacking for BMGs. This thesis presents a systematic study of the atomic-level structures of two representative BMGs, Cu-Zr and Cu-Zr-Al. The interpenetrating Cu-centered icosahedral clusters have been identified to be the primary structural feature. The fraction of icosahedra increases with increasing Cu or Al contents, and with decreasing cooling rate. The effect of Al in improving the icosahedral order is two-fold: the geometric effect due to the atomic-size mismatch and the chemical effect originated from the Cu-Al bond shortening. The resolved structure is used to study the structure-property relationship. The full icosahedra are found to be responsible for the dynamical slowdown of the supercooled liquid, which underlies the non-Arrhenius behavior, and explains the composition dependence of glass transition temperature, glass forming ability, and the room temperature strength. By simulated deformation, the initiation of plasticity and tendency for strain localization are also investigated. The full icosahedra are found to be the most rigid and resistant cluster with solid-like character, while the unstable clusters with liquid-like character serve as the fertile sites for initiating shear transformations. In addition, the elastic moduli are calculated and analyzed, and the origins of the different configurational dependence of shear modulus (G) and bulk modulus ( B) are explained. The

The Influence of Na and Ti on the In Vitro Degradation and Bioactivity in 58S Sol-Gel Bioactive Glass

Directory of Open Access Journals (Sweden)

Shirong Ni

2012-01-01

Full Text Available The aim of this study was to investigate the effect of Na and Ti on the in vitro degradation and bioactivity in the 58S bioactive glass. The degradation was evaluated through the activation energy of Si ion release from bioactive glasses and the weight loss of bioactive glasses in Tris-HCl buffer solution. The in vitro bioactivity of the bioactive glasses was investigated by analysis of apatite-formation ability in the simulated body fluid (SBF. The results showed that Na in the 58S glass accelerated the dissolution rate of the glass, whereas Ti in the 58S glass slowed down the rate of glass solubility. Bioactivity tests showed that Na in glass increased the apatite-forming ability in SBF. In contrast, Ti in glass retards the apatite formation at the initial stage of SBF soaking but does not affect the growth of apatite after long periods of soaking.

The behaviour of selected yttrium containing bioactive glass microspheres in simulated body environments.

Science.gov (United States)

Cacaina, D; Ylänen, H; Simon, S; Hupa, M

2008-03-01

The study aims at the manufacture and investigation of biodegradable glass microspheres incorporated with yttrium potentially useful for radionuclide therapy of cancer. The glass microspheres in the SiO2-Na2O-P2O5-CaO-K2O-MgO system containing yttrium were prepared by conventional melting and flame spheroidization. The behaviour of the yttrium silicate glass microspheres was investigated under in vitro conditions using simulated body fluid (SBF) and Tris buffer solution (TBS), for different periods of time, according to half-life time of the Y-90. The local structure of the glasses and the effect of yttrium on the biodegradability process were evaluated by Fourier Transform Infrared (FT-IR) spectroscopy and Back Scattered Electron Imaging of Scanning Electron Microscopy (BEI-SEM) equipped with Energy Dispersive X-ray (EDX) analysis. UV-VIS spectrometry and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used for analyzing the release behaviour of silica and yttrium in the two used solutions. The results indicate that the addition of yttrium to a bioactive glass increases its structural stability which therefore, induced a different behaviour of the glasses in simulated body environments.

Effect of nitrogen and fluorine on mechanical properties and bioactivity in two series of bioactive glasses.

