A neutron-X-ray, NMR and calorimetric study of glassy Probucol synthesized using containerless techniques

Energy Technology Data Exchange (ETDEWEB)

Weber, J.K.R., E-mail: rweber@anl.gov [Materials Development, Inc., Arlington Heights, IL 60004 (United States); Argonne National Laboratory, Argonne, IL 60439 (United States); Benmore, C.J. [Argonne National Laboratory, Argonne, IL 60439 (United States); Department of Physics, Arizona State University, AZ 85287 (United States); Tailor, A.N.; Tumber, S.K. [Materials Development, Inc., Arlington Heights, IL 60004 (United States); Neuefeind, J. [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Cherry, B. [Magnetic Resonance Research Center, Arizona State University, AZ 85287 (United States); Department of Chemistry and Biochemistry, Arizona State University, AZ 85287 (United States); Yarger, J.L. [Department of Physics, Arizona State University, AZ 85287 (United States); Magnetic Resonance Research Center, Arizona State University, AZ 85287 (United States); Department of Chemistry and Biochemistry, Arizona State University, AZ 85287 (United States); Mou, Q. [Magnetic Resonance Research Center, Arizona State University, AZ 85287 (United States); Department of Chemistry and Biochemistry, Arizona State University, AZ 85287 (United States); Weber, W. [Department of Physics, Arizona State University, AZ 85287 (United States); Department of Chemistry and Biochemistry, Arizona State University, AZ 85287 (United States); Byrn, S.R. [Department of Industrial and Physical Pharmacy, Purdue University, IN 47907 (United States)

2013-10-16

Highlights: • Acoustic levitation was used to make phase-pure glassy forms of pharmaceutical compounds. • Neutrons, X-rays and NMR were used to characterize the glasses. • The glass comprised of slightly distorted molecules packed in a random network. • Potential for new drug synthesis routes is discussed. - Abstract: Acoustic levitation was used to trap 1–3 mm diameter drops of Probucol and other pharmaceutical materials in containerless conditions. Samples were studied in situ using X-ray diffraction and ex situ using neutron diffraction, NMR and DSC techniques. The materials were brought into non-equilibrium states by supersaturating solutions or by supercooling melts. The glass transition and crystallization temperatures of glassy Probucol were 29 ± 1 and 71 ± 1 °C respectively. The glassy form was stable with a shelf life of at least 8 months. A neutron/X-ray difference function of the glass showed that while molecular sub-groups remain rigid, many of the hydrogen correlations observed in the crystal become smeared out in the disordered material. The glass is principally comprised of slightly distorted Form I Probucol molecules with disordered packing rather than large changes in the individual molecular structure. Avoiding surface contact-induced nucleation provided access to highly non-equilibrium phases and enabled synthesis of phase-pure glasses.

Different glassy states, as indicated by a violation of the generalized Cauchy relation

Energy Technology Data Exchange (ETDEWEB)

Krueger, J K [Laboratoire Europeen de Recherche Universitaire Saarland-Lorraine (LERUSL), Universitaet des Saarlandes, Fakultaet fuer Physik und Elektrotechnik 7.2, Gebaeude 38, D-66041 Saarbruecken (Germany); Britz, T [Laboratoire Europeen de Recherche Universitaire Saarland-Lorraine (LERUSL), Universitaet des Saarlandes, Fakultaet fuer Physik und Elektrotechnik 7.2, Gebaeude 38, D-66041 Saarbruecken (Germany); Coutre, A le [Laboratoire Europeen de Recherche Universitaire Saarland-Lorraine (LERUSL), Universitaet des Saarlandes, Fakultaet fuer Physik und Elektrotechnik 7.2, Gebaeude 38, D-66041 Saarbruecken (Germany); Baller, J [Laboratoire Europeen de Recherche Universitaire Saarland-Lorraine (LERUSL), Universitaet des Saarlandes, Fakultaet fuer Physik und Elektrotechnik 7.2, Gebaeude 38, D-66041 Saarbruecken (Germany); Possart, W [Universitaet des Saarlandes, Fakultaet fuer Chemie, Pharmazie und Werkstoffwissenschaften 8.15, Gebaeude 22, D-66041 Saarbruecken (Germany); Alnot, P [Laboratoire Europeen de Recherche Universitaire Saarland-Lorraine (LERUSL), Universitaet des Saarlandes, Fakultaet fuer Physik und Elektrotechnik 7.2, Gebaeude 38, D-66041 Saarbruecken (Germany); Sanctuary, R [Centre Universitaire de Luxembourg, Departement des Sciences, Laboratoire 1.19, 162a Avenue de la Faiencerie, L-1511, Luxembourg (Luxembourg)

2003-07-01

Using Brillouin spectroscopy as a probe for high-frequency clamped acoustic properties, a shear modulus c{sub 44}{sup {infinity}} can be measured in addition to the longitudinal modulus c{sub 11}{sup {infinity}} already well above the thermal glass transition. On slow cooling of the liquid through the thermal glass transition temperature T{sub g}, both moduli show a kink-like behaviour and the function c{sub 11}{sup {infinity}} = c{sub 11}{sup {infinity}}(c{sub 44}{sup {infinity}}) follows a generalized Cauchy relation (gCR) defined by the linear relation c{sub 11}{sup {infinity}} = 3c{sub 44}{sup {infinity}} + constant, which completely hides the glass transition. In this work we show experimentally that on fast cooling this linear transformation becomes violated within the glassy state, but that thermal ageing drives the elastic coefficients towards the gCR, i.e. towards a unique glassy state.

Formulation of thermodynamics for the glassy state : Configurational energy as a modest source of energy

NARCIS (Netherlands)

Nieuwenhuizen, T.M.

2001-01-01

Glass is an under-cooled liquid that very slowly relaxes towards the equilibrium crystalline state. Its energy balance is ill understood, since it is widely believed that the glassy state cannot be described thermodynamically. However, the classical paradoxes involving the Ehrenfest relations and

The sorption induced glass transition in amorphous glassy polymers

NARCIS (Netherlands)

van der Vegt, N.F.A.; Wessling, Matthias; Strathmann, H.; Briels, Willem J.

1999-01-01

Sorption of CO2 in both the glassy and the rubbery state of an amorphous polyethylenelike polymer was investigated using molecular dynamics simulations. The temperature was chosen such that the system was in its glassy state at low solute concentrations and its rubbery state at large solute

Glassy selenium at high pressure: Le Chatelier's principle still works

Science.gov (United States)

Brazhkin, V. V.; Tsiok, O. B.

2017-10-01

Selenium is the only easily vitrified elementary substance. Numerous experimental studies of glassy Se (g -Se) at high pressures show a large spread in the data on the compressibility and electrical resistivity of g -Se. Furthermore, H. Liu et al. [Proc. Natl. Acad. Sci. USA 105, 13229 (2008), 10.1073/pnas.0806857105] have arrived at the surprising conclusion that the volume of glass increases during pressure-induced crystallization. We have performed high-precision measurements of the specific volume and electrical resistivity of glassy selenium (g -Se) at high hydrostatic pressures up to 9 GPa. The measured bulk modulus at normal pressure is B =(9.0 5 ±0.15 ) GPa and its pressure derivative is BP'=6.4 ±0.2 . In the pressure range P <3 GPa, glassy selenium has an anomalously large negative second derivative of the bulk modulus. The electrical resistivity of g -Se decreases almost exponentially with increasing pressure and reaches 20 Ω cm at a pressure of 8.75 GPa. The inelastic behavior and weak relaxation of the volume for g -Se begin at pressures above 3.5 GPa; the volume and logarithm of the electrical resistivity relax significantly (logarithmically with the time) at pressures above 8 GPa. Bulk measurements certainly indicate that the volume of g -Se glass in the crystallization pressure range is larger than the volumes of both appearing crystalline phases (by 2% and 4%). Therefore, the "volume expansion phenomenon" suggested in [H. Liu et al., Proc. Natl. Acad. Sci. USA 105, 13229 (2008), 10.1073/pnas.0806857105] is not observed, and the pressure-induced crystallization of glassy selenium is consistent with the laws of thermodynamics.

New model system in radiation cryochemistry:. hyperquenched glassy water

Science.gov (United States)

Bednarek, Janusz; Plonka, Andrzej; Hallbrucker, Andreas; Mayer, Erwin

1999-08-01

Radicals generated by high-energy irradiation of liquid water, short-lived at ambient temperature, can be studied at cryogenic temperatures after irradiating water and dilute aqueous solutions in their glassy states which can be obtained by so-called hyperquenching of the liquids at cooling rates of ˜10 6-10 7 K s -1. In the glassy states of hyperquenched dilute aqueous solutions there is no problem with phase separation and radiolysis of glassy water is quite distinct from radiolysis of polycrystalline ice obtained from liquid water on slow-cooling in liquid nitrogen.

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.

Thermonuclear reactor materials composed of glassy carbons

International Nuclear Information System (INIS)

Kazumata, Yukio.

1979-01-01

Purpose: To improve the durability to plasma radiation by the use of glassy carbon as the structural materials for the first wall and the blanket in thermonuclear devices. Constitution: The glassy carbon (glass-like carbon) is obtained by forming specific organic substances into a predetermined configuration and carbonizing them by heat decomposition under special conditions. They are impermeable carbon material of 1.40 - 1.70 specific gravity, less graphitizable and being almost in isotropic crystal forms in which isotropic structure such as in graphite is scarcely observed. They have an extremely high hardness, are less likely to be damaged when exposed to radiation and have great strength and corrosion resistance. Accordingly, the service life of the reactor walls and the likes can remarkably be increased by using the materials. (Horiuchi, T.)

Comparison of glassy slag waste forms produced in laboratory crucibles and in a bench-scale plasma furnace

International Nuclear Information System (INIS)

Feng, X.; Wronkiewicz, D.J.; Brown, N.R.; Gong, M.; Whitworth, C.; Filius, K.; Battleson, D.

1994-01-01

Vitrification is currently the best demonstrated available technology for the disposal of high-level radioactive wastes. An innovative vitrification approach known as minimum additive waste stabilization (MAWS) is being developed. Both homogeneous glass and glassy slags have been used in implementing MAWS. Glassy slags (vitro-ceramics) are glass-crystal composites, and they are composed of various metal oxide crystalline phases embedded in an aluminosilicate glass matrix. Glassy slags with compositions developed in crucible melts at Argonne National Laboratory (ANL) were successfully produced in a bench-scale Retech plasma centrifugal furnace (PCF) by MSE, Inc. Detailed examinations of these materials showed that the crucible melts and the PCF produced similar glass and crystalline phases. The two sets of glassy slags exhibited similar chemical durability in terms of normalized releases of their major components. The slags produced in the PCF furnace using metals were usually less oxidized, although this had no effect on the corrosion behavior of the major components of the slags. However, the normalized release rate of cerium was initially lower for the PCF slags. This difference diminished with time as the redox sates of the metal oxides in slags began to be controlled by exposure to air in the tests. Thus, the deference in cerium release due to the differences in slag redox state may be transitory. The cerium solubility is a complex function of redox state and solution pH and Eh

Glassy Dynamics

DEFF Research Database (Denmark)

Jensen, Henrik J.; Sibani, Paolo

2007-01-01

The term glassy dynamics is often used to refer to the extremely slow relaxation observed in several types of many component systems. The time span needed to reach a steady, time independent, state will typically be far beyond experimentally accessible time scales. When melted alloys are cooled...... down they typically do not enter a crystalline ordered state. Instead the atoms retain the amorphous arrangement characteristic of the liquid high temperature phase while the mobility of the molecules decreases very many orders of magnitude. This colossal change in the characteristic dynamical time...

Relaxation and crystallization of amorphous carbamazepine studied by terahertz pulsed spectroscopy

DEFF Research Database (Denmark)

Zeitler, J Axel; Taday, Philip F; Pepper, Michael

2007-01-01

At the example of carbamazepine the crystallization of a small organic molecule from its amorphous phase was studied using in situ variable temperature terahertz pulsed spectroscopy (TPS). Even though terahertz spectra of disordered materials in the glassy state exhibit no distinct spectral featu...

Dislocations and vacancies in two-dimensional mixed crystals of spheres and dimers

KAUST Repository

Gerbode, Sharon J.

2010-10-15

In colloidal crystals of spheres, dislocation motion is unrestricted. On the other hand, recent studies of relaxation in crystals of colloidal dimer particles have demonstrated that the dislocation dynamics in such crystals are reminiscent of glassy systems. The observed glassy dynamics arise as a result of dislocation cages formed by certain dimer orientations. In the current study, we use experiments and simulations to investigate the transition that arises when a pure sphere crystal is doped with an increasing concentration of dimers. Specifically, we focus on both dislocation caging and vacancy motion. Interestingly, we find that any nonzero fraction of dimers introduces finite dislocation cages, suggesting that glassy dynamics are present for any mixed crystal. However, we have also identified a vacancy-mediated uncaging mechanism for releasing dislocations from their cages. This mechanism is dependent on vacancy diffusion, which slows by orders of magnitude as the dimer concentration is increased. We propose that in mixed crystals with low dimer concentrations vacancy diffusion is fast enough to uncage dislocations and delay the onset of glassy dislocation dynamics. © 2010 The American Physical Society.

Dislocations and vacancies in two-dimensional mixed crystals of spheres and dimers

KAUST Repository

Gerbode, Sharon J.; Ong, Desmond C.; Liddell, Chekesha M.; Cohen, Itai

2010-01-01

In colloidal crystals of spheres, dislocation motion is unrestricted. On the other hand, recent studies of relaxation in crystals of colloidal dimer particles have demonstrated that the dislocation dynamics in such crystals are reminiscent of glassy systems. The observed glassy dynamics arise as a result of dislocation cages formed by certain dimer orientations. In the current study, we use experiments and simulations to investigate the transition that arises when a pure sphere crystal is doped with an increasing concentration of dimers. Specifically, we focus on both dislocation caging and vacancy motion. Interestingly, we find that any nonzero fraction of dimers introduces finite dislocation cages, suggesting that glassy dynamics are present for any mixed crystal. However, we have also identified a vacancy-mediated uncaging mechanism for releasing dislocations from their cages. This mechanism is dependent on vacancy diffusion, which slows by orders of magnitude as the dimer concentration is increased. We propose that in mixed crystals with low dimer concentrations vacancy diffusion is fast enough to uncage dislocations and delay the onset of glassy dislocation dynamics. © 2010 The American Physical Society.

Impact of crystallization on the structure and chemical durability of borosilicate glass

International Nuclear Information System (INIS)

Nicoleau, Elodie

2016-01-01

This work describes a new approach to help understand the chemical durability of partially crystallized nuclear waste conditioning matrices. Among the studies carried out on nuclear waste deep geological disposal, long term behavior studies have so far been conducted on homogeneous glassy matrices. However, as the crystalline phases may generate modifications in the chemical composition and properties of such matrices, the description and a better understanding of their effects on the chemical durability of waste packages are of primary importance. A protocol to study the durability of heterogeneous model matrices of nuclear interest containing different types of crystalline phases was developed. It is based on a detailed description of the morphology, microstructure and structure of the glassy matrix and crystalline phases, and on the study of various alteration regimes. Three crystal phases that may form when higher concentrations of waste are immobilized in Uranium Oxide type conditioning glasses were studied: alkali and alkaline earth molybdates, rare earth silicates and ruthenium oxide. The results highlight the roles of the composition and the structure of the surrounding glassy matrix as the parameters piloting the alteration kinetics of the partially crystallized glassy matrices. This behavior is identical whatever the nature of the crystalline phases, as long as these phases do not lead to a composition gradient and do not percolate within the glassy matrix. Given these results, a methodology to study partially crystallized matrices with no composition gradient is then suggested. Its key development lies firstly in the evaluation of the behavior of partially crystallized matrices through the experimental study of the residual glassy matrix in various alteration regimes. This methodology may be adapted to the case of new glass formulations with more complex compositions (e.g. highly waste-loaded glass), which may contain crystals formed during cooling

Time evolution of quenched state and correlation to glassy effects

International Nuclear Information System (INIS)

Kilic, K.; Kilic, A.; Altinkok, A.; Yetis, H.; Cetin, O.; Durust, Y.

2005-01-01

In this work, dynamic changes generated by the driving current were studied in superconducting bulk polycrystalline YBCO sample via transport relaxation measurements (V-t curves). The evolution of nonlinear V-t curves was interpreted in terms of the formation of resistive and nonresistive flow channels and the spatial reorganization of the transport current in a multiply connected network of weak-link structure. The dynamic re-organization of driving current could cause an enhancement or suppression in the superconducting order parameter due to the magnitude of the driving current and coupling strength of weak-link structure along with the chemical and anisotropic states of the sample as the time proceeds. A nonzero voltage decaying with time, correlated to the quenched state, was recorded when the magnitude of initial driving current is reduced to a finite value. It was found that, after sufficiently long waiting time, the evolution of the quenched state could result in a superconducting state, depending on the magnitude of the driving current and temperature. We showed that the decays in voltage over time are consistent with an exponential time dependence which is related to the glassy state. Further, the effect of doping of organic material Bis dimethyl-glyoximato Copper (II) to YBCO could be monitored apparently via the comparison of the V-t curves corresponding to doped and undoped YBCO samples

Early stage crystallization kinetics in metallic glass-forming alloys

International Nuclear Information System (INIS)

Louzguine-Luzgin, Dmitri V.

2014-01-01

Highlights: • Heterogeneous nucleation may precede the homogeneous one in an alloy. • High kinetic constants and the nucleation rate at the initial stage. • Metallic glasses have heterogeneous nucleation sites which saturate later. -- Abstract: The crystallization kinetics and structural changes of a few metallic glassy alloys were monitored using X-ray diffraction, transmission electron microscopy, differential scanning and isothermal calorimetry methods. Microstructural observations were used to estimate the nucleation and growth rates. A clear comparison of the differences in the crystallization kinetics in the metallic glassy samples is observed at the early and later crystallization stages

Ice cloud processing of ultra-viscous/glassy aerosol particles leads to enhanced ice nucleation ability

Directory of Open Access Journals (Sweden)

R. Wagner

2012-09-01

Full Text Available The ice nucleation potential of airborne glassy aqueous aerosol particles has been investigated by controlled expansion cooling cycles in the AIDA aerosol and cloud chamber of the Karlsruhe Institute of Technology at temperatures between 247 and 216 K. Four different solutes were used as proxies for oxygenated organic matter found in the atmosphere: raffinose, 4-hydroxy-3-methoxy-DL-mandelic acid (HMMA, levoglucosan, and a multi-component mixture of raffinose with five dicarboxylic acids and ammonium sulphate. Similar to previous experiments with citric acid aerosols, all particles were found to nucleate ice heterogeneously before reaching the homogeneous freezing threshold provided that the freezing cycles were started well below the respective glass transition temperatures of the compounds; this is discussed in detail in a separate article. In this contribution, we identify a further mechanism by which glassy aerosols can promote ice nucleation below the homogeneous freezing limit. If the glassy aerosol particles are probed in freezing cycles started only a few degrees below their respective glass transition temperatures, they enter the liquid regime of the state diagram upon increasing relative humidity (moisture-induced glass-to-liquid transition before being able to act as heterogeneous ice nuclei. Ice formation then only occurs by homogeneous freezing at elevated supersaturation levels. When ice forms the remaining solution freeze concentrates and re-vitrifies. If these ice cloud processed glassy aerosol particles are then probed in a second freezing cycle at the same temperature, they catalyse ice formation at a supersaturation threshold between 5 and 30% with respect to ice. By analogy with the enhanced ice nucleation ability of insoluble ice nuclei like mineral dusts after they nucleate ice once, we refer to this phenomenon as pre-activation. We propose a number of possible explanations for why glassy aerosol particles that have re

Encoding Gaussian Curvature in Glassy and Elastomeric Liquid Crystal Solids (Postprint)

Science.gov (United States)

2016-05-04

attention to director fields of the form n = cosψ(x2) ê1 + sinψ(x2) ê2, whose alignment angle field varies only with respect to one of the...λ−2 − λ2ν)/L2 < 0. (Online version in colour .) For a fixed two-dimensional metric, the problem of identifying equilibrium configurations that...length of 10 mm. (b) Positive (left) and negative (right) Gaussian curvature in 15µm thick glassy LC solid film at 175◦C. (Online version in colour .) (b

Structural characterization and aging of glassy pharmaceuticals made using acoustic levitation.