Science.gov (United States)

Bachar, Ahmed; Mercier, Cyrille; Tricoteaux, Arnaud; Hampshire, Stuart; Leriche, Anne; Follet, Claudine

2013-07-01

Bioactive glasses are able to bond to bone through formation of carbonated hydroxyapatite in body fluids, and fluoride-releasing bioactive glasses are of interest for both orthopaedic and, in particular, dental applications for caries inhibition. However, because of their poor strength their use is restricted to non-load-bearing applications. In order to increase their mechanical properties, doping with nitrogen has been performed on two series of bioactive glasses: series (I) was a "bioglass" composition (without P2O5) within the quaternary system SiO2-Na2O-CaO-Si3N4 and series (II) was a simple substitution of CaF2 for CaO in series (I) glasses keeping the Na:Ca ratio constant. The objective of this work was to evaluate the effect of the variation in nitrogen and fluorine content on the properties of these glasses. The density, glass transition temperature, hardness and elastic modulus all increased linearly with nitrogen content which indicates that the incorporation of nitrogen stiffens the glass network because N is mainly in 3-fold coordination with Si atoms. Fluorine addition significantly decreases the thermal property values but the mechanical properties of these glasses remain unchanged with fluorine. The combination of both nitrogen and fluorine in oxyfluoronitride glasses gives better mechanical properties at much lower melting temperatures since fluorine reduces the melting point, allows higher solubility of nitrogen and does not affect the higher mechanical properties arising from incorporation of nitrogen. The characterization of these N and F substituted bioactive glasses using (29)Si MAS NMR has shown that the increase in rigidity of the glass network can be explained by the formation of SiO3N, SiO2N2 tetrahedra and Q(4) units with extra bridging anions at the expense of Q(3) units. Bioactivity of the glasses was investigated in vitro by examining apatite formation on the surface of glasses treated in acellular simulated body fluid (SBF) with ion

Bioactive Glass Nanopowder for theTreatment of Oral Bone Defects

Directory of Open Access Journals (Sweden)

MH. Fathi

2007-09-01

Full Text Available Objective: Osseous defects around dental implants are often seen when implants are placed in areas with inadequate alveolar bone, or around failing implants. Bone regenera-tion in these areas using bone grafts or its substitutes may improve dental implants prog-nosis. The aim of this study was to prepare and characterize the bioactive glass nanopow-der and development of its coating for treatment of oral bone defects.Materials and Methods: Bioactive bioglass coating was made on stainless steel plates by sol-gel technique. The powder shape and size was evaluated by transmission electron mi-cropscopy, and thermal properties studied using differential thermal analysis (DTA. Structural characterization techniques (XRD were used to analyze and study the structure and phase present in the prepared bioactive glass nanopowder. This nanopowder was immersed in the simulated body fluid (SBF solution. Fourier transform infrared spec-troscopy (FTIR was utilized to recognize and confirm the formation of apatite layer on prepared bioactive glass nanopowder.Results: The bioglass powder size was less than 100 nanometers which was necessary for better bioactivity, and preparing a homogeneous coating. The formation of apatite layer confirmed the bioactivity of the bioglass nanopowder. Crack-free and homogeneous bioglass coatings were achieved with no observable defects.Conclusion: It was concluded that the prepared bioactive glass nanopowder could be more effective as a bone replacement material than conventional bioactive glass to pro-mote bone formation in osseous defects. The prepared bioactive glass nanopowder could be more useful for treatment of oral bone defects compare to conventional hydroxyapatite or bioactive glass.

Deformation behavior, corrosion resistance, and cytotoxicity of Ni-free Zr-based bulk metallic glasses.

Science.gov (United States)

Liu, L; Qiu, C L; Chen, Q; Chan, K C; Zhang, S M

2008-07-01

Two Ni-free bulk metallic glasses (BMGs) of Zr(60)Nb(5)Cu(22.5)Pd(5)Al(7.5) and Zr(60)Nb(5)Cu(20)Fe(5)Al(10) were successfully prepared by arc-melting and copper mold casting. The thermal stability and crystallization were studied using differential scanning calorimetry. It demonstrates that the two BMGs exhibit very good glass forming ability with a wide supercooled liquid region. A multi-step process of crystallization with a preferential formation of quasicrystals occurred in both BMGs under continuous heating. The deformation behavior of the two BMGs was investigated using quasi-static compression testing. It reveals that the BMGs exhibit not only superior strength but also an extended plasticity. Corrosion behaviors of the BMGs were investigated in phosphate buffered solution by electrochemical polarization. The result shows that the two BMGs exhibit excellent corrosion resistance characterized by low corrosion current densities and wide passive regions. X-ray photoelectron spectroscopy analysis revealed that the passive film formed after anodic polarization was highly enriched in zirconium, niobium, and aluminum oxides. This is attributed to the excellent corrosion resistance. Additionally, the potential cytotoxicity of the two Ni-free BMGs was evaluated through cell culture for 1 week followed by 3-(4,5-Dimethylthiazol-2-yl-)-2,5-diphenyltetrazolium bromide assay and SEM observation. The results indicate that the two Ni-free BMGs exhibit as good biocompatibility as Ti-6Al-4V alloy, and thus show a promising potential for biomedical applications. (c) 2007 Wiley Periodicals, Inc.

Sucrose in the concentrated solution or the supercooled “State”: A review of caramelisation reactions and physical behaviour

OpenAIRE

Quintas, M. A. C.; Fundo, J. F.; Silva, C. L. M.

2010-01-01

Sucrose is probably one of the most studied molecules by food scientists, since it plays an important role as an ingredient or preserving agent in many formulations and technological processes. When sucrose is present in a product with a concentration near or greater than the saturation point—i.e. in the supercooled state—it possesses high potentialities for the food industry in areas as different as pastry industry, dairy and frozen desserts or films and coatings production. This paper prese...

Micro thermal diode with glass thermal insulation structure embedded in a vapor chamber

Science.gov (United States)

Tsukamoto, Takashiro; Hirayanagi, Takashi; Tanaka, Shuji

2017-04-01

This paper reports a micro thermal diode based on one-way working fluid circulation driven by surface tension force. In forward mode, working fluid evaporates and condenses at a heated and cooled area, respectively, and the condensed liquid returns to the evaporation area due to the wettability difference. By this vapor-liquid phase change mechanism, the overall heat transfer coefficient becomes high. On the other hand, in reverse mode, no continuous evaporation-condensation cycle exists. The conductive heat loss in reverse mode was minimized by an embedded glass thermal isolation structure, which makes overall heat transfer coefficient low. The test device was made by a standard MEMS process combined with glass reflow and gold bump sealing. The overall heat transfer coefficients of 13 300 \\text{W}~{{\\text{m}}-2}~\\text{K} for forward mode and 4790 \\text{W}~{{\\text{m}}-2}~\\text{K} for reverse mode were measured. The performance index of the micro thermal diode was about 2.8.

A unified in vitro evaluation for apatite-forming ability of bioactive glasses and their variants.

Science.gov (United States)

Maçon, Anthony L B; Kim, Taek B; Valliant, Esther M; Goetschius, Kathryn; Brow, Richard K; Day, Delbert E; Hoppe, Alexander; Boccaccini, Aldo R; Kim, Ill Yong; Ohtsuki, Chikara; Kokubo, Tadashi; Osaka, Akiyoshi; Vallet-Regí, Maria; Arcos, Daniel; Fraile, Leandro; Salinas, Antonio J; Teixeira, Alexandra V; Vueva, Yuliya; Almeida, Rui M; Miola, Marta; Vitale-Brovarone, Chiara; Verné, Enrica; Höland, Wolfram; Jones, Julian R

2015-02-01

The aim of this study was to propose and validate a new unified method for testing dissolution rates of bioactive glasses and their variants, and the formation of calcium phosphate layer formation on their surface, which is an indicator of bioactivity. At present, comparison in the literature is difficult as many groups use different testing protocols. An ISO standard covers the use of simulated body fluid on standard shape materials but it does not take into account that bioactive glasses can have very different specific surface areas, as for glass powders. Validation of the proposed modified test was through round robin testing and comparison to the ISO standard where appropriate. The proposed test uses fixed mass per solution volume ratio and agitated solution. The round robin study showed differences in hydroxyapatite nucleation on glasses of different composition and between glasses of the same composition but different particle size. The results were reproducible between research facilities. Researchers should use this method when testing new glasses, or their variants, to enable comparison between the literature in the future.