Science.gov (United States)

Benmore, Chris J; Weber, J K R; Tailor, Amit N; Cherry, Brian R; Yarger, Jeffery L; Mou, Qiushi; Weber, Warner; Neuefeind, Joerg; Byrn, Stephen R

2013-04-01

Here, we report the structural characterization of several amorphous drugs made using the method of quenching molten droplets suspended in an acoustic levitator. (13) C NMR, X-ray, and neutron diffraction results are discussed for glassy cinnarizine, carbamazepine, miconazole nitrate, probucol, and clotrimazole. The (13) C NMR results did not find any change in chemical bonding induced by the amorphization process. High-energy X-ray diffraction results were used to characterize the ratio of crystalline to amorphous material present in the glasses over a period of 8 months. All the glasses were stable for at least 6 months except carbamazepine, which has a strong tendency to crystallize within a few months. Neutron and X-ray pair distribution function analyses were applied to the glassy materials, and the results were compared with their crystalline counterparts. The two diffraction techniques yielded similar results in most cases and identified distinct intramolecular and intermolecular correlations. The intramolecular scattering was calculated based on the crystal structure and fit to the measured X-ray structure factor. The resulting intermolecular pair distribution functions revealed broad-nearest and next-nearest neighbor molecule-molecule correlations. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 102:1290-1300, 2013. Copyright © 2013 Wiley Periodicals, Inc.

Crystal Nucleation and Crystal Growth and Mass Transfer in Internally Mixed Sucrose/NaNO3 Particles.

Science.gov (United States)

Ji, Zhi-Ru; Zhang, Yun; Pang, Shu-Feng; Zhang, Yun-Hong

2017-10-19

Secondary organic aerosols (SOA) can exist in a glassy or semisolid state under low relative humidity (RH) conditions, in which the particles show nonequilibrium kinetic characteristics with changing ambient RH. Here, we selected internally mixed sucrose/NaNO 3 droplets with organic to inorganic molar ratios (OIRs) of 1:8, 1:4, 1:2, and 1:1 as a proxy for multicomponent ambient aerosols to study crystal nucleation and growth processes and water transport under a highly viscous state with the combination of an RH-controlling system and a vacuum Fourier transform infrared (FTIR) spectrometer. The initial efflorescence RH (ERH) of NaNO 3 decreased from ∼45% for pure NaNO 3 droplets to ∼38.6 and ∼37.9% for the 1:8 and 1:4 sucrose/NaNO 3 droplets, respectively, while no crystallization of NaNO 3 occurred for the 1:2 and 1:1 droplets in the whole RH range. Thus, the addition of sucrose delayed the ERH and even completely inhibited nucleation of NaNO 3 in the mixed droplets. In addition, the crystal growth of NaNO 3 was suppressed in the 1:4 and 1:8 droplets most likely due to the slow diffusion of Na + and NO 3 - ions at low RH. Water uptake/release of sucrose/NaNO 3 particles quickly arrived at equilibrium at high RH, while the hygroscopic process was kinetically controlled under low RH. The half-time ratio between the liquid water content and the RH was used to describe the mass transfer behavior. For the 1:1 droplets, no mass limitation was observed with the ratio approaching to 1 when the RH was higher than 53%. The ratio increased 1 order of magnitude under an ultraviscous state with RH ranging from 53 to 15% and increased a further 1 order of magnitude at RH < 15% under a glassy state.

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.

Deformation and structure evolution of glassy poly(lactic acid) below the glass transition temperature

DEFF Research Database (Denmark)

Zhou, Chengbo; Li, Hongfei; Zhang, Yao

2015-01-01

, the onset of the mesocrystal formation is delayed to a higher strain value, whereas corresponding to the same critical orientation degree of amorphous chains (f(am) approximate to 0.45). The DSC results indicated that the post-T-g endothermic peak corresponding to the melting of mesocrystal appears...... and shifts to a higher temperature with increasing stretching temperature, followed by the down-shifts (to a lower temperature) of the exothermic peak of cold crystallization of PLA. The appearance of a small exothermic peak just before the melting peak related to the transition of the alpha' to alpha...... crystal implies the formation of an alpha' crystal during cold crystallization in the drawn PLA samples. The structure evolution of glassy PLA stretched below T-g was discussed in details....

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.

The mechanism of deceleration of nucleation and crystal growth by the small addition of transition metals to lithium disilicate glasses

Science.gov (United States)

Thieme, Katrin; Avramov, Isak; Rüssel, Christian

2016-01-01

The addition of small amounts of niobium or tantalum oxide to lithium disilicate glass provokes a drastic decrease of the steady-state nucleation rates and the crystal growth velocities. The viscosity of the residual glassy matrix is considered as a function of the crystallization degree in the course of a non-isothermal crystallization. For simplification, a homogeneous distribution of the added oxides in the glass matrix is assumed. While the viscosity initially decreases, it significantly increases again for higher crystallization degrees hindering crystal growth. However, it was shown that the additives are enriched at the crystal interface. Several possible reasons for the inhibition of nucleation and growth kinetics such as viscosity, interfacial energy crystal/glassy phase, thermodynamic driving force or impingement rate are discussed. Since the crystallization front is blocked by the additives the impingement rate is decreased with increasing additive concentration. Since small concentrations of Nb2O5 and Ta2O5 have a drastic effect on the nucleation, these components should be enriched at the interface crystal/glass. This will only take place, if it leads to a decrease in the interfacial energy. Since this effect alone should result in an increase of the nucleation rate, it must be overcompensated by kinetic effects. PMID:27150844

Similar and dissimilar friction welding of Zr-Cu-Al bulk glassy alloys

International Nuclear Information System (INIS)

Shin, Hyung-Seop; Park, Jung-Soo; Jung, Yoon-Chul; Ahn, Jung-Ho; Yokoyama, Yoshihiko; Inoue, Akihisa

2009-01-01

The friction welding of three kinds of Zr-Cu-Al bulk glassy alloys (BGAs) which show eutectic or hypoeutectic compositions to similar and dissimilar BGAs and crystalline metals has been tried. The shape and volume of the protrusion formed at the weld interface were investigated. In order to characterize the friction welded interface, micrographic observation and X-ray diffraction analysis on the weld cross-section were carried out. A successful joining of Zr-Cu-Al bulk glassy alloys to similar and dissimilar BGAs was achieved without occurrence of crystallizations at the weld interface through the precise control of friction conditions. In addition, the joining of Zr 50 Cu 40 Al 10 BGA to crystalline alloys was tried, but it was only successful for specific material combinations. The residual strength after welding of dissimilar BGAs was evaluated by the four-point bending test.

Glassy aerosols with a range of compositions nucleate ice heterogeneously at cirrus temperatures

Directory of Open Access Journals (Sweden)

T. W. Wilson

2012-09-01

Full Text Available Atmospheric secondary organic aerosol (SOA is likely to exist in a semi-solid or glassy state, particularly at low temperatures and humidities. Previously, it has been shown that glassy aqueous citric acid aerosol is able to nucleate ice heterogeneously under conditions relevant to cirrus in the tropical tropopause layer (TTL. In this study we test if glassy aerosol distributions with a range of chemical compositions heterogeneously nucleate ice under cirrus conditions. Three single component aqueous solution aerosols (raffinose, 4-hydroxy-3-methoxy-DL-mandelic acid (HMMA and levoglucosan and one multi component aqueous solution aerosol (raffinose mixed with five dicarboxylic acids and ammonium sulphate were studied in both the liquid and glassy states at a large cloud simulation chamber. The investigated organic compounds have similar functionality to oxidised organic material found in atmospheric aerosol and have estimated temperature/humidity induced glass transition thresholds that fall within the range predicted for atmospheric SOA. A small fraction of aerosol particles of all compositions were found to nucleate ice heterogeneously in the deposition mode at temperatures relevant to the TTL (<200 K. Raffinose and HMMA, which form glasses at higher temperatures, nucleated ice heterogeneously at temperatures as high as 214.6 and 218.5 K respectively. We present the calculated ice active surface site density, n_s, of the aerosols tested here and also of glassy citric acid aerosol as a function of relative humidity with respect to ice (RH_i. We also propose a parameterisation which can be used to estimate heterogeneous ice nucleation by glassy aerosol for use in cirrus cloud models up to ~220 K. Finally, we show that heterogeneous nucleation by glassy aerosol may compete with ice nucleation on mineral dust particles in mid-latitudes cirrus.

Structural state diagram of concentrated suspensions of jammed soft particles in oscillatory shear flow

Science.gov (United States)

Khabaz, Fardin; Cloitre, Michel; Bonnecaze, Roger T.

2018-03-01

In a recent study [Khabaz et al., Phys. Rev. Fluids 2, 093301 (2017), 10.1103/PhysRevFluids.2.093301], we showed that jammed soft particle glasses (SPGs) crystallize and order in steady shear flow. Here we investigate the rheology and microstructures of these suspensions in oscillatory shear flow using particle-dynamics simulations. The microstructures in both types of flows are similar, but their evolutions are very different. In both cases the monodisperse and polydisperse suspensions form crystalline and layered structures, respectively, at high shear rates. The crystals obtained in the oscillatory shear flow show fewer defects compared to those in the steady shear. SPGs remain glassy for maximum oscillatory strains less than about the yield strain of the material. For maximum strains greater than the yield strain, microstructural and rheological transitions occur for SPGs. Polydisperse SPGs rearrange into a layered structure parallel to the flow-vorticity plane for sufficiently high maximum shear rates and maximum strains about 10 times greater than the yield strain. Monodisperse suspensions form a face-centered cubic (FCC) structure when the maximum shear rate is low and hexagonal close-packed (HCP) structure when the maximum shear rate is high. In steady shear, the transition from a glassy state to a layered one for polydisperse suspensions included a significant induction strain before the transformation. In oscillatory shear, the transformation begins to occur immediately and with different microstructural changes. A state diagram for suspensions in large amplitude oscillatory shear flow is found to be in close but not exact agreement with the state diagram for steady shear flow. For more modest amplitudes of around one to five times the yield strain, there is a transition from a glassy structure to FCC and HCP crystals, at low and high frequencies, respectively, for monodisperse suspensions. At moderate frequencies, the transition is from glassy to HCP via

How mechanical behavior of glassy polymers enables us to characterize melt deformation: elastic yielding in glassy state after melt stretching?

Science.gov (United States)

Wang, Shi-Qing; Zhao, Zhichen; Tsige, Mesfin; Zheng, Yexin

Fast melt deformation well above the glass transition temperature Tg is known to produce elastic stress in an entangled polymer due to the chain entropy loss at the length scale of the network mesh size. Here chains of high molecular weight are assumed to form an entanglement network so that such a polymer behaves transiently like vulcanized rubber capable of affine deformation. We consider quenching a melt-deformed glassy polymer to well below Tg to preserve the elastic stress. Upon heating such a sample to Tg, the sample can return to the shape it took before melt deformation. This is the basic principle behind the design of all polymer-based shape-memory materials. This work presents intriguing evidence based on both experiment and computer simulation that the chain network, deformed well above Tg, can drive the glassy polymer to undergo elastic yielding. Our experimental systems include polystyrene, poly(methyl methacrylate) and polycarbonate; the molecular dynamics simulation is based on Kremer-Grest bead-spring model. National Science Foundation (DMR-1444859 and DMR-1609977).

Determining the structural relaxation times deep in the glassy state of the pharmaceutical Telmisartan

Energy Technology Data Exchange (ETDEWEB)

Adrjanowicz, K; Paluch, M [Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice (Poland); Ngai, K L [Naval Research Laboratory, Washington, DC 20375-5320 (United States)

2010-03-31

By using the dielectric relaxation method proposed recently by Casalini and Roland (2009 Phys. Rev. Lett. 102 035701), we were able to determine the structural alpha-relaxation times deep in the glassy state of the pharmaceutical, Telmisartan. Normally, deep in the glassy state tau{sub a}lpha is so long that it cannot be measured but tau{sub b}eta, which is usually much shorter, can be directly determined. The method basically takes advantage of the connection between the alpha-relaxation and the secondary beta-relaxation of the Johari-Goldstein kind, including a relation between their relaxation times tau{sub a}lpha and tau{sub b}eta, respectively. Thus, tau{sub a}lpha of Telmisartan were determined by monitoring the change of the dielectric beta-loss, epsilon'', with physical aging time at temperatures well below the vitrification temperature. The values of tau{sub a}lpha were compared with those expected by the coupling model (CM). Unequivocal comparison cannot be made in the case of Telmisartan because its beta-loss peak is extremely broad, and the CM predicts only an order of magnitude agreement between the primitive relaxation frequency and the beta-peak frequency. We also made an attempt to analyze all isothermal and aging susceptibility data after transformation into the electric modulus representation. The tau{sub a}lpha found in the glass state by using the method of Casalini and Roland in the modulus representation are similar to those obtained in the susceptibility representation. However, it is remarkable that the stretching parameter beta{sub KWWM} = 0.51 in the electric modulus representation gives more precise fits to the aging data than in the susceptibility representation with beta{sub KWW} = 0.61. Our results suggest that the electric modulus representation may be useful as an alternative to analyze aging data, especially in the case of highly polar glassformers having a large ratio of low frequency and high frequency dielectric

Glassy behavior in the layered perovskites La2−xSrxCoO4(1.1≤x≤1.3)

International Nuclear Information System (INIS)

Mukherjee, S.; Mukherjee, Rajarshi; Banerjee, S.; Ranganathan, R.; Kumar, Uday

2012-01-01

The glassy behavior of the phase segregated state in the layered cobaltite La 2−x Sr x CoO 4 has been studied. The role of the inter-cluster interactions as well as the disordered spins at the paramagnetic–ferromagnetic interface, behind the observed glassy behavior have been investigated. The disordered spins at the interface appear to be strongly pinned, and they contribute little to the observed glassy behavior. On the other hand, the inter-cluster interactions play the key role. Both the Co 4+ and Co 3+ ions are in the intermediate spin state. - Highlights: ► Phase segregated state of cobaltite La 2−x Sr x CoO 4 for (1.1≤x≤1.3) to find the origin of the observed glassy behavior. ► Result of the frequency dependent ac susceptibility measurement excludes the possibility of any spin glass phase, hints strong inter-cluster interactions. ► Relaxation experiments confirm the system to be a collection of clusters with two preferred sizes. ► The glassy behavior originates from strong inter-cluster interactions.

Permeation of Mixed Penetrants through Glassy Polymer Membranes.

Science.gov (United States)

1985-03-15

and LOPE. Also, ESCA was used in conjunction with plasma etching to determine the effects of the gas phase fluorine concentration and fluorination...at 35 3C. ARD-AISS5 65 PERMEATION OF MIXED PENETRANTS THROUGH GLASSY POLYMER 213 MENBRANES (U) NORTH CAROLINA STATE UNIV AT RALEIGH R T CHERN ET AL. 15

Single-Photon Source for Quantum Information Based on Single Dye Molecule Fluorescence in Liquid Crystal Host

International Nuclear Information System (INIS)

Lukishova, S.G.; Knox, R.P.; Freivald, P.; McNamara, A.; Boyd, R.W.; Stroud, Jr. C.R.; Schmid, A.W.; Marshall, K.L.

2006-01-01

This paper describes a new application for liquid crystals: quantum information technology. A deterministically polarized single-photon source that efficiently produces photons exhibiting antibunching is a pivotal hardware element in absolutely secure quantum communication. Planar-aligned nematic liquid crystal hosts deterministically align the single dye molecules which produce deterministically polarized single (antibunched) photons. In addition, 1-D photonic bandgap cholesteric liquid crystals will increase single-photon source efficiency. The experiments and challenges in the observation of deterministically polarized fluorescence from single dye molecules in planar-aligned glassy nematic-liquid-crystal oligomer as well as photon antibunching in glassy cholesteric oligomer are described for the first time

Two-phonon bound states in imperfect crystals

International Nuclear Information System (INIS)

Behera, S.N.; Samsur, Sk.