Multiphase, multi-electrode Joule heat computations for glass melter and in situ vitrification simulations

International Nuclear Information System (INIS)

Lowery, P.S.; Lessor, D.L.

1991-02-01

Waste glass melter and in situ vitrification (ISV) processes represent the combination of electrical thermal, and fluid flow phenomena to produce a stable waste-from product. Computational modeling of the thermal and fluid flow aspects of these processes provides a useful tool for assessing the potential performance of proposed system designs. These computations can be performed at a fraction of the cost of experiment. Consequently, computational modeling of vitrification systems can also provide and economical means for assessing the suitability of a proposed process application. The computational model described in this paper employs finite difference representations of the basic continuum conservation laws governing the thermal, fluid flow, and electrical aspects of the vitrification process -- i.e., conservation of mass, momentum, energy, and electrical charge. The resulting code is a member of the TEMPEST family of codes developed at the Pacific Northwest Laboratory (operated by Battelle for the US Department of Energy). This paper provides an overview of the numerical approach employed in TEMPEST. In addition, results from several TEMPEST simulations of sample waste glass melter and ISV processes are provided to illustrate the insights to be gained from computational modeling of these processes. 3 refs., 13 figs

Stationary and Dynamic Permeability and Coupling Coefficient Measurements in Sintered Glass Bead Systems

Science.gov (United States)

Gueven, I.; Steeb, H.; Luding, S.

2014-12-01

Electrokinetic waves describe the coupling between seismic and electromagnetic waves that exist in porous media. The coupling between them arise from an electrochemical boundary layer between grain and fluid interface of saturated porous media. Acoustical waves cause a disturbance of the electrical fluid charge within the double layer, which therefore creates an electric streaming current (seismoelectric effect). Inversely, electromagnetic waves can generate mechanical signals (electroseismic effect). Electrokinetic conversion potentially combines high seismic resolution with good electromagnetic hydrocarbon sensitivity. The (stationary and frequency-dependent) streaming potential coefficient is a key property, which gives rise to the coupling between electromagnetic and acoustical waves. It depends strongly on the fluid conductivity, porosity, tortuosity, permeability, pore throat and zeta potential of porous media. We examine experimentally both, the stationary and dynamic permeabilities and coupling coefficients of sintered glass bead systems. For this purpose a multi-purpose measuring cell was developed which allows us to carry out - besides common ultrasound experiments - also to perform stationary and frequency-dependent permeability and coupling coefficient measurements. For the experiments sintered mono- and slightly polydisperse glass bead samples with different glass bead diameters between 0.4 and 8mm and porosities ranging between 21 and 39% were used. The stationary and dynamic permeability and streaming potential measurements are supported by μCT scans which enable us a deeper insight into the porous medium. Based on the μCT scans of the produced sintered glass bead samples essential influence parameters, like tortuosity, porosity, effective particle diameters and pore throats in different regions of the entire scanned region have been analyzed in detail to understand the laboratory experiments, cf. Illustration 1. In addition lattice Boltzmann

Kinetic details of crystallization in supercooled liquid Pb during the isothermal relaxation

International Nuclear Information System (INIS)

Zhou Lili; Liu Rangsu; Tian Zean; Liu Hairong; Hou Zhaoyang; Peng Ping; Zhu Xuanmin; Liu Quanhui

2012-01-01

The kinetic details of crystallization in supercooled liquid Pb during the isothermal relaxation process have been investigated by molecular dynamics simulations, and the microstructure evolution analyzed by the cluster-type index method (CTIM) and the tracing method. It has been found that, the dynamic features are consistently correlated with the microstructure evolution and the crystallization characteristics in the mean square displacement (MSD) and the non-Gaussian parameter (NGP): the β relaxation regime corresponds to the minor structural rearrangement because of the “cage effect”, and the atoms attempt to escape from the “cages”; the α relaxation regime is related to a more diffusive movement of atoms, and the appearance of the second plateau in MSD and the non-zero plateau in NGP corresponds to the completion of crystallization. In addition, three distinct stages of nucleation, growth of nuclei and coarsening of crystallites in the crystallization process have been clearly revealed.

Enhanced bioactivity, biocompatibility and mechanical behavior of strontium substituted bioactive glasses.

Science.gov (United States)

Arepalli, Sampath Kumar; Tripathi, Himanshu; Hira, Sumit Kumar; Manna, Partha Pratim; Pyare, Ram; S P Singh

2016-12-01

Strontium contained biomaterials have been reported as a potential bioactive material for bone regeneration, as it reduces bone resorption and stimulates bone formation. In the present investigation, the bioactive glasses were designed to partially substitute SrO for SiO2 in Na2O-CaO-SrO-P2O5-SiO2 system. This work demonstrates that the substitution of SrO for SiO2 has got significant benefit than substitution for CaO in the bioactive glass. Bioactivity was assessed by the immersion of the samples in simulated body fluid for different intervals. The formation of hydroxy carbonate apatite layer was identified by X-ray diffractometry, scanning electron microscopy (SEM) and energy dispersive spectroscopy. The elastic modulus of the bioactive glasses was measured and found to increase with increasing SrO for SiO2. The blood compatibility of the samples was evaluated. In vitro cell culture studies of the samples were performed using human osteosarcoma U2-OS cell lines and found a significant improvement in cell viability and proliferation. The investigation showed enhancement in bioactivity, mechanical and biological properties of the strontia substituted for silica in glasses. Thus, these bioactive glasses would be highly potential for bone regeneration. Copyright © 2016 Elsevier B.V. All rights reserved.

In Vitro Bioactivity and Antimicrobial Tuning of Bioactive Glass Nanoparticles Added with Neem (Azadirachta indica) Leaf Powder

Science.gov (United States)

Prabhu, M.; Ruby Priscilla, S.; Kavitha, K.; Manivasakan, P.; Rajendran, V.; Kulandaivelu, P.

2014-01-01

Silica and phosphate based bioactive glass nanoparticles (58SiO2-33CaO-9P2O5) with doping of neem (Azadirachta indica) leaf powder and silver nanoparticles were prepared and characterised. Bioactive glass nanoparticles were produced using sol-gel technique. In vitro bioactivity of the prepared samples was investigated using simulated body fluid. X-ray diffraction (XRD) pattern of prepared glass particles reveals amorphous phase and spherical morphology with a particle size of less than 50 nm. When compared to neem doped glass, better bioactivity was attained in silver doped glass through formation of hydroxyapatite layer on the surface, which was confirmed through XRD, Fourier transform infrared (FTIR), and scanning electron microscopy (SEM) analysis. However, neem leaf powder doped bioactive glass nanoparticles show good antimicrobial activity against Staphylococcus aureus and Escherichia coli and less bioactivity compared with silver doped glass particles. In addition, the biocompatibility of the prepared nanocomposites reveals better results for neem doped and silver doped glasses at lower concentration. Therefore, neem doped bioactive glass may act as a potent antimicrobial agent for preventing microbial infection in tissue engineering applications. PMID:25276834

In vitro bioactivity and antimicrobial tuning of bioactive glass nanoparticles added with neem (Azadirachta indica) leaf powder.

Science.gov (United States)

Prabhu, M; Ruby Priscilla, S; Kavitha, K; Manivasakan, P; Rajendran, V; Kulandaivelu, P

2014-01-01

Silica and phosphate based bioactive glass nanoparticles (58SiO2-33CaO-9P2O5) with doping of neem (Azadirachta indica) leaf powder and silver nanoparticles were prepared and characterised. Bioactive glass nanoparticles were produced using sol-gel technique. In vitro bioactivity of the prepared samples was investigated using simulated body fluid. X-ray diffraction (XRD) pattern of prepared glass particles reveals amorphous phase and spherical morphology with a particle size of less than 50 nm. When compared to neem doped glass, better bioactivity was attained in silver doped glass through formation of hydroxyapatite layer on the surface, which was confirmed through XRD, Fourier transform infrared (FTIR), and scanning electron microscopy (SEM) analysis. However, neem leaf powder doped bioactive glass nanoparticles show good antimicrobial activity against Staphylococcus aureus and Escherichia coli and less bioactivity compared with silver doped glass particles. In addition, the biocompatibility of the prepared nanocomposites reveals better results for neem doped and silver doped glasses at lower concentration. Therefore, neem doped bioactive glass may act as a potent antimicrobial agent for preventing microbial infection in tissue engineering applications.