1980-01-01

The question of the occurrence of two-phonon bound states in imperfect crystals is investigated. It is shown that the anharmonicity mediated two-phonon bound state which is present in perfect crystals gets modified due to the presence of impurities. Moreover, the possibility of the occurrence of a purely impurity mediated two-phonon bound state is demonstrated. The bound state frequencies are calculated using the simple Einstein oscillator model for the host phonons. The two-phonon density of states for the imperfect crystal thus obtained has peaks at the combination and difference frequencies of two host phonons besides the peaks at the bound state frequencies. For a perfect crystal the theory predicts a single peak at the two-phonon bound state frequency in conformity with experimental observations and other theoretical calculations. Experimental data on the two-phonon infrared absorption and Raman scattering from mixed crystals of Gasub(1-c)Alsub(c)P and Gesub(1-c)Sisub(c) are analysed to provide evidence in support of impurity-mediated two-phonon bound states. The relevance of the zero frequency (difference spectrum) peak to the central peak, observed in structural phase transitions, is conjectured. (author)

Glassy carbon coated graphite for nuclear applications

International Nuclear Information System (INIS)

Delpeux S; Cacciaguerra T; Duclaux L

2005-01-01

Taking into account the problems caused by the treatment of nuclear wastes, the molten salts breeder reactors are expected to a great development. They use a molten fluorinated salt (mixture of LiF, BeF 2 , ThF 4 , and UF 4 ) as fuel and coolant. The reactor core, made of graphite, is used as a neutrons moderator. Despite of its compatibility with nuclear environment, it appears crucial to improve the stability and inertness of graphite against the diffusion of chemicals species leading to its corrosion. One way is to cover the graphite surface by a protective impermeable deposit made of glassy carbon obtained by the pyrolysis of phenolic resin or polyvinyl chloride precursors. The main difficulty in the synthesis of glassy carbon is to create exclusively, in the primary pyrolysis product, a micro-porosity of about twenty Angstroms which closes later at higher temperature. Therefore, the evacuation of the volatile products occurring mainly between 330 and 600 C, must progress slowly to avoid the material to crack. In this study, the optimal parameters for the synthesis of glassy carbon as well as glassy carbon deposits on nuclear-type graphite pieces are discussed. Both thermal treatment of phenolic and PVC resins have been performed. The structure and micro-texture of glassy carbon have been investigated by X-ray diffraction, scanning and transmission electron microscopies and helium pycno-metry. Glassy carbon samples (obtained at 1200 C) show densities ranging from 1.3 to 1.55 g/cm 3 and closed pores with nano-metric size (∼ 5 to 10 nm) appear clearly on the TEM micrographs. Then, a thermal treatment to 2700 C leads to the shrinkage of the entangled graphene ribbons, in good agreement with the proposed texture model for glassy carbon. Glassy carbon deposits on nuclear graphite have been developed by an impregnation method. The uniformity of the deposit depends clearly on the surface texture and the chemistry of the graphite substrate. The deposit regions where

Glassy carbon coated graphite for nuclear applications

Energy Technology Data Exchange (ETDEWEB)

Delpeux, S.; Cacciaguerra, T.; Duclaux, L. [Orleans Univ., CRMD, CNRS, 45 (France)

2005-07-01

Taking into account the problems caused by the treatment of nuclear wastes, the molten salts breeder reactors are expected to a great development. They use a molten fluorinated salt (mixture of LiF, BeF{sub 2}, ThF{sub 4}, and UF{sub 4}) as fuel and coolant. The reactor core, made of graphite, is used as a neutrons moderator. Despite of its compatibility with nuclear environment, it appears crucial to improve the stability and inertness of graphite against the diffusion of chemicals species leading to its corrosion. One way is to cover the graphite surface by a protective impermeable deposit made of glassy carbon obtained by the pyrolysis of phenolic resin [1,2] or polyvinyl chloride [3] precursors. The main difficulty in the synthesis of glassy carbon is to create exclusively, in the primary pyrolysis product, a micro-porosity of about twenty Angstroms which closes later at higher temperature. Therefore, the evacuation of the volatile products occurring mainly between 330 and 600 C, must progress slowly to avoid the material to crack. In this study, the optimal parameters for the synthesis of glassy carbon as well as glassy carbon deposits on nuclear-type graphite pieces are discussed. Both thermal treatment of phenolic and PVC resins have been performed. The structure and micro-texture of glassy carbon have been investigated by X-ray diffraction, scanning and transmission electron microscopies and helium pycno-metry. Glassy carbon samples (obtained at 1200 C) show densities ranging from 1.3 to 1.55 g/cm{sup 3} and closed pores with nano-metric size ({approx} 5 to 10 nm) appear clearly on the TEM micrographs. Then, a thermal treatment to 2700 C leads to the shrinkage of the entangled graphene ribbons (Fig 1), in good agreement with the proposed texture model for glassy carbon (Fig 2) [4]. Glassy carbon deposits on nuclear graphite have been developed by an impregnation method. The uniformity of the deposit depends clearly on the surface texture and the chemistry

Effect of cooling rate on microstructure and deformation behavior of Ti-based metallic glassy/crystalline powders

Energy Technology Data Exchange (ETDEWEB)

Wang, D.J. [State Key Laboratory of Advanced Welding Production Technology, Harbin Institute of Technology, Harbin 150001 (China); School of Mechanical and Mining Engineering, University of Queensland, Brisbane, QLD 4072 (Australia); Huang, Y.J. [State Key Laboratory of Advanced Welding Production Technology, Harbin Institute of Technology, Harbin 150001 (China); Shen, J., E-mail: junshen@hit.edu.cn [State Key Laboratory of Advanced Welding Production Technology, Harbin Institute of Technology, Harbin 150001 (China); Wu, Y.Q.; Huang, H. [School of Mechanical and Mining Engineering, University of Queensland, Brisbane, QLD 4072 (Australia); Zou, J., E-mail: j.zou@uq.edu.au [School of Mechanical and Mining Engineering, University of Queensland, Brisbane, QLD 4072 (Australia); Centre for Microscopy and Microanalysis, University of Queensland, Brisbane, QLD 4072 (Australia)

2010-08-20

The microstructures and deformation behavior of Ti-based metallic powders were comprehensively investigated. It has been found that, with increasing the powder size, the phase constituent alters from pure glassy to glassy with crystalline phases (face centered cubic structured NiSnZr and hexagonal structured Ti{sub 3}Sn phases). Our results suggest that the synergetic effect of the thermodynamics and kinetics determines the subsequent characteristics of the crystalline precipitations. Through comparative nanoindentation tests, it was found that the small powders exhibit more pop-in events and a larger pile-up ratio, suggesting that the plastic deformation of the metallic powders is governed by the combined effects of the free volume and the crystallization, which are determined by the cooling rate.

Effect of high-order multicomponent on formation and properties of Zr-based bulk glassy alloys

Energy Technology Data Exchange (ETDEWEB)

Inoue, A., E-mail: ainouebmg@yahoo.co.jp [International Institute of Green Materials, Josai International University, Togane 283-8555 (Japan); School of Materials Science and Engineering, Tianjin University, Tianjin 300072 (China); Department of Physics, King Abdulaziz University, Jeddah 22254 (Saudi Arabia); Wang, Z.; Louzguine-Luzgin, D.V. [WPI Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Han, Y. [School of Materials Science and Engineering, Tianjin University, Tianjin 300072 (China); Kong, F.L. [International Institute of Green Materials, Josai International University, Togane 283-8555 (Japan); Shalaan, E.; Al-Marzouki, F. [Department of Physics, King Abdulaziz University, Jeddah 22254 (Saudi Arabia)

2015-07-25

Highlights: • A multicomponent Zr{sub 55}Al{sub 10}Fe{sub 6}Co{sub 6}Ni{sub 6}Cu{sub 6}Pd{sub 6}Ag{sub 5} bulk glassy alloy was formed. • The high-order multiplication suppression of the decrease in mechanical strength. • The BGAs show good corrosion resistance and slow growth rate of primary precipitates. - Abstract: We examined the formation, thermal stability, mechanical properties and corrosion behavior of a multicomponent Zr{sub 55}Al{sub 10}Fe{sub 6}Co{sub 6}Ni{sub 6}Cu{sub 6}Pd{sub 6}Ag{sub 5} bulk glassy alloy, with the aim of clarifying the effect of high-order multiplication of the number of components on their properties. The bulk glassy alloy rods of 2 and 6 mm in diameter were formed by suction casting even at the low total content of typical glass-forming 3-d late transition metals like Co, Ni and Cu. The Vickers hardness is different in the center region and in the outer surface region. The difference seems to reflect the relaxation level of glassy structure. The Young’s modulus and the compressive fracture strength are nearly the same for the base Zr{sub 55}Al{sub 10}Ni{sub 5}Cu{sub 30} alloy in spite of the existence of immiscible atomic pairs. Moreover, the multicomponent alloy exhibits better corrosion resistance than that for the base alloy. The glassy phase changes to a supercooled liquid state at 720 K and then starts to crystallize at 754 K with a single exothermic peak, in contrast to the appearance of a wide supercooled liquid region for the base alloy. The primary crystalline phase precipitates with very short incubation time and very low growth rate, which are different from those for the base alloy. The extremely low growth rate of the crystallites is presumably due to the reduction of diffusivity of late transition metal elements resulting from multiplication. Thus, the high-order multiplication has the features of (1) the maintenance of high glass-forming ability even at the lower Co, Ni and Cu content and in the absence of

Shear-transformation-zone theory of linear glassy dynamics.

Science.gov (United States)

Bouchbinder, Eran; Langer, J S

2011-06-01

We present a linearized shear-transformation-zone (STZ) theory of glassy dynamics in which the internal STZ transition rates are characterized by a broad distribution of activation barriers. For slowly aging or fully aged systems, the main features of the barrier-height distribution are determined by the effective temperature and other near-equilibrium properties of the configurational degrees of freedom. Our theory accounts for the wide range of relaxation rates observed in both metallic glasses and soft glassy materials such as colloidal suspensions. We find that the frequency-dependent loss modulus is not just a superposition of Maxwell modes. Rather, it exhibits an α peak that rises near the viscous relaxation rate and, for nearly jammed, glassy systems, extends to much higher frequencies in accord with experimental observations. We also use this theory to compute strain recovery following a period of large, persistent deformation and then abrupt unloading. We find that strain recovery is determined in part by the initial barrier-height distribution, but that true structural aging also occurs during this process and determines the system's response to subsequent perturbations. In particular, we find by comparison with experimental data that the initial deformation produces a highly disordered state with a large population of low activation barriers, and that this state relaxes quickly toward one in which the distribution is dominated by the high barriers predicted by the near-equilibrium analysis. The nonequilibrium dynamics of the barrier-height distribution is the most important of the issues raised and left unresolved in this paper.

Controllable Tamm states in magnetophotonic crystal

International Nuclear Information System (INIS)

Merzlikin, A.M.; Vinogradov, A.P.; Dorofeenko, A.V.; Inoue, M.; Levy, M.; Granovsky, A.B.

2007-01-01

We study the Tamm states existing at the interface of a 1D magnetophotonic crystal made of magneto-optic material and a material with natural anisotropy. It is shown that in such a photonic crystal (PC) Yeh's band gap may exist, which causes a special type of the Tamm state. As this state is due to magneto-optic properties, it is controllable by an external magnetic field

Controllable Tamm states in magnetophotonic crystal

Energy Technology Data Exchange (ETDEWEB)

Merzlikin, A.M. [Institute for Theoretical and Applied Electromagnetics, Russian Academy of Science, 13/19 Izhorskaya ul., 125412 Moscow (Russian Federation); Vinogradov, A.P. [Institute for Theoretical and Applied Electromagnetics, Russian Academy of Science, 13/19 Izhorskaya ul., 125412 Moscow (Russian Federation)]. E-mail: a-vinogr@yandex.ru; Dorofeenko, A.V. [Institute for Theoretical and Applied Electromagnetics, Russian Academy of Science, 13/19 Izhorskaya ul., 125412 Moscow (Russian Federation); Inoue, M. [Department of Electrical and Electronic Engineering, Toyohashi University of Technology, 1-1 Hibari-Ga-Oka, Tempaku, Toyohashi 441-8580 (Japan); Levy, M. [Department of Physics, Michigan Technological University, 1400 Townsend Drive Houghton, MI 49931-1295 (United States); Granovsky, A.B. [Faculty of Physics, M.V. Lomonosov Moscow State University, Vorob' evy Gory, 119992 Moscow (Russian Federation)

2007-05-15

We study the Tamm states existing at the interface of a 1D magnetophotonic crystal made of magneto-optic material and a material with natural anisotropy. It is shown that in such a photonic crystal (PC) Yeh's band gap may exist, which causes a special type of the Tamm state. As this state is due to magneto-optic properties, it is controllable by an external magnetic field.

Density of states functions for photonic crystals

International Nuclear Information System (INIS)

McPhedran, R.C.; McOrist, J.; Sterke, C.M. de; Nicorovici, N.A.; Botten, L.C.; Asatryan, A.A.

2004-01-01

We discuss density of states functions for photonic crystals, in the context of the two-dimensional problem for arrays of cylinders of arbitrary cross section. We introduce the mutual density of states (MDOS), and show that this function can be used to calculate both the local density of states (LDOS), which gives position information for emission of radiation from photonic crystals, and the spectral density of states (SDOS), which gives angular information. We establish the connection between MDOS, LDOS, SDOS and the conventional density of states, which depends only on frequency. We relate all four functions to the band structure and propagating states within the crystal, and give numerical examples of the relation between band structure and density of states functions

Thermal conductivity of Glycerol's liquid, glass, and crystal states, glass-liquid-glass transition, and crystallization at high pressures.

Science.gov (United States)

Andersson, Ove; Johari, G P

2016-02-14

To investigate the effects of local density fluctuations on phonon propagation in a hydrogen bonded structure, we studied the thermal conductivity κ of the crystal, liquid, and glassy states of pure glycerol as a function of the temperature, T, and the pressure, p. We find that the following: (i) κcrystal is 3.6-times the κliquid value at 140 K at 0.1 MPa and 2.2-times at 290 K, and it varies with T according to 138 × T(-0.95); (ii) the ratio κliquid (p)/κliquid (0.1 MPa) is 1.45 GPa(-1) at 280 K, which, unexpectedly, is about the same as κcrystal (p)/κcrystal (0.1 MPa) of 1.42 GPa(-1) at 298 K; (iii) κglass is relatively insensitive to T but sensitive to the applied p (1.38 GPa(-1) at 150 K); (iv) κglass-T plots show an enhanced, pressure-dependent peak-like feature, which is due to the glass to liquid transition on heating; (v) continuous heating cold-crystallizes ultraviscous glycerol under pressure, at a higher T when p is high; and (vi) glycerol formed by cooling at a high p and then measured at a low p has a significantly higher κ than the glass formed by cooling at a low p. On heating at a fixed low p, its κ decreases before its glass-liquid transition range at that p is reached. We attribute this effect to thermally assisted loss of the configurational and vibrational instabilities of a glass formed at high p and recovered at low p, which is different from the usual glass-aging effect. While the heat capacity, entropy, and volume of glycerol crystal are less than those for its glass and liquid, κcrystal of glycerol, like its elastic modulus and refractive index, is higher. We discuss these findings in terms of the role of fluctuations in local density and structure, and the relations between κ and the thermodynamic quantities.

Multiscale simulations of PS-SiO2 nanocomposites: from melt to glassy state.

Science.gov (United States)

Mathioudakis, I G; Vogiatzis, G G; Tzoumanekas, C; Theodorou, D N

2016-09-28

The interaction energetics, molecular packing, entanglement network properties, segmental dynamics, and elastic constants of atactic polystyrene-amorphous silica nanocomposites in the molten and the glassy state are studied via molecular simulations using two interconnected levels of representation: (a) a coarse-grained one, wherein each polystyrene repeat unit is mapped onto a single "superatom" and the silica nanoparticle is viewed as a solid sphere. Equilibration at all length scales at this level is achieved via connectivity-altering Monte Carlo simulations. (b) A united-atom (UA) level, wherein the polymer chains are represented in terms of a united-atom forcefield and the silica nanoparticle is represented in terms of a simplified, fully atomistic model. Initial configurations for UA molecular dynamics (MD) simulations are obtained by reverse mapping well-equilibrated coarse-grained configurations. By analysing microcanonical UA MD trajectories, the polymer density profile is studied and the polymer is found to exhibit layering in the vicinity of the nanoparticle surface. An estimate of the enthalpy of mixing between polymer and nanoparticles, derived from the UA simulations, compares favourably against available experimental values. The dynamical behaviour of polystyrene (in neat and filled melt systems) is characterized in terms of bond orientation and dihedral angle time autocorrelation functions. At low concentration in the molten polymer matrix, silica nanoparticles are found to cause a slight deceleration of the segmental dynamics close to their surface compared to the bulk polymer. Well-equilibrated coarse-grained long-chain configurations are reduced to entanglement networks via topological analysis with the CReTA algorithm, yielding a slightly lower density of entanglements in the filled than in the neat systems. UA melt configurations are glassified by MD cooling. The elastic moduli of the resulting glassy nanocomposites are computed through an

Time effects and glassy state behaviour in superconducting Y1Ba2Cu3O7-x

International Nuclear Information System (INIS)

Altinkok, A.; Yetis, H.; Olutas, M.; Kilic, K.; Kilic, A.

2007-01-01

The quenched disorder in the moving entity is investigated in a polycrystalline bulk sample of Y 1 Ba 2 Cu 3 O 7-x (YBCO) by slow transport relaxation measurements (V-t curves) on long time scales. The time evolution of sample voltage (V-t curve) are correlated to spatial reorganization of the driving current together with increasing or decreasing of resistive and non-resistive flow channels in a multiple connected network. In addition, it is shown that the voltage decays appearing in V-t curves are characterized by an exponential time dependence which is analogous to the glassy state relaxation

Glassy behavior in the layered perovskites La{sub 2-x}Sr{sub x}CoO{sub 4}(1.1{<=}x{<=}1.3)

Energy Technology Data Exchange (ETDEWEB)

Mukherjee, S., E-mail: sanseb68@yahoo.co.in [Department of Physics, University of Burdwan, Burdwan 713104 (India); Mukherjee, Rajarshi [Department .of Physics, University of Burdwan, Burdwan 713104 (India); Banerjee, S.; Ranganathan, R. [Saha Institute of Nuclear Physics, Kolkata 700 064 (India); Kumar, Uday [Department of Physical Sciences, Indian Institute of Science Education and Research - Kolkata, Mohonpur 741252 (India)

2012-03-15

The glassy behavior of the phase segregated state in the layered cobaltite La{sub 2-x}Sr{sub x}CoO{sub 4} has been studied. The role of the inter-cluster interactions as well as the disordered spins at the paramagnetic-ferromagnetic interface, behind the observed glassy behavior have been investigated. The disordered spins at the interface appear to be strongly pinned, and they contribute little to the observed glassy behavior. On the other hand, the inter-cluster interactions play the key role. Both the Co{sup 4+} and Co{sup 3+} ions are in the intermediate spin state. - Highlights: Black-Right-Pointing-Pointer Phase segregated state of cobaltite La{sub 2-x}Sr{sub x}CoO{sub 4} for (1.1{<=}x{<=}1.3) to find the origin of the observed glassy behavior. Black-Right-Pointing-Pointer Result of the frequency dependent ac susceptibility measurement excludes the possibility of any spin glass phase, hints strong inter-cluster interactions. Black-Right-Pointing-Pointer Relaxation experiments confirm the system to be a collection of clusters with two preferred sizes. Black-Right-Pointing-Pointer The glassy behavior originates from strong inter-cluster interactions.

In situ nanocalorimetry of thin glassy organic films

Science.gov (United States)

León-Gutierrez, E.; Garcia, G.; Lopeandía, A. F.; Fraxedas, J.; Clavaguera-Mora, M. T.; Rodríguez-Viejo, J.

2008-11-01

In this work, we describe the design and first experimental results of a new setup that combines evaporation of liquids in ultrahigh vacuum conditions with in situ high sensitivity thermal characterization of thin films. Organic compounds are deposited from the vapor directly onto a liquid nitrogen cooled substrate, permitting the preparation and characterization of glassy films. The substrate consists of a microfabricated, membrane-based nanocalorimeter that permits in situ measurements of heat capacity under ultrafast heating rates (up to 105 K/s) in the temperature range of 100-300 K. Three glass forming liquids—toluene, methanol, and acetic acid—are characterized. The spikes in heat capacity related to the glass-transition temperature, the fictive temperature and, in some cases, the onset temperature of crystallization are determined for several heating rates.

Dielectric relaxation studies in super-cooled liquid and glassy phases of anti-cancerous alkaloid: Brucine

Science.gov (United States)

Afzal, Aboothahir; Shahin Thayyil, M.; Sulaiman, M. K.; Kulkarni, A. R.

2018-05-01

Brucine has good anti-tumor effects, on both liver cancer and breast cancer. It has bioavailability of 40.83%. Since the bioavailability of the drug is low, an alternative method to increase its bioavailability and solubility is by changing the drug into glassy form. We used Differential Scanning Calorimetry (DSC) for studying the glass forming ability of the drug. Brucine was found to be a very good glass former glass transition temperature 365 K. Based on the DSC analysis we have used broadband dielectric spectroscopy (BDS) for studying the drug in the super cooled and glassy state. BDS is an effective tool to probe the molecular dynamics in the super cooled and glassy state. Molecular mobility is found to be present even in the glassy state of this active pharmaceutical ingredient (API) which is responsible for the instability. Our aim is to study the factors responsible for instability of this API in amorphous form. Cooling curves for dielectric permittivity and dielectric loss revealed the presence of structural (α) and secondary relaxations (β and γ). Temperature dependence of relaxation time is fitted by Vogel-Fulcher-Tammann equation and found the values of activation energy of the α relaxation, fragility and glass transition temperature. Paluch's anti correlation is also verified, that the width of the α-loss peak at or near the glass transition temperature Tg is strongly anticorrelated with the polarity of the molecule. The larger the dielectric relaxation strength Δɛ (Tg) of the system, the narrower is the α-loss peak (higher value of βKWW).

Low temperature thermal conductivities of glassy carbons

International Nuclear Information System (INIS)

Anderson, A.C.

1979-01-01

The thermal conductivity of glassy carbon in the temperature range 0.1 to 100 0 K appears to depend only on the temperature at which the material was pyrolyzed. The thermal conductivity can be related to the microscopic structure of glassy carbon. The reticulated structure is especially useful for thermal isolation at cryogenic temperatures

Crystallized Schroedinger cat states

International Nuclear Information System (INIS)

Castanos, O.; Lopez-Pena, R.; Man'ko, V.I.

1995-01-01

Crystallized Schroedinger cat states (male and female) are introduced on the base of extension of group construction for the even and odd coherent states of the electromagnetic field oscillator. The Wigner and Q functions are calculated and some are plotted for C 2 , C 3 , C 4 , C 5 , C 3v Schroedinger cat states. Quadrature means and dispersions for these states are calculated and squeezing and correlation phenomena are studied. Photon distribution functions for these states are given explicitly and are plotted for several examples. A strong oscillatory behavior of the photon distribution function for some field amplitudes is found in the new type of states

Treatment of early glassy cell carcinoma of uterine cervix

International Nuclear Information System (INIS)

Kim, Ok Bae; Kim, Jin Hee; Choi, Tae Jin

2006-01-01

The purpose of this study was to investigate the clinical findings, treatment, and outcome of patients with glassy cell carcinoma of cervix. We reviewed all cases of glassy cell carcinoma of the uterine cervix confirmed and treated at the Dongsan Medical Center, Keimyung University, between January 1993 and December 2005. There were 7 cases with histopathologically confirmed gassy cell carcinoma. A tumor was diagnosed as glassy cell carcinoma if over 50% of the tumor cell type displayed glassy cell features. Six patients with stage IB had radical hysterectomy and bilateral pelvic node dissection, and 2 of them received adjuvant external pelvic irradiation with concurrent chemotherapy. Remaining one patient with stage IIA had curative concurrent chemoradiotherapy with external pelvic irradiation and brachytherapy. There were 7 patients diagnosed as glassy cell carcinoma among the 3,745 (0.2%) patients of carcinoma of uterine cervix. The mean age of 7 patients was 44 years with range of 35 to 53 years of age. The most frequent symptom was vaginal bleeding (86%). By the punch biopsy undertaken before treatment of 7 cases, 2 only cases could diagnose as glassy cell carcinoma of uterine cervix, but remaining of them confirmed by surgical pathological examination. The mean follow up duration was 73 months with range of 13 to 150 months. All 7 patients were alive without disease after treatment. Glassy cell carcinoma of the uterine cervix is a distinct clinicopathologic entity that demonstrates an aggressive biologic behavior. However for early-stage disease, we may have more favorable clinical outcome with radical surgery followed by chemoradiotherapy

EDTA modified glassy carbon electrode: Preparation and characterization

International Nuclear Information System (INIS)

Ustuendag, Zafer; Solak, Ali Osman

2009-01-01

EDTA-phenoxyamide modified glassy carbon electrode (EDTA-GC) was prepared at a glassy carbon electrode by surface synthesis. In the first step, nitrophenyl was grafted to the glassy carbon (GC) surface via the electrochemical reduction of its tetraflouroborate diazonium salt. In the second step, nitrophenyl-modified electrode (NP-GC) was subjected to the cathodic potential scan to reduce the nitro to amine group. p-Aminophenyl modified glassy carbon electrode (AP-GC) was dipped into a EDTA solution containing 1-ethyl-3(3-(dimethlyamino)propyl)-carbodiimide (EDC) as an activating agent. Thus formed ((2-anilino-2-oxoethyl){2-[bis(carboxymethyl)amino]-ethyl}amino)acetic acid modified GC electrode was denoted as EDTA-GC and characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), ellipsometry and X-ray photoelectron spectroscopy (XPS). Complexation of the EDTA-GC surface with Pb 2+ ions was investigated if this electrode could be used as a metal sensor.

Boron ion irradiation induced structural and surface modification of glassy carbon

International Nuclear Information System (INIS)

Kalijadis, Ana; Jovanović, Zoran; Cvijović-Alagić, Ivana; Laušević, Zoran

2013-01-01

The incorporation of boron into glassy carbon was achieved by irradiating two different types of targets: glassy carbon polymer precursor and carbonized glassy carbon. Targets were irradiated with a 45 keV B 3+ ion beam in the fluence range of 5 × 10 15 –5 × 10 16 ions cm −2 . For both types of targets, the implanted boron was located in a narrow region under the surface. Following irradiation, the polymer was carbonized under the same condition as the glassy carbon samples (at 1273 K) and examined by Raman spectroscopy, temperature programmed desorption, hardness and cyclic voltammetry measurements. Structural analysis showed that during the carbonization process of the irradiated polymers, boron is substitutionally incorporated into the glassy carbon structure, while for irradiated carbonized glassy carbon samples, boron irradiation caused an increase of the sp 3 carbon fraction, which is most pronounced for the highest fluence irradiation. Further analyses showed that different nature of boron incorporation, and thus changed structural parameters, are crucial for obtaining glassy carbon samples with modified mechanical, chemical and electrochemical properties over a wide range

Irradiation-induced defects in graphite and glassy carbon studied by positron annihilation

International Nuclear Information System (INIS)

Hasegawa, M.; Kajino, M.; Kuwahara, H.; Yamaguchi, S.; Kuramoto, E.; Takenaka, M.

1992-01-01

ACAR and positron lifetime measurements have been made on, HOPG, isotropic fine-grained graphites, glassy carbons and C 60 /C 70 . HOPG showed a marked bimodal ACAR distribution along the c-axis. By irradiation of 1.0 X 10 19 fast neutrons/cm 2 remarkable narrowing in the ACAR curves and disappearance of the bimodal distribution were observed. Lifetime in HOPG increased from 225 psec to 289 psec (positron-lifetime in vacancies and their small clusters) by the irradiation. The irradiation on isotropic graphites and glassy carbons, however, gave slight narrowing in ACAR curves and decrease in lifetimes (360 psec → 300psec). This suggests irradiation-induced vacancy trapping in crystallites. In C 60 /C 70 powder two lifetime components were detected: τ 1 =177psec, τ 2 =403psec (I 2 =58%). The former is less than the bulk lifetime of HOPG, while the latter being very close to lifetimes in the isotropic graphites and glassy carbons. This and recent 2D-ACAR study of HOPG surface [15] strongly suggest free and defect surface states around ''soccer ball'' cages

Interpretation of the Raman spectra of the glassy states of SixS1−x and SixSe1−x

International Nuclear Information System (INIS)

Devi, V. Radhika; Zabidi, Noriza Ahmad; Shrivastava, Keshav N.

2013-01-01

We use the density-functional theory to make models of Si x S y and Si x Se y for the values of x,y = 1–6. The vibrational frequencies are calculated for each model. The stable clusters are selected on the basis of positive vibrational frequencies. In the case of Si x S 1−x , the values of the vibrational frequencies calculated from the first principles for Si 2 S(triangular)cluster of atoms, 364.1 cm −1 and 380.8 cm −1 , agree with the experimentally measured values of 367 cm −1 and 381 cm −1 , indicating that Si 2 S clusters occur in the glassy state of SiS. The calculated values of the vibrational frequencies of SiSe 4 (pyramidal) which agree with the experimental Raman frequencies of glassy Si x Se 1−x are 114, 166 and 361 cm −1 . The calculated values for Si 2 Se 4 (bipyramidal) which agree with the experimental data of Si x Se 1−x are 166 and 464 cm −1 . In Si 4 Se (pyramidal) the values 246 and 304 cm −1 agree with the measured values. In Si 4 Se 2 (bipyramidal), the calculated values 162, 196 and 304 cm −1 agree with the measured values. The calculated values of 473 cm −1 for Si 6 Se 2 (bipyramidal) also agree with the experimentally measured values. We thus find that pyramidal structures are present in the amorphous Si x Se 1−x glassy state. - Highlights: • A first principles calculation is performed to calculate the vibrational frequencies. • The calculated frequencies of clusters agree with measured Raman values. • The structures, bond lengths and symmetries are determined. • The importance of Jahn–Teller effect in SiS and in SiSe is clearly seen. • The clusters of SiS and SiSe are found to stabilize in different symmetries

Resonant Photonic States in Coupled Heterostructure Photonic Crystal Waveguides

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Sabarinathan J

2010-01-01

Full Text Available Abstract In this paper, we study the photonic resonance states and transmission spectra of coupled waveguides made from heterostructure photonic crystals. We consider photonic crystal waveguides made from three photonic crystals A, B and C, where the waveguide heterostructure is denoted as B/A/C/A/B. Due to the band structure engineering, light is confined within crystal A, which thus act as waveguides. Here, photonic crystal C is taken as a nonlinear photonic crystal, which has a band gap that may be modified by applying a pump laser. We have found that the number of bound states within the waveguides depends on the width and well depth of photonic crystal A. It has also been found that when both waveguides are far away from each other, the energies of bound photons in each of the waveguides are degenerate. However, when they are brought close to each other, the degeneracy of the bound states is removed due to the coupling between them, which causes these states to split into pairs. We have also investigated the effect of the pump field on photonic crystal C. We have shown that by applying a pump field, the system may be switched between a double waveguide to a single waveguide, which effectively turns on or off the coupling between degenerate states. This reveals interesting results that can be applied to develop new types of nanophotonic devices such as nano-switches and nano-transistors.

EDTA modified glassy carbon electrode: Preparation and characterization

Energy Technology Data Exchange (ETDEWEB)

Ustuendag, Zafer [Dumlupinar University, Faculty of Arts and Sciences, Department of Chemistry, Kuetahya (Turkey); Solak, Ali Osman [Ankara University, Faculty of Science, Department of Chemistry, Degol Street, Tandogan, 06100 Ankara (Turkey)], E-mail: osolak@science.ankara.edu.tr

2009-11-01

EDTA-phenoxyamide modified glassy carbon electrode (EDTA-GC) was prepared at a glassy carbon electrode by surface synthesis. In the first step, nitrophenyl was grafted to the glassy carbon (GC) surface via the electrochemical reduction of its tetraflouroborate diazonium salt. In the second step, nitrophenyl-modified electrode (NP-GC) was subjected to the cathodic potential scan to reduce the nitro to amine group. p-Aminophenyl modified glassy carbon electrode (AP-GC) was dipped into a EDTA solution containing 1-ethyl-3(3-(dimethlyamino)propyl)-carbodiimide (EDC) as an activating agent. Thus formed ((2-anilino-2-oxoethyl){l_brace}2-[bis(carboxymethyl)amino]-ethyl{r_brace}amino)acetic acid modified GC electrode was denoted as EDTA-GC and characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), ellipsometry and X-ray photoelectron spectroscopy (XPS). Complexation of the EDTA-GC surface with Pb{sup 2+} ions was investigated if this electrode could be used as a metal sensor.

Growth of single crystals of BaFe12O19 by solid state crystal growth

International Nuclear Information System (INIS)

Fisher, John G.; Sun, Hengyang; Kook, Young-Geun; Kim, Joon-Seong; Le, Phan Gia

2016-01-01

Single crystals of BaFe 12 O 19 are grown for the first time by solid state crystal growth. Seed crystals of BaFe 12 O 19 are buried in BaFe 12 O 19 +1 wt% BaCO 3 powder, which are then pressed into pellets containing the seed crystals. During sintering, single crystals of BaFe 12 O 19 up to ∼130 μm thick in the c-axis direction grow on the seed crystals by consuming grains from the surrounding polycrystalline matrix. Scanning electron microscopy-energy dispersive spectroscopy analysis shows that the single crystal and the surrounding polycrystalline matrix have the same chemical composition. Micro-Raman scattering shows the single crystal to have the BaFe 12 O 19 structure. The optimum growth temperature is found to be 1200 °C. The single crystal growth behavior is explained using the mixed control theory of grain growth. - Highlights: • Single crystals of BaFe 12 O 19 are grown by solid state crystal growth. • A single crystal up to ∼130 μm thick (c-axis direction) grows on the seed crystal. • The single crystal and surrounding ceramic matrix have similar composition. • Micro-Raman scattering shows the single crystal has the BaFe 12 O 19 structure.

Annealing effect on thermal conductivity and microhardness of carbon nanotube containing Se80Te16Cu4 glassy composites

Science.gov (United States)

Upadhyay, A. N.; Tiwari, R. S.; Singh, Kedar

2018-02-01

This study deals with the effect of thermal annealing on structural/microstructural, thermal and mechanical behavior of pristine Se80Te16Cu4 and carbon nanotubes (CNTs) containing Se80Te16Cu4 glassy composites. Pristine Se80Te16Cu4, 3 and 5 wt%CNTs-Se80Te16Cu4 glassy composites are annealed in the vicinity of glass transition temperature to onset crystallization temperature (340-380 K). X-ray diffraction (XRD) pattern revealed formation of polycrystalline phases of hexagonal CuSe and trigonal selenium. The indexed d-values in XRD patterns are in well conformity with the d-values obtained after the indexing of the ring pattern of selected area electron diffraction pattern of TEM images. The SEM investigation exhibited that the grain size of the CNTs containing Se80Te16Cu4 glassy composites increased with increasing annealing temperature and decreased at further higher annealing temperature. Thermal conductivity, microhardness exhibited a substantial increase with increasing annealing temperature of 340-360 K and slightly decreases for 380 K. The variation of thermal conductivity and microhardness can be explained by cross-linking formation and voids reduction.

Some Recent Developments in Structure and Glassy Behavior of Proteins

Science.gov (United States)

Hu, Chin-Kun

2012-02-01

We have used ARVO developed by us to find that the ratio of volume and surface area of proteins in Protein Data Bank distributed in a very narrow region [1]. Such result is useful for the determination of protein 3D structures. It has been widely known that a spin glass model can be used to understand the slow relaxation behavior of a glass at low temperatures [2]. We have used molecular dynamics and simple models of polymer chains to study relaxation and aggregation of proteins under various conditions and found that polymer chains with neighboring monomers connected by rigid bonds can relax very slowly and show glassy behavior [3]. We have also found that native collagen fibrils show glassy behavior at room temperatures [4]. The results of [3] and [4] about the glassy behavior of polymers or proteins are useful for understanding the mechanism for a biological system to maintain in a non-equilibrium state, including the ancient seed [5], which can maintain in a non-equilibrium state for a very long time. (1) M.-C. Wu, M. S. Li, W.-J. Ma, M. Kouza, and C.-K. Hu, EPL, in press (2011); (2) C. Dasgupta, S.-K. Ma, and C.-K. Hu. Phys. Rev. B 20, 3837-3849 (1979); (3) W.-J. Ma and C.-K. Hu, J. Phys. Soc. Japan 79, 024005, 024006, 054001, and 104002 (2010), C.-K. Hu and W.-J. Ma, Prog. Theor. Phys. Supp. 184, 369 (2010); S. G. Gevorkian, A. E. Allahverdyan, D. S. Gevorgyan and C.-K. Hu, EPL 95, 23001 (2011); S. Sallon, et al. Science 320, 1464 (2008).

Dielectric studies of molecular motions in glassy and liquid nicotine

Energy Technology Data Exchange (ETDEWEB)

Kaminski, K [Institute of Physics, Silesian University, ulica Uniwersytecka 4, 40-007 Katowice (Poland); Paluch, M [Institute of Physics, Silesian University, ulica Uniwersytecka 4, 40-007 Katowice (Poland); Ziolo, J [Institute of Physics, Silesian University, ulica Uniwersytecka 4, 40-007 Katowice (Poland); Ngai, K L [Naval Research Laboratory, Washington DC 20375-5320 (United States)

2006-06-21

The dielectric permittivity and loss spectra of glassy and liquid states of nicotine have been measured over the frequency range 10{sup -2}-10{sup 9} Hz. The relaxation spectra are similar to common small molecular glass-forming substances, showing the structural {alpha}-relaxation and its precursor, the Johari-Goldstein {beta}-relaxation. The {alpha}-relaxation is well described by the Fourier transform of the Kohlrausch-Williams-Watts stretched exponential function with an approximately constant stretch exponent that is equal to 0.70 as the glass transition temperature is approached. The dielectric {alpha}-relaxation time measured over 11 orders of magnitude cannot be described by a single Vogel-Fulcher-Tamman-Hesse equation. The most probable Johari-Goldstein {beta}-relaxation time determined from the dielectric spectra is in good agreement with the primitive relaxation time of the coupling model calculated from parameters of the structural {alpha}-relaxation. The shape of the dielectric spectra of nicotine is compared with that of other glass-formers having about the same stretch exponent, and they are shown to be nearly isomorphic. The results indicate that the molecular dynamics of nicotine conform to the general pattern found in other glass-formers, and the presence of the universal Johari-Goldstein secondary relaxation, which plays a role in the crystallization of amorphous pharmaceuticals.