Structure, biodegradation behavior and cytotoxicity of alkali-containing alkaline-earth phosphosilicate glasses

Energy Technology Data Exchange (ETDEWEB)

Kansal, Ishu; Reddy, AlluAmarnath [Department of Materials and Ceramics Engineering, University of Aveiro, CICECO, 3810-193 Aveiro (Portugal); Muñoz, Francisco [Ceramics and Glass Institute (CSIC), Kelsen 5, 28049 Madrid (Spain); Choi, Seong-Jun [Department of Nanobiomedical Science and BK21 PLUS NBM Global Research Center for Regenerative Medicine, Dankook University, Cheonan 330714 (Korea, Republic of); Institute of Tissue Regeneration Engineering (ITREN), Dankook University, Cheonan 330714 (Korea, Republic of); Kim, Hae-Won [Department of Nanobiomedical Science and BK21 PLUS NBM Global Research Center for Regenerative Medicine, Dankook University, Cheonan 330714 (Korea, Republic of); Institute of Tissue Regeneration Engineering (ITREN), Dankook University, Cheonan 330714 (Korea, Republic of); Department of Biomaterials Science, College of Dentistry, Dankook University, Cheonan 330714 (Korea, Republic of); Tulyaganov, Dilshat U. [Turin Polytechnic University in Tashkent, 100095 Tashkent (Uzbekistan); Ferreira, José M.F., E-mail: jmf@ua.pt [Department of Materials and Ceramics Engineering, University of Aveiro, CICECO, 3810-193 Aveiro (Portugal)

2014-11-01

We report on the effect of sodium on the structure, chemical degradation and bioactivity of glasses in the CaO–MgO–SiO{sub 2}–P{sub 2}O{sub 5}–CaF{sub 2} system. The {sup 29}Si and {sup 31}P magic angle spinning-nuclear magnetic resonance spectroscopy of melt-quenched glasses with varying Na{sub 2}O/MgO ratios exhibit a silicate glass network with the dominance of Q{sup 2}(Si) units and phosphorus mainly forming orthophosphate species. Sodium incorporation in the glasses did not induce a significant structural change in the silicate network, while it did influence the phosphate environment due to its lower ionic field strength in comparison with that of magnesium. The apatite forming ability of glasses has been investigated by immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1 h and 7 days while their chemical degradation has been studied in Tris–HCl in accordance with ISO-10993-14. Increasing Na{sup +}/Mg{sup 2+} ratio caused a decrease in the chemical durability of glasses and in the apatite forming ability especially during initial steps of interaction between glass and SBF solution. The cellular responses were observed in vitro on bulk glass samples using mouse-derived pre-osteoblastic MC3T3-E1 cell line. The preliminary study suggested that the increasing alkali-concentration in glasses led to cytotoxicity in the cell culture medium. - Highlights: • Na{sup +} did not induce significant structural changes in chemical Si environment. • Sodium is more prone to affect the chemical environment around P. • Increasing Na{sup +}/Mg{sup 2+} ratios hinder bio-mineralization and chemical durability. • Alkali-containing glasses confer cyto-toxicity to the cell culture medium.

Structure, biodegradation behavior and cytotoxicity of alkali-containing alkaline-earth phosphosilicate glasses

International Nuclear Information System (INIS)

Kansal, Ishu; Reddy, AlluAmarnath; Muñoz, Francisco; Choi, Seong-Jun; Kim, Hae-Won; Tulyaganov, Dilshat U.; Ferreira, José M.F.

2014-01-01

We report on the effect of sodium on the structure, chemical degradation and bioactivity of glasses in the CaO–MgO–SiO 2 –P 2 O 5 –CaF 2 system. The 29 Si and 31 P magic angle spinning-nuclear magnetic resonance spectroscopy of melt-quenched glasses with varying Na 2 O/MgO ratios exhibit a silicate glass network with the dominance of Q 2 (Si) units and phosphorus mainly forming orthophosphate species. Sodium incorporation in the glasses did not induce a significant structural change in the silicate network, while it did influence the phosphate environment due to its lower ionic field strength in comparison with that of magnesium. The apatite forming ability of glasses has been investigated by immersion of glass powders in simulated body fluid (SBF) for time durations varying between 1 h and 7 days while their chemical degradation has been studied in Tris–HCl in accordance with ISO-10993-14. Increasing Na + /Mg 2+ ratio caused a decrease in the chemical durability of glasses and in the apatite forming ability especially during initial steps of interaction between glass and SBF solution. The cellular responses were observed in vitro on bulk glass samples using mouse-derived pre-osteoblastic MC3T3-E1 cell line. The preliminary study suggested that the increasing alkali-concentration in glasses led to cytotoxicity in the cell culture medium. - Highlights: • Na + did not induce significant structural changes in chemical Si environment. • Sodium is more prone to affect the chemical environment around P. • Increasing Na + /Mg 2+ ratios hinder bio-mineralization and chemical durability. • Alkali-containing glasses confer cyto-toxicity to the cell culture medium

Modeling principles applied to the simulation of a joule-heated glass melter

International Nuclear Information System (INIS)

Routt, K.R.

1980-05-01

Three-dimensional conservation equations applicable to the operation of a joule-heated glass melter were rigorously examined and used to develop scaling relationships for modeling purposes. By rigorous application of the conservation equations governing transfer of mass, momentum, energy, and electrical charge in three-dimensional cylindrical coordinates, scaling relationships were derived between a glass melter and a physical model for the following independent and dependent variables: geometrical size (scale), velocity, temperature, pressure, mass input rate, energy input rate, voltage, electrode current, electrode current flux, total power, and electrical resistance. The scaling relationships were then applied to the design and construction of a physical model of the semiworks glass melter for the Defense Waste Processing Facility. The design and construction of such a model using glycerine plus LiCl as a model fluid in a one-half-scale Plexiglas tank is described

Electrochromic Glasses.

Science.gov (United States)

1980-07-31

this glass and that dipole-dipole correlations contribute to the "ferroelectric-like" character of this amorphous system. The TeO2 -W03 glasses can only...shows the dielectric constant and Fig. I(b) glass from pure TeO2 ot pure WO. In addition, glass the tan 8 of the WO glass as a function of temperature... glasses containing WO, in various glass forming nitworks of LifO-B1O0, Na:O-BzO,, and TeO2 were prepared from reagent grade oxides at 800 C - 9SO C in

Plasma spraying of bioactive glass-ceramics containing bovine bone

Directory of Open Access Journals (Sweden)

Annamária Dobrádi

2017-06-01

Full Text Available Natural bone derived glass-ceramics are promising biomaterials for implants. However, due to their price and weak mechanical properties they are preferably applied as coatings on load bearing implants. This paper describes result obtained by plasma spraying of bioactive glass-ceramics containing natural bone onto selected implant materials, such as stainless steel, alumina, and titanium alloy. Adhesion of plasma sprayed coating was tested by computed X-ray tomography and SEM of cross sections. The results showed defect free interface between the coating and substrate, without cracks or gaps. Dissolution rate of the coating in simulated body fluid (SBF was readily controlled by the bone additives (phase composition, as well as microstructure. The SBF treatment of the plasma sprayed coating did not influence the boundary between the coating and substrate.