A study on the positron annihilation of glassy Bi1Sr1Ca1Cu2Ox quenched from the molten liquid

International Nuclear Information System (INIS)

Hong Zhang; Xiao-Guang Wang; Le Luo; Shu-Hui Hu

1989-01-01

Some experimental results about the change of positron lifetime and Doppler broadening in glassy Bi 1 Sr 1 Ca 1 Cu 2 O x samples after post-annealing are reported. X-ray diffraction was used to examine the existing phases. Positron annihilation measurements indicate that there are two crystallization transformations from 20 0 to 830 0 C

Glassy carbon based supercapacitor stacks

Energy Technology Data Exchange (ETDEWEB)

Baertsch, M; Braun, A; Koetz, R; Haas, O [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

Considerable effort is being made to develop electrochemical double layer capacitors (EDLC) that store relatively large quantities of electrical energy and possess at the same time a high power density. Our previous work has shown that glassy carbon is suitable as a material for capacitor electrodes concerning low resistance and high capacity requirements. We present the development of bipolar electrochemical glassy carbon capacitor stacks of up to 3 V. Bipolar stacks are an efficient way to meet the high voltage and high power density requirements for traction applications. Impedance and cyclic voltammogram measurements are reported here and show the frequency response of a 1, 2, and 3 V stack. (author) 3 figs., 1 ref..

Raman spectroscopy adds complementary detail to the high-resolution x-ray crystal structure of photosynthetic PsbP from Spinacia oleracea.

Directory of Open Access Journals (Sweden)

Vladimir Kopecky

Full Text Available Raman microscopy permits structural analysis of protein crystals in situ in hanging drops, allowing for comparison with Raman measurements in solution. Nevertheless, the two methods sometimes reveal subtle differences in structure that are often ascribed to the water layer surrounding the protein. The novel method of drop-coating deposition Raman spectropscopy (DCDR exploits an intermediate phase that, although nominally "dry," has been shown to preserve protein structural features present in solution. The potential of this new approach to bridge the structural gap between proteins in solution and in crystals is explored here with extrinsic protein PsbP of photosystem II from Spinacia oleracea. In the high-resolution (1.98 Å x-ray crystal structure of PsbP reported here, several segments of the protein chain are present but unresolved. Analysis of the three kinds of Raman spectra of PsbP suggests that most of the subtle differences can indeed be attributed to the water envelope, which is shown here to have a similar Raman intensity in glassy and crystal states. Using molecular dynamics simulations cross-validated by Raman solution data, two unresolved segments of the PsbP crystal structure were modeled as loops, and the amino terminus was inferred to contain an additional beta segment. The complete PsbP structure was compared with that of the PsbP-like protein CyanoP, which plays a more peripheral role in photosystem II function. The comparison suggests possible interaction surfaces of PsbP with higher-plant photosystem II. This work provides the first complete structural picture of this key protein, and it represents the first systematic comparison of Raman data from solution, glassy, and crystalline states of a protein.

Formation of a glassy phase in ceramic-like coatings

International Nuclear Information System (INIS)

Sazonova, M.V.; Gorbatova, G.N.

1986-01-01

The authors investigate the synthesis directly in coatings of a borosilicate melt that could fill the role of glassy matrix, thereby avoiding fusion and processing of the glassy material. The effect of added boron on the formation of coatings based on molybdenum disilicide and tungsten disilicide in air at 900 degrees C is presented. Without an additive no coating forms; there is no adhesion to the graphite and a continuous film does not form. As a result of boron oxidation an easily fused glassy matrix forms, which bonds the molybdenum disilicide or tungsten disilicide particles together and ensures adhesion to the graphite

Two-dimensionally confined topological edge states in photonic crystals

International Nuclear Information System (INIS)

Barik, Sabyasachi; Miyake, Hirokazu; DeGottardi, Wade; Waks, Edo; Hafezi, Mohammad

2016-01-01

We present an all-dielectric photonic crystal structure that supports two-dimensionally confined helical topological edge states. The topological properties of the system are controlled by the crystal parameters. An interface between two regions of differing band topologies gives rise to topological edge states confined in a dielectric slab that propagate around sharp corners without backscattering. Three-dimensional finite-difference time-domain calculations show these edges to be confined in the out-of-plane direction by total internal reflection. Such nanoscale photonic crystal architectures could enable strong interactions between photonic edge states and quantum emitters. (paper)

Crystal-field-modulated magnon squeezing states in a ferromagnet

International Nuclear Information System (INIS)

Peng Feng

2003-01-01

The magnon squeezing states in some magnetic crystals allow a reduction in the quantum fluctuations of the spin component to below the zero-point quantum noise level of the coherent magnon states. It is known that there are the magnon squeezing states in an antiferromagnet. However, their generating mechanism is not suitable for the ferromagnet. In this paper, we discuss the possibility of generating the magnon squeezing states in a ferromagnet, and discuss the effect of the crystal field on the magnon squeezing states

Crystallization processes in Ni-Ti-B glassy alloys of near-ternary-eutectic composition

International Nuclear Information System (INIS)

Merk, N.; Morris, D.G.; Stadelmann, P.

1987-01-01

The crystallization kinetics and mechanisms of three Ni-Ti-B glasses have been examined with a view to elucidating the roles of chemical composition and quenched structure on behaviour. Alloys of composition near a ternary-eutectic point have been chosen because they represent a real and complex situation where several crystalline phases may form simultaneously. Crystallization processes are analysed in terms of nucleation and growth stages. Different nucleation mechanisms seem to be best explained in terms of the short range ordered structure of the quenched glass. Analysis of crystal glass interface energies indicates that it is not this energy term which controls the nucleation of crystals on annealing. Crystal growth may involve a eutectic mechanism or a single-phase mechanism controlled by interface or matrix-diffusion kinetics. Crystallization is fastest when eutectic nucleation and growth occurs. Formation of the eutectic colony requires the initial formation of the phase of complex structure followed by the phase of simpler structure

Atmospheric pressure plasma treatment of glassy carbon for adhesion improvement

DEFF Research Database (Denmark)

Kusano, Yukihiro; Mortensen, Henrik Junge; Stenum, Bjarne

2007-01-01

density increased with the plasma treatments. Adhesion test of the treated glassy carbon covered with cured epoxy showed cohesive failure, indicating strong bonding after the treatments. This is in contrast to the adhesion tests of untreated samples where the epoxy readily peeled off the glassy carbon....

Growth of single crystals of BaFe12O19 by solid state crystal growth

Science.gov (United States)

Fisher, John G.; Sun, Hengyang; Kook, Young-Geun; Kim, Joon-Seong; Le, Phan Gia

2016-10-01

Single crystals of BaFe12O19 are grown for the first time by solid state crystal growth. Seed crystals of BaFe12O19 are buried in BaFe12O19+1 wt% BaCO3 powder, which are then pressed into pellets containing the seed crystals. During sintering, single crystals of BaFe12O19 up to ∼130 μm thick in the c-axis direction grow on the seed crystals by consuming grains from the surrounding polycrystalline matrix. Scanning electron microscopy-energy dispersive spectroscopy analysis shows that the single crystal and the surrounding polycrystalline matrix have the same chemical composition. Micro-Raman scattering shows the single crystal to have the BaFe12O19 structure. The optimum growth temperature is found to be 1200 °C. The single crystal growth behavior is explained using the mixed control theory of grain growth.

Variational Approach in the Theory of Liquid-Crystal State

Science.gov (United States)

Gevorkyan, E. V.

2018-03-01

The variational calculus by Leonhard Euler is the basis for modern mathematics and theoretical physics. The efficiency of variational approach in statistical theory of liquid-crystal state and in general case in condensed state theory is shown. The developed approach in particular allows us to introduce correctly effective pair interactions and optimize the simple models of liquid crystals with help of realistic intermolecular potentials.

Nonequilibrium steady state and induced currents of a mesoscopically glassy system: interplay of resistor-network theory and Sinai physics.

Science.gov (United States)

Hurowitz, Daniel; Rahav, Saar; Cohen, Doron

2013-12-01

We introduce an explicit solution for the nonequilibrium steady state (NESS) of a ring that is coupled to a thermal bath, and is driven by an external hot source with log-wide distribution of couplings. Having time scales that stretch over several decades is similar to glassy systems. Consequently there is a wide range of driving intensities where the NESS is like that of a random walker in a biased Brownian landscape. We investigate the resulting statistics of the induced current I. For a single ring we discuss how sign of I fluctuates as the intensity of the driving is increased, while for an ensemble of rings we highlight the fingerprints of Sinai physics on the distribution of the absolute value of I.

Quasi-equilibrium in glassy dynamics: an algebraic view

International Nuclear Information System (INIS)

Franz, Silvio; Parisi, Giorgio

2013-01-01

We study a chain of identical glassy systems in a constrained equilibrium, where each bond of the chain is forced to remain at a preassigned distance to the previous one. We apply this description to mean-field glassy systems in the limit of a long chain where each bond is close to the previous one. We show that this construction defines a pseudo-dynamic process that in specific conditions can formally describe real relaxational dynamics for long times. In particular, in mean-field spin glass models we can recover in this way the equations of Langevin dynamics in the long time limit at the dynamical transition temperature and below. We interpret the formal identity as evidence that in these situations the configuration space is explored in a quasi-equilibrium fashion. Our general formalism, which relates dynamics to equilibrium, puts slow dynamics in a new perspective and opens the way to the computation of new dynamical quantities in glassy systems. (paper)

Time effects and glassy state behaviour in superconducting Y{sub 1}Ba{sub 2}Cu{sub 3}O{sub 7-x}

Energy Technology Data Exchange (ETDEWEB)

Altinkok, A.; Yetis, H.; Olutas, M.; Kilic, K. [Abant Izzet Baysal University, Department of Physics, Turgut Gulez Research Laboratory, 14280 Bolu (Turkey); Kilic, A. [Abant Izzet Baysal University, Department of Physics, Turgut Gulez Research Laboratory, 14280 Bolu (Turkey)], E-mail: kilic_a@ibu.edu.tr

2007-10-01

The quenched disorder in the moving entity is investigated in a polycrystalline bulk sample of Y{sub 1}Ba{sub 2}Cu{sub 3}O{sub 7-x} (YBCO) by slow transport relaxation measurements (V-t curves) on long time scales. The time evolution of sample voltage (V-t curve) are correlated to spatial reorganization of the driving current together with increasing or decreasing of resistive and non-resistive flow channels in a multiple connected network. In addition, it is shown that the voltage decays appearing in V-t curves are characterized by an exponential time dependence which is analogous to the glassy state relaxation.

Electronic states in crystals of finite size quantum confinement of bloch waves

CERN Document Server

Ren, Shang Yuan

2017-01-01

This book presents an analytical theory of the electronic states in ideal low dimensional systems and finite crystals based on a differential equation theory approach. It provides precise and fundamental understandings on the electronic states in ideal low-dimensional systems and finite crystals, and offers new insights into some of the basic problems in low-dimensional systems, such as the surface states and quantum confinement effects, etc., some of which are quite different from what is traditionally believed in the solid state physics community. Many previous predictions have been confirmed in subsequent investigations by other authors on various relevant problems. In this new edition, the theory is further extended to one-dimensional photonic crystals and phononic crystals, and a general theoretical formalism for investigating the existence and properties of surface states/modes in semi-infinite one-dimensional crystals is developed. In addition, there are various revisions and improvements, including us...

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors.

Science.gov (United States)

Zheng, Wei; van den Hurk, Remko; Cao, Yong; Du, Rongbing; Sun, Xuejun; Wang, Yiyu; McDermott, Mark T; Evoy, Stephane

2016-03-14

Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

Aryl Diazonium Chemistry for the Surface Functionalization of Glassy Biosensors

Directory of Open Access Journals (Sweden)

Wei Zheng

2016-03-01

Full Text Available Nanostring resonator and fiber-optics-based biosensors are of interest as they offer high sensitivity, real-time measurements and the ability to integrate with electronics. However, these devices are somewhat impaired by issues related to surface modification. Both nanostring resonators and photonic sensors employ glassy materials, which are incompatible with electrochemistry. A surface chemistry approach providing strong and stable adhesion to glassy surfaces is thus required. In this work, a diazonium salt induced aryl film grafting process is employed to modify a novel SiCN glassy material. Sandwich rabbit IgG binding assays are performed on the diazonium treated SiCN surfaces. Fluorescently labelled anti-rabbit IgG and anti-rabbit IgG conjugated gold nanoparticles were used as markers to demonstrate the absorption of anti-rabbit IgG and therefore verify the successful grafting of the aryl film. The results of the experiments support the effectiveness of diazonium chemistry for the surface functionalization of SiCN surfaces. This method is applicable to other types of glassy materials and potentially can be expanded to various nanomechanical and optical biosensors.

Role of Disorder in the Thermodynamics and Atomic Dynamics of Glasses

DEFF Research Database (Denmark)

Chumakov, A.I.; Monaco, G.; Fontana, A.

2014-01-01

We measured the density of vibrational states (DOS) and the specific heat of various glassy and crystalline polymorphs of SiO2. The typical (ambient) glass shows a well-known excess of specific heat relative to the typical crystal (α-quartz). This, however, holds when comparing a lower......-density glass to a higherdensity crystal. For glassy and crystalline polymorphs with matched densities, the DOS of the glass appears as the smoothed counterpart of the DOS of the corresponding crystal; it reveals the same number of the excess states relative to the Debye model, the same number of all states...... in the low-energy region, and it provides the same specific heat. This shows that glasses have higher specific heat than crystals not due to disorder, but because the typical glass has lower density than the typical crystal....

Diffusion coefficients of tracers in glassy polymer systems prepared by gamma radiolysis

International Nuclear Information System (INIS)

Tonge, M.P.; Gilbert, R.G.

1996-01-01

Diffusion-controlled reactions are common in free radical polymerisation reactions, especially in glassy polymer matrices. Such reactions commonly have an important influence on the polymerisation process and final polymer properties. For example, the dominant growth-stopping event (bimolecular termination) is generally diffusion-controlled. In glassy polymer systems, where molecular mobility is very low, the chain growth mechanism (propagation) may become diffusion-controlled. At present, the mechanism for propagation in glassy polymers is poorly understood, but it is expected by the Smoluchowski expression applied to propagation to depend strongly on the diffusion coefficient of monomer. The objective of this study is to measure reliable diffusion coefficients of small tracer molecules in glassy polymers, and compare these with propagation rate coefficients in similar systems, by the prediction above. Samples were initially prepared in a sealed sampled cell containing monomer, inert diluent, and tracer dye. After irradiation for several days, complete conversion of monomer to polymer can be obtained. The diffusion coefficients for two tracer dyes have been measured as a function of weight fraction polymer glassy poly(methyl methacrylate) samples

Patterned solid state growth of barium titanate crystals

Science.gov (United States)

Ugorek, Michael Stephen

An understanding of microstructure evolution in ceramic materials, including single crystal development and abnormal/enhanced grain growth should enable more controlled final ceramic element structures. In this study, two different approaches were used to control single crystal development in a patterned array. These two methods are: (1) patterned solid state growth in BaTiO 3 ceramics, and (2) metal-mediated single crystal growth in BaTiO 3. With the patterned solid state growth technique, optical photolithography was used to pattern dopants as well as [001] and [110] BaTiO3 single crystal template arrays with a 1000 microm line pattern array with 1000 microm spacings. These patterns were subsequently used to control the matrix grain growth evolution and single crystal development in BaTiO3. It was shown that the growth kinetics can be controlled by a small initial grain size, atmosphere conditions, and the introduction of a dopant at selective areas/interfaces. By using a PO2 of 1x10-5 atm during high temperature heat treatment, the matrix coarsening has been limited (to roughly 2 times the initial grain size), while retaining single crystal boundary motion up to 0.5 mm during growth for dwell times up to 9 h at 1300°C. The longitudinal and lateral growth rates were optimized at 10--15 microm/h at 1300°C in a PO2 of 1x10 -5 atm for single crystal growth with limited matrix coarsening. Using these conditions, a patterned microstructure in BaTiO3 was obtained. With the metal-mediated single crystal growth technique, a novel approach for fabricating 2-2 single crystal/polymer composites with a kerf texture development were studied using both [001] and [110] BaTiO3 single crystals templates. By using a PO 2 of 1x10-11 atm during high temperature heat treatment, matrix coarsening was limited while enabling single crystal boundary motion up to 0.35 mm during growth between 1250°C and 1300°C with growth rates ˜ 3--4 microm/h for both single crystal orientations. By

Surface states in photonic crystals

Directory of Open Access Journals (Sweden)

Vojtíšek P.

2013-05-01

Full Text Available Among many unusual and interesting physical properties of photonic crystals (PhC, in recent years, the propagation of surface electromagnetic waves along dielectric PhC boundaries have attracted considerable attention, also in connection to their possible applications. Such surfaces states, produced with the help of specialized defects on PhC boundaries, similarly to surfaces plasmons, are localized surfaces waves and, as such, can be used in various sensing applications. In this contribution, we present our recent studies on numerical modelling of surface states (SS for all three cases of PhC dimensionality. Simulations of these states were carried out by the use of plane wave expansion (PWE method via the MIT MPB package.

Electrochemical and microstructural characterization of platinum supported on glassy carbon

Directory of Open Access Journals (Sweden)

Terzić Sanja

2007-01-01

Full Text Available The effect of the electrochemical oxidation of glassy carbon on the deposition of platinum particles and the electrocatalytic activity of platinum supported on oxidized glassy carbon were studied for methanol oxidation in H2SO4 solution. Platinum was potentiostatically deposited from H2SO4 + 6mM H2PtCl6 solution. Glassy carbon was anodically polarized in 1 M NaOH at 1.41 V (SCE for 35 and 95 s and in 0.5 M H2SO4 at 2V (SCE for 35; 95 s and 2.25 V for 35 and 95 s. Electrochemical treatment of the GC support leads to a better distribution of platinum on the substrate and has remarkable effect on the activity. The activity of the Pt/GCox electrode for methanol oxidation is larger than that of polycrystalline Pt and by more than one order of magnitude larger than that of a Pt/GC electrode. This increase in activity indicates the pronounced role of the organic residues of the GC support on the properties of Pt particles deposited on glassy carbon.

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.

Impact of the structural state on the mechanical properties in a Zr–Co–Al bulk metallic glass

International Nuclear Information System (INIS)

Qiao, J.C.; Pelletier, J.M.; Esnouf, C.; Liu, Y.; Kato, H.