The crystallization behaviour and bioactivity of wollastonite glass-ceramic based on Na2O–K2O–CaO–SiO2–F glass system

Directory of Open Access Journals (Sweden)

S.M. Salman

2015-09-01

Full Text Available The study concerns about the crystallization behaviour and in vitro bioactivity of a glass-ceramic prepared from a series of glasses in the Na2O–K2O–CaO–SiO2–F system. A minor amount of cerium oxide was also added instead of calcium oxide in some selective glass batches. The main crystalline phases, formed after the appropriate heat treatments, were wollastonite solid solution and pseudo-wollastonite-like phases. There is a preferential tendency for wollastonite (CaSiO3 to accommodate K, Na, F, and Ce ions in its structure forming wollastonite solid solution with variable formulas. The bioactivity of the resulting crystalline materials was examined in vitro by immersion in simulated body fluid at 37 °C. An increase of the surface bioactivity of glass-ceramic with the Na2O/K2O replacement was observed which is attributed to the augmentation solubility of the crystalline sample. On the other hand, the bioactivity of the crystalline sample with CeO2/CaO replacement was improved by the crystallization of pseudo-wollastonite phase together with wollastonite solid solution phase.

fluid and electrolyte balance during the comrades marathon

African Journals Online (AJOL)

collapsed after running 19 miles and died the next day. In the Paris ... and a glass or cup of fluid = 200 m!. Blood was .... 8 hours. Average. 5100. 133. Water Deficit during the Race (Tables I - Ill). Those whose sweat loss was the greatest had the best in- takes. All of those who sweat loss exceeded 9 litres drank more than 4t ...

The melting of stable glasses is governed by nucleation-and-growth dynamics

International Nuclear Information System (INIS)

Jack, Robert L.; Berthier, Ludovic

2016-01-01

We discuss the microscopic mechanisms by which low-temperature amorphous states, such as ultrastable glasses, transform into equilibrium fluids, after a sudden temperature increase. Experiments suggest that this process is similar to the melting of crystals, thus differing from the behaviour found in ordinary glasses. We rationalize these observations using the physical idea that the transformation process takes place close to a “hidden” equilibrium first-order phase transition, which is observed in systems of coupled replicas. We illustrate our views using simulation results for a simple two-dimensional plaquette spin model, which is known to exhibit a range of glassy behaviour. Our results suggest that nucleation-and-growth dynamics, as found near ordinary first-order transitions, is also the correct theoretical framework to analyse the melting of ultrastable glasses. Our approach provides a unified understanding of multiple experimental observations, such as propagating melting fronts, large kinetic stability ratios, and “giant” dynamic length scales. We also provide a comprehensive discussion of available theoretical pictures proposed in the context of ultrastable glass melting.

Relaxations in spin glasses: Similarities and differences from ordinary glasses

International Nuclear Information System (INIS)

Ngai, K.L.; Rajagopal, A.K.; Huang, C.Y.

1984-01-01

Relaxation phenomena have become a major concern in the physics of spin glasses. There are certain resemblances of these relaxation properties to those of ordinary glasses. In this work, we compare the relaxation properties of spin glasses near the freezing temperature with those of glasses near the glass transition temperature. There are similarities between the two types of glasses. Moreover, the relaxation properties of many glasses and spin glasses are in conformity with two coupled ''universality'' relations predicted by a recent model of relaxations in condensed matter

Glass science tutorial: Lecture No. 7, Waste glass technology for Hanford

International Nuclear Information System (INIS)

Kruger, A.A.

1995-07-01

This paper presents the details of the waste glass tutorial session that was held to promote knowledge of waste glass technology and how this can be used at the Hanford Reservation. Topics discussed include: glass properties; statistical approach to glass development; processing properties of nuclear waste glass; glass composition and the effects of composition on durability; model comparisons of free energy of hydration; LLW glass structure; glass crystallization; amorphous phase separation; corrosion of refractories and electrodes in waste glass melters; and glass formulation for maximum waste loading

Interaction of HEPES buffer with glass-ceramic scaffold: Can HEPES replace TRIS in SBF?