2014-01-01

Highlights: • Atomic mobility in metallic glass was studied by DMA, HRTEM and nanoindentation. • Physical ageing and crystallization reduce the atomic mobility. • Plastic deformation, i.e. cold-rolling enhances the atomic mobility. • Atomic mobility in glassy materials can be described by quasi-point defects model. - Abstract: This paper reports on the use of differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and nanoindentation technique to investigate atomic mobility in Zr 56 Co 28 Al 16 bulk metallic glass in the as-cast state, after thermal annealing and after cold rolling. From the DMA results together with nanoindentation data point of view, the atomic mobility is significantly modified by the thermo-mechanical history. On the one hand, atomic mobility in bulk metallic glass is reduced after physical aging or crystallization. On the other hand, the atomic mobility in metallic glass is enhanced by cold rolling. To analyze the atomic mobility in amorphous materials, a physical theory is introduced. This model invoked the concept of quasi-point defects, which correspond to the density fluctuations in the glassy materials. Correlated movements of atoms are assisted by these quasi-point defects and the correlation factor χ is connected to the concentration of these “defects” in metallic glasses: (i) physical aging and crystallization decreases the parameter χ and (ii) the concentration of defects augments via plastic deformation (i.e. cold-rolling), suggesting that the correlation factor χ reflects the atomic mobility for glassy materials in a quantitative manner. This correlation bridges the gap between the mechanical properties on macroscopic scale and atomic mobility in microstructural regions in metallic glasses

Surface states in crystals with low-index surfaces

International Nuclear Information System (INIS)

Wang Hui-Ping; Tao Rui-Bao

2015-01-01

For most of the conventional crystals with low-index surfaces, the hopping between the nearest neighbor (1NN) crystal planes (CPs) is dominant and the ones from the nNN (2 ≤ n < ∞) CPs are relatively weak, considered as small perturbations. The recent theoretical analysis [1] has demonstrated the absence of surface states at the level of the hopping approximation between the 1NN CPs when the original infinite crystal has the geometric reflection symmetry (GRS) for each CP. Meanwhile, based on the perturbation theory, it has also been shown that small perturbations from the hopping between the nNN (2 ≤ n < ∞) CPs and surface relaxation have no impact on the above conclusion. However, for the crystals with strong intrinsic spin-orbit coupling (SOC), the dominant terms of intrinsic SOC associate with two 1NN bond hoppings. Thus SOC will significantly contribute the hoppings from the 1NN and/or 2NN CPs except the ones within each CP. Here, we will study the effect of the hopping between the 2NN CPs on the surface states in model crystals with three different type structures (Type I: “···–P–P–P–P–···”, Type II: “···–P–Q–P–Q–···” and Type III: “···–P=Q–P=Q–···” where P and Q indicate CPs and the signs “−” and “=” mark the distance between the 1NN CPs). In terms of analytical and numerical calculations, we study the behavior of surface states in three types after the symmetric/asymmetric hopping from the 2NN CPs is added. We analytically prove that the symmetric hopping from the 2NN CPs cannot induce surface states in Type I when each CP has only one electron mode. The numerical calculations also provide strong support for the conclusion, even up to 5NN. However, in general, the coupling from the 2NN CPs (symmetric and asymmetric) is favorable to generate surface states except Type I with single electron mode only. (paper)

Crystal structure and solid-state properties of discrete hexa cationic ...

Indian Academy of Sciences (India)

Subsequently, weight loss of 33% in two stages from 242 to 691◦C can be assigned to the decomposition of triazole ligands. 3.3 Description of the crystal structure. The solid-state structure of ZnT was unambiguously determined by the single crystal X-ray diffraction tech- nique (figures 2 and 3). Compound ZnT crystallizes in.

Development of n- and p-type Doped Perovskite Single Crystals Using Solid-State Single Crystal Growth (SSCG) Technique

Science.gov (United States)

2017-10-09

for AGG should be minimal. For this purpose, the seeds for AGG may also be provided externally. This process is called the solid-state single...bonding process . Figure 31 shows (a) the growth of one large single crystal from one small single crystal seed as well as (b) the growth of one...one bi-crystal seed : One large bi-crystal can be grown from one small bi-crystal by SSCG process . Fig. 32. Diffusion bonding process for

Electrical properties of carbon nanotubes modified GaSe glassy system

Science.gov (United States)

Khan, Hana; Khan, Zubair M. S. H.; Islam, Shama; Rahman, Raja Saifu; Husain, M.; Zulfequar, M.

2018-05-01

In this paper we report the investigation of the effect of Carbon Nanotubes (CNT) addition on the electrical properties of GaSe Glassy system. Dielectric constant and dielectric loss of GaSe glassy system are found to increase on CNT addition. The conductivity of GaSe glasy systems is also found to increase on CNT addition. This behavior is attributed to the excellent conduction properties of Carbon Nanotube.

Crystallization and evaluation of hen egg-white lysozyme crystals for protein pH titration in the crystalline state.

Science.gov (United States)

Iwai, Wakari; Yagi, Daichi; Ishikawa, Takuya; Ohnishi, Yuki; Tanaka, Ichiro; Niimura, Nobuo

2008-05-01

To observe the ionized status of the amino acid residues in proteins at different pH (protein pH titration in the crystalline state) by neutron diffraction, hen egg-white lysozyme was crystallized over a wide pH range (2.5-8.0). Crystallization phase diagrams at pH 2.5, 6.0 and 7.5 were determined. At pH diagram, and at pH > 4.5 the border shifted to the right (higher precipitant concentration). The qualities of these crystals were characterized using the Wilson plot method. The qualities of all crystals at different pH were more or less equivalent (B-factor values within 25-40). It is expected that neutron diffraction analysis of these crystals of different pH provides equivalent data in quality for discussions of protein pH titration in the crystalline state of hen egg-white lysozyme.

Grain-boundary, glassy-phase identification and possible artifacts

International Nuclear Information System (INIS)

Simpson, Y.K.; Carter, C.B.; Sklad, P.; Bentley, J.

1985-01-01

Specimen artifacts such as grain boundary grooving, surface damage of the specimen, and Si contamination are shown experimentally to arise from the ion milling used in the preparation of transmission electron microscopy specimens. These artifacts in polycrystalline, ceramic specimens can cause clean grain boundaries to appear to contain a glassy phase when the dark-field diffuse scattering technique, the Fresnel fringe technique, and analytical electron microscopy (energy dispersive spectroscopy) are used to identify glassy phases at a grain boundary. The ambiguity in interpreting each of these techniques due to the ion milling artifacts will be discussed from a theoretical view point and compared to experimental results obtained for alumina

Crystallization and evaluation of hen egg-white lysozyme crystals for protein pH titration in the crystalline state

International Nuclear Information System (INIS)

Iwai, Wakari; Yagi, Daichi; Ishikawa, Takuya; Ohnishi, Yuki; Tanaka, Ichiro; Niimura, Nobuo

2008-01-01

Hen egg-white lysozyme was crystallized over a wide pH range (2.5–8.0) and the quality of the crystals was characterized. Crystallization phase diagrams at pH 2.5, 6.0 and 7.5 were determined To observe the ionized status of the amino acid residues in proteins at different pH (protein pH titration in the crystalline state) by neutron diffraction, hen egg-white lysozyme was crystallized over a wide pH range (2.5–8.0). Crystallization phase diagrams at pH 2.5, 6.0 and 7.5 were determined. At pH < 4.5 the border between the metastable region and the nucleation region shifted to the left (lower precipitant concentration) in the phase diagram, and at pH > 4.5 the border shifted to the right (higher precipitant concentration). The qualities of these crystals were characterized using the Wilson plot method. The qualities of all crystals at different pH were more or less equivalent (B-factor values within 25–40). It is expected that neutron diffraction analysis of these crystals of different pH provides equivalent data in quality for discussions of protein pH titration in the crystalline state of hen egg-white lysozyme

Fine kinetics of natural physical ageing in glassy As10Se90

International Nuclear Information System (INIS)

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

2014-01-01

Sigmoid behavior of natural physical ageing in glassy As 10 Se 90 reveals multi-step-wise growing kinetics of enthalpy losses. Phenomenological description of this kinetics can be adequately developed in terms of first-order relaxation processes, tending atomic structure from initial towards more thermodynamically equilibrium state. This kinetics is shown to obey characteristic stretched exponential behavior originated from a number of growing steps, attributed to the interconnected processes of chalcogen chain alignment and cooperative shrinkage of glass network

Dynamics of Spontaneous Emission Controlled by Local Density of States in Photonic Crystals

DEFF Research Database (Denmark)

Lodahl, Peter; Nikolaev, Ivan S.; van Driel, A. Floris

2006-01-01

We have measured time-resolved spontaneous emission from quantum dots in 3D photonic crystals. Due to the spatially dependent local density of states, the distribution of decay rates varies strongly with the photonic crystal lattice parameter.......We have measured time-resolved spontaneous emission from quantum dots in 3D photonic crystals. Due to the spatially dependent local density of states, the distribution of decay rates varies strongly with the photonic crystal lattice parameter....

EXPERIMENTAL ANALYSIS OF BIOLOGICAL PARAMETERS AND VECTOR ABILITY OF GLASSY-WINGED SHARPSHOOTERS FROM ALLOPATRIC POPULATIONS IN CALIFORNIA

Science.gov (United States)

The glassy-winged sharpshooter (GWSS), Homalodisca vitripennis (Germar), is native to the southeastern United States and northeastern Mexico. It was detected in southern California in the late 1980s and in the San Joaquin Valley in 1999, where it transmits the bacterium Xylella fastidiosa to grapev...

Control of nucleation and crystal growth of a silicate apatitic phase in a glassy matrix

International Nuclear Information System (INIS)

Ligny, D.; Caurant, D.; Bardez, I.; Dussossoy, J.L.; Loiseau, P.; Neuville, D.R.

2004-01-01

Nucleation and growth of crystal in an oxide glass was studied in a Si B Al Zr Nd Ca Na O system. The nucleation and growth process were monitored by thermal analysis and isothermal experiments. The effect of the network modifier was studied. Therefore for a Ca rich sample the crystallization is homogeneous in the bulk showing a slow increase of crystallinity as temperature increases. On the other hand, a Na rich sample undergoes several crystallization processes in the bulk or from the surface, leading to bigger crystals. The activation energy of the viscous flow and the glass transition are of same magnitude when that of crystallization is a lot smaller. Early diffusion of element is done with a mechanism different than the configurational rearrangements of the liquid sate. The global density and small size of the crystals within the Ca rich matrix confirmed that it would be a profitable waste form for minor actinides. (authors)

Ultra-fast solid state electro-optical modulator based on liquid crystal polymer and liquid crystal composites

Energy Technology Data Exchange (ETDEWEB)

Ouskova, Elena; Sio, Luciano De, E-mail: luciano@beamco.com; Vergara, Rafael; Tabiryan, Nelson [Beam Engineering for Advanced Measurements Company, Winter Park, Florida 32789 (United States); White, Timothy J.; Bunning, Timothy J. [Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio 45433-7707 (United States)

2014-12-08

A different generation of polymer-dispersed liquid crystals (PDLCs) based on a liquid crystalline polymer host is reported wherein the fluid behavior of the reactive mesogenic monomer is an enabler to concentration windows (liquid crystal polymer/liquid crystal) (and subsequent morphologies) not previously explored. These liquid crystal (LC) polymer/LC composites, LCPDLCs, exhibit excellent optical and electro-optical properties with negligible scattering losses in both the ON and OFF states. These systems thus have application in systems where fast phase modulation of optical signal instead of amplitude control is needed. Polarized optical microscopy and high resolution scanning electron microscopy confirm a bicontinuous morphology composed of aligned LC polymer coexisting with a phase separated LC fluid. Operating voltages, switching times, and spectra of LCPDLCs compare favourably to conventional PDLC films. The LCPDLCs exhibit a low switching voltage (4–5 V/μm), symmetric and submillisecond (200 μs) on/off response times, and high transmission in both the as formed and switched state in a phase modulation geometry.

Crystal Ball evidence for new states

International Nuclear Information System (INIS)

Coyne, D.G.

1981-09-01

Evidence for three new particles observed in the Crystal Ball detector is presented. The first particle, at 3592 MeV, is seen inclusively in γ transitions from psi', and is thus a candidate for eta/sub c/'. The other two, at 1440 and 1640 MeV, are best seen in exclusive decays of psi involving a prompt γ, and are thus candidates for bound states of two gluons. Detailed reasons are presented to support the contention that these states are distinct from previously observed candidates such as E(1420). Alternative hypotheses are discussed

Voltammetric quantitation of nitazoxanide by glassy carbon electrode

Directory of Open Access Journals (Sweden)

Rajeev Jain

2013-12-01

Full Text Available The present study reports voltammetric reduction of nitazoxanide in Britton–Robinson (B–R buffer by cyclic and square-wave voltammetry at glassy carbon electrode. A versatile fully validated voltammetric method for quantitative determination of nitazoxanide in pharmaceutical formulation has been proposed. A squrewave peak current was linear over the nitazoxanide concentration in the range of 20–140 µg/mL. The limit of detection (LOD and limit of quantification (LOQ was calculated to be 5.23 μg/mL and 17.45 μg/mL, respectively. Keywords: Nitazoxanide, Squarewave voltammetry, Glassy carbon electrode, Pharmaceutical formulation

Fabrication and nano-imprintabilities of Zr-, Pd- and Cu-based glassy alloy thin films

International Nuclear Information System (INIS)

Takenaka, Kana; Saidoh, Noriko; Nishiyama, Nobuyuki; Inoue, Akihisa

2011-01-01

With the aim of investigating nano-imprintability of glassy alloys in a film form, Zr 49 Al 11 Ni 8 Cu 32 , Pd 39 Cu 29 Ni 13 P 19 and Cu 38 Zr 47 Al 9 Ag 6 glassy alloy thin films were fabricated on Si substrate by a magnetron sputtering method. These films exhibit a very smooth surface, a distinct glass transition phenomenon and a large supercooled liquid region of about 80 K, which are suitable for imprinting materials. Moreover, thermal nano-imprintability of these obtained films is demonstrated by using a dot array mold with a dot diameter of 90 nm. Surface observations revealed that periodic nano-hole arrays with a hole diameter of 90 nm were successfully imprinted on the surface of these films. Among them, Pd-based glassy alloy thin film indicated more precise pattern imprintability, namely, flatter residual surface plane and sharper hole edge. It is said that these glassy alloy thin films, especially Pd-based glassy alloy thin film, are one of the promising materials for fabricating micro-machines and nano-devices by thermal imprinting.

Partially and fully de-alloyed glassy ribbons based on Au: Application in methanol electro-oxidation studies

Energy Technology Data Exchange (ETDEWEB)

Paschalidou, Eirini Maria, E-mail: epaschal@unito.it [Dipartimento di Chimica e Centro Interdipartimentale NIS (Nanostructured Surfaces and Interfaces), Università di Torino, Via Pietro Giuria 7, 10125, Torino (Italy); Scaglione, Federico [Dipartimento di Chimica e Centro Interdipartimentale NIS (Nanostructured Surfaces and Interfaces), Università di Torino, Via Pietro Giuria 7, 10125, Torino (Italy); Gebert, Annett; Oswald, Steffen [Leibniz Institut für Festkörper- und Werkstoffforschung IFW, Helmholtzstraße 20, 01069, Dresden (Germany); Rizzi, Paola; Battezzati, Livio [Dipartimento di Chimica e Centro Interdipartimentale NIS (Nanostructured Surfaces and Interfaces), Università di Torino, Via Pietro Giuria 7, 10125, Torino (Italy)

2016-05-15

In this work, electrochemical de-alloying of an amorphous alloy, Au{sub 40}Cu{sub 28}Ag{sub 7}Pd{sub 5}Si{sub 20}, cast in ribbon form by melt spinning, has been performed, obtaining self standing nanoporous materials suitable for use as electrodes for electrocatalytic applications. The de-alloying encompasses removal of less noble elements and the crystallization of Au, resulting in interconnected ligaments whose size and morphology are described as a function of time. Depending on de-alloying time, the crystals may contain residual amounts of Cu, Ag and Pd, as shown by Auger Electron Spectroscopy (AES), Energy Dispersive Spectroscopy (EDS) and Cyclic Voltammetry (CV) in a basic solution. Current density peaks in the 0.16–0.28 V range (vs Ag/AgCl) indicate that the porous ribbons are active for the electro-oxidation of methanol. The partially de-alloyed samples, which still partially contain the amorphous phase because of the shorter etching times, have finer ligaments and display peaks at lower potential. However, the current density decreases rapidly during repeated potential scans. This is attributed to the obstruction of Au sites, mainly by the Cu oxides formed during the scans. The fully de-alloyed ribbons display current peaks at about 0.20 V and remain active for hundreds of scans at more than 60% of the initial current density. They can be fully re-activated to achieve the same performance levels after a brief immersion in nitric acid. The good activity is due to trapped Ag and Pd atoms in combination with ligament morphology. - Graphical abstract: Fine ligaments and pores made by de-alloying a glassy ribbon of a Au-based alloy, homogeneously produced across the thickness (25 μm) for studying methanol's electro-oxidation behavior. - Highlights: • Size and composition of nanoporous layers tailored in de-alloying Au-based glassy ribbons. • From amorphous precursor fine crystals occur in ligaments with residual Pd and Ag. • Fully de

Immobilization of DNA at Glassy Ccarbon Electrodes: A Critical Study of Adsorbed Layer

Directory of Open Access Journals (Sweden)

G. A. Rivas

2005-11-01

Full Text Available In this work we present a critical study of the nucleic acid layer immobilized atglassy carbon electrodes. Different studies were performed in order to assess the nature of theinteraction between DNA and the electrode surface. The adsorption and electrooxidation of DNAdemonstrated to be highly dependent on the surface and nature of the glassy carbon electrode. TheDNA layer immobilized at a freshly polished glassy carbon electrode was very stable even afterapplying highly negative potentials. The electron transfer of potassium ferricyanide, catechol anddopamine at glassy carbon surfaces modified with thin (obtained by adsorption under controlledpotential conditions and thick (obtained by casting the glassy carbon surface with highly concentratedDNA solutions DNA layers was slower than that at the bare glassy carbon electrode, although thiseffect was dependent on the thickness of the layer and was not charge selective. Raman experimentsshowed an important decrease of the vibrational modes assigned to the nucleobases residues,suggesting a strong interaction of these residues with the electrode surface. The hybridization ofoligo(dG21 and oligo(dC21 was evaluated from the guanine oxidation signal and the reduction of theredox indicator Co(phen33+ . In both cases the chronopotentiometric response indicated that thecompromise of the bases in the interaction of DNA with the electrode surface is too strong, preventingfurther hybridization. In summary, glassy carbon is a useful electrode material to detect DNA in adirect and very sensitive way, but not to be used for the preparation of biorecognition layers by directadsorption of the probe sequence on the electrode surface for detecting the hybridization event.

Crystal structure optimisation using an auxiliary equation of state

Science.gov (United States)

Jackson, Adam J.; Skelton, Jonathan M.; Hendon, Christopher H.; Butler, Keith T.; Walsh, Aron

2015-11-01

Standard procedures for local crystal-structure optimisation involve numerous energy and force calculations. It is common to calculate an energy-volume curve, fitting an equation of state around the equilibrium cell volume. This is a computationally intensive process, in particular, for low-symmetry crystal structures where each isochoric optimisation involves energy minimisation over many degrees of freedom. Such procedures can be prohibitive for non-local exchange-correlation functionals or other "beyond" density functional theory electronic structure techniques, particularly where analytical gradients are not available. We present a simple approach for efficient optimisation of crystal structures based on a known equation of state. The equilibrium volume can be predicted from one single-point calculation and refined with successive calculations if required. The approach is validated for PbS, PbTe, ZnS, and ZnTe using nine density functionals and applied to the quaternary semiconductor Cu2ZnSnS4 and the magnetic metal-organic framework HKUST-1.

Crystal structure optimisation using an auxiliary equation of state

International Nuclear Information System (INIS)

Jackson, Adam J.; Skelton, Jonathan M.; Hendon, Christopher H.; Butler, Keith T.; 3 Institute and Department of Materials Science and Engineering, Yonsei University, Seoul 120-749 (Korea, Republic of))" data-affiliation=" (Centre for Sustainable Chemical Technologies and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Global E3 Institute and Department of Materials Science and Engineering, Yonsei University, Seoul 120-749 (Korea, Republic of))" >Walsh, Aron

2015-01-01

Standard procedures for local crystal-structure optimisation involve numerous energy and force calculations. It is common to calculate an energy–volume curve, fitting an equation of state around the equilibrium cell volume. This is a computationally intensive process, in particular, for low-symmetry crystal structures where each isochoric optimisation involves energy minimisation over many degrees of freedom. Such procedures can be prohibitive for non-local exchange-correlation functionals or other “beyond” density functional theory electronic structure techniques, particularly where analytical gradients are not available. We present a simple approach for efficient optimisation of crystal structures based on a known equation of state. The equilibrium volume can be predicted from one single-point calculation and refined with successive calculations if required. The approach is validated for PbS, PbTe, ZnS, and ZnTe using nine density functionals and applied to the quaternary semiconductor Cu 2 ZnSnS 4 and the magnetic metal-organic framework HKUST-1

Crystal structure optimisation using an auxiliary equation of state

Energy Technology Data Exchange (ETDEWEB)

Jackson, Adam J.; Skelton, Jonathan M.; Hendon, Christopher H.; Butler, Keith T. [Centre for Sustainable Chemical Technologies and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Walsh, Aron, E-mail: a.walsh@bath.ac.uk [Centre for Sustainable Chemical Technologies and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (United Kingdom); Global E" 3 Institute and Department of Materials Science and Engineering, Yonsei University, Seoul 120-749 (Korea, Republic of)

2015-11-14

Standard procedures for local crystal-structure optimisation involve numerous energy and force calculations. It is common to calculate an energy–volume curve, fitting an equation of state around the equilibrium cell volume. This is a computationally intensive process, in particular, for low-symmetry crystal structures where each isochoric optimisation involves energy minimisation over many degrees of freedom. Such procedures can be prohibitive for non-local exchange-correlation functionals or other “beyond” density functional theory electronic structure techniques, particularly where analytical gradients are not available. We present a simple approach for efficient optimisation of crystal structures based on a known equation of state. The equilibrium volume can be predicted from one single-point calculation and refined with successive calculations if required. The approach is validated for PbS, PbTe, ZnS, and ZnTe using nine density functionals and applied to the quaternary semiconductor Cu{sub 2}ZnSnS{sub 4} and the magnetic metal-organic framework HKUST-1.

On the spherical nanoindentation creep of metallic glassy thin films at room temperature

Energy Technology Data Exchange (ETDEWEB)

Zhang, T.H.; Ye, J.H. [Institution of Micro/Nano-Mechanical Testing Technology & Application, College of Mechanical Engineering, Zhejiang University of Technology, Hangzhou 310014 (China); Feng, Y.H. [State Key Laboratory of Nonlinear Mechanics (LNM), Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190 (China); Ma, Y., E-mail: may@zjut.edu.cn [Institution of Micro/Nano-Mechanical Testing Technology & Application, College of Mechanical Engineering, Zhejiang University of Technology, Hangzhou 310014 (China)

2017-02-08

Metallic glassy thin films with eight kind of compositions were successfully prepared on Si substrate by magnetron sputtering. The room-temperature creep tests were performed at plastic regions for each sample relying on spherical nanoindetation. The creep deformations were studied by recording the total creep displacement and strain after 2000 s holding. More pronounced creep deformation was observed in the sample with lower glass transition temperature (T{sub g}). Strain rate sensitivity (SRS) was then calculated from the steady-state creep and exhibited a negative correlation with increasing T{sub g}. It is suggested that creep mechanism of the nano-sized metallic glass was T{sub g}-dependent, according to the demarcation of SRS values. Based on the obtained SRS, shear transformation zone (STZ) size in each sample could be estimated. The results indicated that an STZ involves about 25–60 atoms for the employed eight samples and is strongly tied to T{sub g}. The characteristic of STZ size in metallic glassy thin films was discussed in terms of applied method and deformation modes.

Spatially heterogeneous ages in glassy dynamics

International Nuclear Information System (INIS)

Castillo, Horacio E.; Chamon, Claudio Chamon; Cugliandolo, Leticia F.; Iguain, Jose Luis; Kennett, Malcolm P.

2003-09-01

We construct a framework for the study of fluctuations in the nonequilibrium relaxation of glassy systems with and without quenched disorder. We study two types of two-time local correlators with the aim of characterizing the heterogeneous evolution in these systems: in one case we average the local correlators over histories of the thermal noise, in the other case we simply coarse-grain the local correlators obtained for a given noise realization. We explain why the noise-averaged correlators describe the fingerprint of quenched disorder when it exists, while the coarse-grained correlators are linked to noise-induced mesoscopic fluctuations. We predict constraints on the distribution of the fluctuations of the coarse-grained quantities. In particular, we show that locally defined correlations and responses are connected by a generalized local out-of-equilibrium fluctuation-dissipation relation. We argue that large size heterogeneities in the age of the system survive in the long-time limit. A symmetry of the underlying theory, namely invariance under reparametrizations of the time coordinates, underlies these results. We establish a connection between the probabilities of spatial distributions of local coarse-grained quantities and the theory of dynamic random manifolds. We define, and discuss the behavior of, a two-time dependent correlation length from the spatial decay of the fluctuations in the two-time local functions. We characterize the fluctuations in the system in terms of their fractal properties. For concreteness, we present numerical tests performed on disordered spin models in finite and infinite dimensions. Finally, we explain how these ideas can be applied to the analysis of the dynamics of other glassy systems that can be either spin models without disorder or atomic and molecular glassy systems. (author)

Dielectric relaxation in glassy Se75In25− xPbx alloys

Indian Academy of Sciences (India)

In this paper we report the effect of Pb incorporation in the dielectric properties of a-Se75In25 glassy alloy. The temperature and frequency dependence of the dielectric constants and the dielectric losses in glassy Se75In25−Pb ( = 0, 5, 10 and 15) alloys in the frequency range (1 kHz–5 MHz) and temperature range ...

New model system in radiation cryochemistry. Hyperquenched glassy water

International Nuclear Information System (INIS)

Plonka, A.

1998-01-01

Complete text of publication follows. Since the radical generated by high-energy irradiation of liquid water are short-lived at ambient temperature, they are often studied at cryogenic temperatures after irradiating either crystalline ice or highly concentrated aqueous electrolyte solution glasses. While these studies provided a wealth of information, they also bear disadvantages in that further reactions of these radicals may not be those occurring in liquid water because of formation of other radicals from the solute in the case of the electrolyte solution glass and/or perturbation of the water structure by the solute. Furthermore, in slow-cooled aqueous solutions where ice is formed and phase separation of the solute occurs, the radicals trapped in the ice compartments are unable to interact with solutes because these are dissolved in the 'freeze-concentration' regions. These problems can in principle be overcome by investigating water and dilute aqueous solutions in their glassy states which can be obtained by rapid quenching of the liquids. Glassy water can now routinely be made in gram-quantities by so-called 'hyperquenching' of micrometer-sized water droplets on a solid cryoplate. The cooling rates are of the order of 10 6 - 10 7 K s -1 . Our results show that indeed in the hyperquenched dilute aqueous solutions there is no problem with phase separation and radiolysis of hyperquenched water is quite distinct from radiolysis of polycrystalline ice obtained from liquid water quenched in the liquid nitrogen

Topologically protected bound states in photonic parity-time-symmetric crystals.

Science.gov (United States)

Weimann, S; Kremer, M; Plotnik, Y; Lumer, Y; Nolte, S; Makris, K G; Segev, M; Rechtsman, M C; Szameit, A

2017-04-01

Parity-time (PT)-symmetric crystals are a class of non-Hermitian systems that allow, for example, the existence of modes with real propagation constants, for self-orthogonality of propagating modes, and for uni-directional invisibility at defects. Photonic PT-symmetric systems that also support topological states could be useful for shaping and routing light waves. However, it is currently debated whether topological interface states can exist at all in PT-symmetric systems. Here, we show theoretically and demonstrate experimentally the existence of such states: states that are localized at the interface between two topologically distinct PT-symmetric photonic lattices. We find analytical closed form solutions of topological PT-symmetric interface states, and observe them through fluorescence microscopy in a passive PT-symmetric dimerized photonic lattice. Our results are relevant towards approaches to localize light on the interface between non-Hermitian crystals.

Interpretation of the Raman spectra of the glassy states of Si{sub x}S{sub 1−x} and Si{sub x}Se{sub 1−x}

Energy Technology Data Exchange (ETDEWEB)

Devi, V. Radhika [M.L.R. Institute of Technology, Affiliated to Jawaharlal Nehru Technological University, Dundigal, Hyderabad 500043 (India); Zabidi, Noriza Ahmad [Department of Physics, Centre for Defence Foundation Studies, National Defence University of Malaysia, Kem Sungai Besi, Kuala Lumpur 57000 (Malaysia); Shrivastava, Keshav N., E-mail: keshav1001@yahoo.com [School of Physics, University of Hyderabad, Hyderabad 50046 (India); Department of Physics, University of Malaya, Kuala Lumpur 50603 (Malaysia)

2013-09-16

We use the density-functional theory to make models of Si{sub x}S{sub y} and Si{sub x}Se{sub y} for the values of x,y = 1–6. The vibrational frequencies are calculated for each model. The stable clusters are selected on the basis of positive vibrational frequencies. In the case of Si{sub x}S{sub 1−x}, the values of the vibrational frequencies calculated from the first principles for Si{sub 2}S(triangular)cluster of atoms, 364.1 cm{sup −1} and 380.8 cm{sup −1}, agree with the experimentally measured values of 367 cm{sup −1} and 381 cm{sup −1}, indicating that Si{sub 2}S clusters occur in the glassy state of SiS. The calculated values of the vibrational frequencies of SiSe{sub 4} (pyramidal) which agree with the experimental Raman frequencies of glassy Si{sub x}Se{sub 1−x} are 114, 166 and 361 cm{sup −1}. The calculated values for Si{sub 2}Se{sub 4} (bipyramidal) which agree with the experimental data of Si{sub x}Se{sub 1−x} are 166 and 464 cm{sup −1}. In Si{sub 4}Se (pyramidal) the values 246 and 304 cm{sup −1} agree with the measured values. In Si{sub 4}Se{sub 2} (bipyramidal), the calculated values 162, 196 and 304 cm{sup −1} agree with the measured values. The calculated values of 473 cm{sup −1} for Si{sub 6}Se{sub 2} (bipyramidal) also agree with the experimentally measured values. We thus find that pyramidal structures are present in the amorphous Si{sub x}Se{sub 1−x} glassy state. - Highlights: • A first principles calculation is performed to calculate the vibrational frequencies. • The calculated frequencies of clusters agree with measured Raman values. • The structures, bond lengths and symmetries are determined. • The importance of Jahn–Teller effect in SiS and in SiSe is clearly seen. • The clusters of SiS and SiSe are found to stabilize in different symmetries.

"Non-equilibrium" block copolymer micelles with glassy cores: a predictive approach based on theory of equilibrium micelles.

Science.gov (United States)

Nagarajan, Ramanathan

2015-07-01

Micelles generated in water from most amphiphilic block copolymers are widely recognized to be non-equilibrium structures. Typically, the micelles are prepared by a kinetic process, first allowing molecular scale dissolution of the block copolymer in a common solvent that likes both the blocks and then gradually replacing the common solvent by water to promote the hydrophobic blocks to aggregate and create the micelles. The non-equilibrium nature of the micelle originates from the fact that dynamic exchange between the block copolymer molecules in the micelle and the singly dispersed block copolymer molecules in water is suppressed, because of the glassy nature of the core forming polymer block and/or its very large hydrophobicity. Although most amphiphilic block copolymers generate such non-equilibrium micelles, no theoretical approach to a priori predict the micelle characteristics currently exists. In this work, we propose a predictive approach for non-equilibrium micelles with glassy cores by applying the equilibrium theory of micelles in two steps. In the first, we calculate the properties of micelles formed in the mixed solvent while true equilibrium prevails, until the micelle core becomes glassy. In the second step, we freeze the micelle aggregation number at this glassy state and calculate the corona dimension from the equilibrium theory of micelles. The condition when the micelle core becomes glassy is independently determined from a statistical thermodynamic treatment of diluent effect on polymer glass transition temperature. The predictions based on this "non-equilibrium" model compare reasonably well with experimental data for polystyrene-polyethylene oxide diblock copolymer, which is the most extensively studied system in the literature. In contrast, the application of the equilibrium model to describe such a system significantly overpredicts the micelle core and corona dimensions and the aggregation number. The non-equilibrium model suggests ways to

Potentiometric application of boron- and phosphorus-doped glassy carbon electrodes

Directory of Open Access Journals (Sweden)

ZORAN V. LAUSEVIC

2001-03-01

Full Text Available Acomparative study was carried out of the potentiometric application of boronand phosphorus-doped and undoped glassy carbon samples prepared at the same heat treatment temperature (HTT 1000°C. The electrochemical activities of the obtained electrode materials were investigated on the example of argentometric titrations. It was found that the electrochemical behaviour of the doped glassy carbon samples are very similar to a Sigri (undoped glassy carbon sample (HTT 2400°C. The experiments showed that the potentiometric response depends on the polarization mode, the nature of the sample, the pretreatment of the electrode surface, and the nature of the supporting electrolyte. The amounts of iodide, bromide, and of chloridewere determined to be 1.27 mg, 0.80 mg and 0.54 mg, respectively, with a maximum relative standard deviation of less than 1.1%. The obtained results are in good agreement with the results of comparative potentiometric titrations using a silver indicator electrode. The titrationmethod was applied to the indirect determination of pyridoxine hydrochloride, i.e., vitamin B6.

mwnts composite film modified glassy carbon electrode

African Journals Online (AJOL)

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ABSTRACT: A poly p-aminosalicylic acid (Poly(p-ASA)) and multiwall carbon nanotubes. (MWCNTs) composite modified glassy carbon (GC) electrode was constructed by casting the MWNTs on the GC electrode surface followed by electropolymerization of the p-ASA on the MWCNTs/GCE. The electrochemical behaviours ...

Voltammetric pH sensing using carbon electrodes: glassy carbon behaves similarly to EPPG.

Science.gov (United States)

Lu, Min; Compton, Richard G

2014-09-21

Developing and building on recent work based on a simple sensor for pH determination using unmodified edge plane pyrolytic graphite (EPPG) electrodes, we present a voltammetric method for pH determination using a bare unmodified glassy carbon (GC) electrode. By exploiting the pH sensitive nature of quinones present on carbon edge-plane like sites within the GC, we show how GC electrodes can be used to measure pH. The electro-reduction of surface quinone groups on the glassy carbon electrode was characterised using cyclic voltammetry (CV) and optimised with square-wave voltammetry (SWV) at 298 K and 310 K. At both temperatures, a linear correlation was observed, corresponding to a 2 electron, 2 proton Nernstian response over the aqueous pH range 1.0 to 13.1. As such, unmodified glassy carbon electrodes are seen to be pH dependent, and the Nernstian response suggests its facile use for pH sensing. Given the widespread use of glassy carbon electrodes in electroanalysis, the approach offers a method for the near-simultaneous measurement and monitoring of pH during such analyses.

The glass transition, crystallization and melting in Au-Pb-Sb alloys

Science.gov (United States)

Lee, M. C.; Allen, J. L.; Fecht, H. J.; Perepezko, J. H.; Ohsaka, K.

1988-01-01

The glass transition, crystallization and melting of Au(55)Pb(22.5)Sb(22.5) alloys have been studied by differential scanning calorimetry DSC. Crystallization on heating above the glass transition temperature Tg (45 C) begins at 64 C. Further crystallization events are observed at 172 C and 205 C. These events were found to correspond to the formation of the intermetallic compounds AuSb2, Au2Pb, and possibly AuPb2, respectively. Isothermal DSC scans of the glassy alloy above Tg were used to monitor the kinetics of crystallization. The solidification behavior and heat capacity in the glass-forming composition range were determined with droplet samples. An undercooling level of 0.3T(L) below the liquidus temperature T(L) was achieved, resulting in crystallization of different stable and metastable phases. The heat capacity C(P) of the undercooled liquid was measured over an undercooling range of 145 C.

Thermodynamic Modeling of Gas Transport in Glassy Polymeric Membranes.

Science.gov (United States)

Minelli, Matteo; Sarti, Giulio Cesare

2017-08-19

Solubility and permeability of gases in glassy polymers have been considered with the aim of illustrating the applicability of thermodynamically-based models for their description and prediction. The solubility isotherms are described by using the nonequilibrium lattice fluid (NELF) (model, already known to be appropriate for nonequilibrium glassy polymers, while the permeability isotherms are described through a general transport model in which diffusivity is the product of a purely kinetic factor, the mobility coefficient, and a thermodynamic factor. The latter is calculated from the NELF model and mobility is considered concentration-dependent through an exponential relationship containing two parameters only. The models are tested explicitly considering solubility and permeability data of various penetrants in three glassy polymers, PSf, PPh and 6FDA-6FpDA, selected as the reference for different behaviors. It is shown that the models are able to calculate the different behaviors observed, and in particular the permeability dependence on upstream pressure, both when it is decreasing as well as when it is increasing, with no need to invoke the onset of additional plasticization phenomena. The correlations found between polymer and penetrant properties with the two parameters of the mobility coefficient also lead to the predictive ability of the transport model.

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.

Relation between time-temperature transformation and continuous heating transformation diagrams of metallic glassy alloys

International Nuclear Information System (INIS)

Louzguine-Luzgin, Dmitri V.; Inoue, Akihisa

2005-01-01

The time-temperature transformation (TTT) diagrams for the onset of devitrification of the Ge-Ni-La and Cu-Hf-Ti glassy alloys were calculated from the isothermal differential calorimetry data using an Arrhenius equation. The continuous heating transformation (CHT) diagrams for the onset of devitrification of the glassy alloys were subsequently recalculated from TTT diagrams. The recalculation method used for conversion of the TTT into CHT diagrams produces reasonable results and is not sensitive to the type of the devitrification reaction (polymorphous or primary transformation). The diagrams allow to perform a comparison of the stabilities of glassy alloys on a long-term scale. The relationship between these diagrams is discussed

Playback interference of glassy-winged sharp shooter communication

Science.gov (United States)

Animal communication is vital to reproduction, particularly for securing a mate. Insects commonly communicate by exchanging vibrational signals that are transmitted through host plants. The glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, is an important vector of Xylella fastidiosa, a pl...

Glass formation and crystallization in Zr based alloys

International Nuclear Information System (INIS)

Dey, G. K.

2011-01-01

Metallic glasses have come in to prominence in recent times because their nanocrystalline atomic arrangement imparts many useful and unusual properties to these metallic solids. Though these have been produced for the last four decades, the necessity of rapid solidification at cooling rates of 10 5 K/sec or higher for their production, have restricted their geometry to thin ribbons and prevented their application to many areas despite their excellent properties. It has been shown in recent investigations that, many Zr base multicomponent alloys can be obtained in glassy state by cooling at much lower rate typically 10 2 to 10 3 K/sec. This has enabled production of these alloys in the glassy stat in bulk. By now, bulk metallic glasses have been produced in Mg, Ln, Zr, Fe, Pd-Cu, Pd-Fe, Ti and Ni- based alloys. Production of these glasses in bulk has opened avenue for their application in many areas where their excellent mechanical properties an corrosion resistance can be exploited. The transformation of the amorphous phase in these alloys to one or more crystalline phases, is an interesting phase transformation and can lead to formation of crystals in a variety of morphologies and a wide range of crystal sizes, including nanometer size crystals or nanocrystals. The bulk amorphous alloys exhibit higher fracture stress, combined with higher hardness and lower young's modulus than those of any crystalline alloy. The Zr- and Ti-based bulk amorphous alloy exhibit high bending and flexural strength values which are typically 2.0 to 2.5 time higher than those for crystalline counterparts. The composites of bulk metallic glass containing crystalline phases have been found to have special properties. This has been demonstrated in the case of composites of bulk metallic glass and tungsten wires wit the glass forming the matrix. Such a composite has a very high impact strength and is especially suitable for application as an armour penetrator in various types of shells used

Steady-state crack growth in single crystals under Mode I loading

DEFF Research Database (Denmark)

Juul, Kristian Jørgensen; Nielsen, Kim Lau; Niordson, Christian Frithiof

2017-01-01

The active plastic zone that surrounds the tip of a sharp crack growing under plane strain Mode I loading conditions at a constant velocity in a single crystal is studied. Both the characteristics of the plastic zone and its effect on the macroscopic toughness is investigated in terms of crack tip...... that the largest shielding effect develops in HCP crystals, while the lowest shielding exists for FCC crystals. Rate-sensitivity is found to affect the plastic zone size, but the characteristics overall remain similar for each individual crystal structure. An increasing rate-sensitivity at low crack velocities...... shielding due to plasticity (quantified by employing the Suo, Shih, and Varias set-up). Three single crystals (FCC, BCC, HCP) are modelled in a steady-state elastic visco-plastic framework, with emphasis on the influence of rate-sensitivity and crystal structures. Distinct velocity discontinuities...

A novel laser-based method for controlled crystallization in dental prosthesis materials

Science.gov (United States)

Cam, Peter; Neuenschwander, Beat; Schwaller, Patrick; Köhli, Benjamin; Lüscher, Beat; Senn, Florian; Kounga, Alain; Appert, Christoph

2015-02-01

Glass-ceramic materials are increasingly becoming the material of choice in the field of dental prosthetics, as they can feature both high strength and very good aesthetics. It is believed that their color, microstructure and mechanical properties can be tuned such as to achieve an optimal lifelike performance. In order to reach that ultimate perfection a controlled arrangement of amorphous and crystalline phases in the material is required. A phase transformation from amorphous to crystalline is achieved by a heat treatment at defined temperature levels. The traditional approach is to perform the heat treatment in a furnace. This, however, only allows a homogeneous degree of crystallization over the whole volume of the parent glass material. Here a novel approach using a local heat treatment by laser irradiation is presented. To investigate the potential of this approach the crystallization process of SiO2-Li2O-Al2O3-based glass has been studied with laser systems (pulsed and continuous wave) operating at different wavelengths. Our results show the feasibility of gradual and partial crystallization of the base material using continuous laser irradiation. A dental prosthesis machined from an amorphous glassy state can be effectively treated with laser irradiation and crystallized within a confined region of a few millimeters starting from the body surface. Very good aesthetics have been achieved. Preliminary investigation with pulsed nanosecond lasers of a few hundreds nanoseconds pulse width has enabled more refinement of crystallization and possibility to place start of phase change within the material bulk.

Relationship between low-temperature boson heat capacity peak and high-temperature shear modulus relaxation in a metallic glass

International Nuclear Information System (INIS)

Vasiliev, A. N.; Voloshok, T. N.; Granato, A. V.; Joncich, D. M.; Mitrofanov, Yu. P.; Khonik, V. A.

2009-01-01

Low-temperature (2 K≤T≤350 K) heat capacity and room-temperature shear modulus measurements (ν=1.4 MHz) have been performed on bulk Pd 41.25 Cu 41.25 P 17.5 in the initial glassy, relaxed glassy, and crystallized states. It has been found that the height of the low-temperature Boson heat capacity peak strongly correlates with the changes in the shear modulus upon high-temperature annealing. It is this behavior that was earlier predicted by the interstitialcy theory, according to which dumbbell interstitialcy defects are responsible for a number of thermodynamic and kinetic properties of crystalline, (supercooled) liquid, and solid glassy states.

Fine kinetics of natural physical ageing in glassy As{sub 10}Se{sub 90}

Energy Technology Data Exchange (ETDEWEB)

Balitska, V. [Institute of Materials, Scientific Research Company “Carat”, 202 Stryjska Str., 79031 Lviv (Ukraine); Lviv State University of Vital Activity Safety, 35, Kleparivska Str., Lviv 79007 (Ukraine); Golovchak, R. [Department of Physics and Astronomy, Austin Peay State University, Clarksville, TN 37044 (United States); Kozdras, A. [Faculty of Physics of Opole Technical University, 75, Ozimska Str., Opole 45370 (Poland); Shpotyuk, O., E-mail: shpotyuk@novas.lviv.ua [Institute of Materials, Scientific Research Company “Carat”, 202 Stryjska Str., 79031 Lviv (Ukraine); Institute of Physics, Jan Dlugosz University, Al. Armii Krajowej 13/15, Czestochowa 42201 (Poland)

2014-02-01

Sigmoid behavior of natural physical ageing in glassy As{sub 10}Se{sub 90} reveals multi-step-wise growing kinetics of enthalpy losses. Phenomenological description of this kinetics can be adequately developed in terms of first-order relaxation processes, tending atomic structure from initial towards more thermodynamically equilibrium state. This kinetics is shown to obey characteristic stretched exponential behavior originated from a number of growing steps, attributed to the interconnected processes of chalcogen chain alignment and cooperative shrinkage of glass network.

Annealing effects on the migration of ion-implanted cadmium in glassy carbon

Energy Technology Data Exchange (ETDEWEB)

Hlatshwayo, T.T., E-mail: thulani.hlatshwayo@up.ac.za [Physics Department, University of Pretoria, Pretoria (South Africa); Sebitla, L.D. [Physics Department, University of Pretoria, Pretoria (South Africa); Physics Department, University of Botswana, Gaborone (Botswana); Njoroge, E.G.; Mlambo, M.; Malherbe, J.B. [Physics Department, University of Pretoria, Pretoria (South Africa)

2017-03-15

The migration behaviour of cadmium (Cd) implanted into glassy carbon and the effects of annealing on radiation damage introduced by ion implantation were investigated. The glassy carbon substrates were implanted with Cd at a dose of 2 × 10{sup 16} ions/cm{sup 2} and energy of 360 keV. The implantation was performed at room temperature (RT), 430 °C and 600 °C. The RT implanted samples were isochronally annealed in vacuum at 350, 500 and 600 °C for 1 h and isothermally annealed at 350 °C up to 4 h. The as-implanted and annealed samples were characterized by Raman spectroscopy and Rutherford backscattering spectrometry (RBS). Raman results revealed that implantation at room temperature amorphized the glassy carbon structure while high temperature implantations resulted in slightly less radiation damage. Isochronal annealing of the RT implanted samples resulted in some recrystallization as a function of increasing temperature. The original glassy carbon structure was not achieved at the highest annealing temperature of 600 °C. Diffusion of Cd in glassy carbon was already taking place during implantation at 430 °C. This diffusion of Cd was accompanied by significant loss from the surface during implantation at 600 °C. Isochronal annealing of the room temperature implanted samples at 350 °C for 1 h caused Cd to diffuse towards the bulk while isothermal annealing at 500 and 600 °C resulted in the migration of implanted Cd toward the surface accompanied by a loss of Cd from the surface. Isothermal annealing at 350 °C for 1 h caused Cd to diffuse towards the bulk while for annealing time >1 h Cd diffused towards the surface. These results were interpreted in terms of trapping and de-trapping of implanted Cd by radiation damage.

Controlling the volatility of the written optical state in electrochromic DNA liquid crystals

Science.gov (United States)

Liu, Kai; Varghese, Justin; Gerasimov, Jennifer Y.; Polyakov, Alexey O.; Shuai, Min; Su, Juanjuan; Chen, Dong; Zajaczkowski, Wojciech; Marcozzi, Alessio; Pisula, Wojciech; Noheda, Beatriz; Palstra, Thomas T. M.; Clark, Noel A.; Herrmann, Andreas

2016-05-01

Liquid crystals are widely used in displays for portable electronic information display. To broaden their scope for other applications like smart windows and tags, new material properties such as polarizer-free operation and tunable memory of a written state become important. Here, we describe an anhydrous nanoDNA-surfactant thermotropic liquid crystal system, which exhibits distinctive electrically controlled optical absorption, and temperature-dependent memory. In the liquid crystal isotropic phase, electric field-induced colouration and bleaching have a switching time of seconds. Upon transition to the smectic liquid crystal phase, optical memory of the written state is observed for many hours without applied voltage. The reorientation of the DNA-surfactant lamellar layers plays an important role in preventing colour decay. Thereby, the volatility of optoelectronic state can be controlled simply by changing the phase of the material. This research may pave the way for developing a new generation of DNA-based, phase-modulated, photoelectronic devices.

Crystal structure and spin state of mixed-crystals of iron with zinc and cobalt for the assembled complexes bridged by 1,3-bis(4-pyridyl)propanes

Energy Technology Data Exchange (ETDEWEB)

Dote, Haruka [Hiroshima University, Graduate School of Science (Japan); Nakashima, Satoru, E-mail: snaka@hiroshima-u.ac.jp [Hiroshima University, Natural Science Center for Basic Research and Development (Japan)

2012-03-15

Mixed crystals of cobalt and zinc were synthesized using 1,3-bis(4-pyridyl)propane (bpp) as bridging ligand and NCS{sup - } as anion. Red crystals and blue crystals were obtained. Powder X-ray diffraction patterns showed that the former is in 2D interpenetrated structure, while the latter has the same structure with Zn(NCS){sub 2}(bpp). Iron ion was introduced both into the red crystals and blue crystals of the mixed crystals of cobalt with zinc. {sup 57}Fe Moessbauer spectrum of the red crystals showed a main doublet of Fe{sup II} high-spin state at 78 K, while the spectrum of blue crystals did not show Fe{sup II} high-spin state at 78 K.

Crystal structure and spin state of mixed-crystals of iron with zinc and cobalt for the assembled complexes bridged by 1,3-bis(4-pyridyl)propanes

International Nuclear Information System (INIS)

Dote, Haruka; Nakashima, Satoru

2012-01-01

Mixed crystals of cobalt and zinc were synthesized using 1,3–bis(4–pyridyl)propane (bpp) as bridging ligand and NCS  −  as anion. Red crystals and blue crystals were obtained. Powder X-ray diffraction patterns showed that the former is in 2D interpenetrated structure, while the latter has the same structure with Zn(NCS) 2 (bpp). Iron ion was introduced both into the red crystals and blue crystals of the mixed crystals of cobalt with zinc. 57 Fe Mössbauer spectrum of the red crystals showed a main doublet of Fe II high-spin state at 78 K, while the spectrum of blue crystals did not show Fe II high-spin state at 78 K.

Abstracts of 12. Conference on Solid State Crystals Materials Science and Applications

International Nuclear Information System (INIS)

1996-01-01

The solid state crystals are the modern materials being very interesting from the view point of actual and possible applications in microelectronics, optics, laser materials, detectors etc. 12. Conference on Solid State Crystals, Materials Science and Applications, Zakopane'99 created the review forum for broad range of investigations on topics related to; crystal growth and doping, new materials preparation, thin layer structure, physical properties and special methods for electrical, magnetic, optical and mechanical properties measurements of obtained materials. The insulating, semiconducting and superconducting monocrystals, polycrystals and also amorphous glasses have been investigated and their possible applications discussed. 52 oral lectures and 128 posters have been presented in the course of the conference

A glassy lava flow from Toconce volcano and its relation with the Altiplano-Puna Magma Body in Central Andes

Science.gov (United States)

Godoy, B.; Rodriguez, I.; Aguilera, F.

2012-12-01

Toconce is a composite stratovolcano located at the San Pedro - Linzor volcanic chain (SPLVC). This volcanic chain distributes within the Altiplano-Puna region (Central Andes) which is characterized by extensive rhyodacitic-to-rhyolitic ignimbritic fields, and voluminous domes of dacitic-to-rhyolitic composition (de Silva, 1989). The felsic melts that gave origin to ignimbrites and domes at this area were generated by mixing of mantle-derived magmas and anatectic melts assimilated during their ascent through the thick crust. Thus, partially molten layers exist in the upper crust below the APVC (de Silva et al., 2006). Evidence of large volumes of such melts has been also proposed by geophysical methods (i.e. the Altiplano-Puna Magma Body; Chmielowsky et al., 1999) In this work, petrography and whole rock, mineralogical and melt inclusions geochemistry of a glassy lava flow of Toconce volcano are presented. Petrographically, this lava flow shows a porphyric texture, with euhdral to subhedral plagioclase, ortho- and clino-pyroxene phenocrysts immersed in a glassy groundmass. Geochemically, the lava flow has 64.7% wt. SiO2. The glassy groundmass (~70% wt. SiO2) is more felsic than all the lavas in the volcanic chain (47-68% wt., Godoy et al., 2011). Analyzed orthopyroxene-hosted melt inclusions show an even higher SiO2 content (72-75% wt.), and a decreasing on Al2O3, Na2O, and CaO content with differentiation. Crystallization pressures of this lava flow, obtained using Putirka's two-pyroxene and clinopyroxene-liquid models (Putirka, 2008), range between 6 and 9 kbar. According to crystallization pressures, and major element composition, a felsic source located at shallow crustal pressures - where plagioclase is a stable mineralogical phase - originated the inclusions. This could be related to the presence of the Altiplano-Puna Magma Body (APMB) located below SPLVC. On the other hand, glassy groundmass, and disequilibrium textures in minerals of this lava flow could

Hysteresis, reentrance, and glassy dynamics in systems of self-propelled rods.

Science.gov (United States)

Kuan, Hui-Shun; Blackwell, Robert; Hough, Loren E; Glaser, Matthew A; Betterton, M D

2015-01-01

Nonequilibrium active matter made up of self-driven particles with short-range repulsive interactions is a useful minimal system to study active matter as the system exhibits collective motion and nonequilibrium order-disorder transitions. We studied high-aspect-ratio self-propelled rods over a wide range of packing fractions and driving to determine the nonequilibrium state diagram and dynamic properties. Flocking and nematic-laning states occupy much of the parameter space. In the flocking state, the average internal pressure is high and structural and mechanical relaxation times are long, suggesting that rods in flocks are in a translating glassy state despite overall flock motion. In contrast, the nematic-laning state shows fluidlike behavior. The flocking state occupies regions of the state diagram at both low and high packing fraction separated by nematic-laning at low driving and a history-dependent region at higher driving; the nematic-laning state transitions to the flocking state for both compression and expansion. We propose that the laning-flocking transitions are a type of glass transition that, in contrast to other glass-forming systems, can show fluidization as density increases. The fluid internal dynamics and ballistic transport of the nematic-laning state may promote collective dynamics of rod-shaped micro-organisms.

Effect of cellulose nanocrystals (CNC) on rheological and mechanical properties and crystallization behavior of PLA/CNC nanocomposites.

Science.gov (United States)

Kamal, Musa R; Khoshkava, Vahid

2015-06-05

In earlier work, we reported that spray freeze drying of cellulose nanocrystals (CNC) yields porous agglomerate structures. On the other hand, the conventional spray dried CNC (CNCSD) and the freeze dried CNC (CNCFD) produce compact solid structures with very low porosity. As it is rather difficult to obtain direct microscopic evidence of the quality of dispersion of CNC in polymer nanocomposites, it was shown that supporting evidence of the quality and influence of dispersion in a polypropylene (PP)/CNC nanocomposite could be obtained by studying the rheological behavior, mechanical properties and crystallization characteristics of PP/CNC nanocomposites. In an effort to produce a sustainable, fully biosourced, biodegradable nanocomposite, this manuscript presents the results of a study of the rheological, mechanical and crystallization behavior of PLA/CNCSFD nanocomposites obtained by melt processing. The results are analyzed to determine CNC network formation, rheological percolation threshold concentrations, mechanical properties in the rubbery and glassy states, and the effect of CNCSFD on crystalline nucleation and crystallization rates of PLA. These results suggest that the porosity and network structure of CNCSFD agglomerates contribute significantly to good dispersion of CNC in the PLA matrix. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrically tunable robust edge states in graphene-based topological photonic crystal slabs

Science.gov (United States)

Song, Zidong; Liu, HongJun; Huang, Nan; Wang, ZhaoLu

2018-03-01

Topological photonic crystals are optical structures supporting topologically protected unidirectional edge states that exhibit robustness against defects. Here, we propose a graphene-based all-dielectric photonic crystal slab structure that supports two-dimensionally confined topological edge states. These topological edge states can be confined in the out-of-plane direction by two parallel graphene sheets. In the structure, the excitation frequency range of topological edge states can be dynamically and continuously tuned by varying bias voltage across the two parallel graphene sheets. Utilizing this kind of architecture, we construct Z-shaped channels to realize topological edge transmission with diffrerent frequencies. The proposal provides a new degree of freedom to dynamically control topological edge states and potential applications for robust integrated photonic devices and optical communication systems.

Electrochemical oxidation of niclosamide at a glassy carbon ...

African Journals Online (AJOL)

Cyclic voltammetry, square-wave voltammetry and controlled potential electrolysis have been used to study the electrochemical oxidation behaviour of niclosamide at a glassy carbon electrode. The number of electrons transferred, the wave characteristics, the diffusion coefficient and reversibility of the reactions have been ...

Polyamorphism in Water: Amorphous Ices and their Glassy States

Science.gov (United States)

Amann-Winkel, K.; Boehmer, R.; Fujara, F.; Gainaru, C.; Geil, B.; Loerting, T.

2015-12-01

Water is ubiquitous and of general importance for our environment. But it is also known as the most anomalous liquid. The fundamental origin of the numerous anomalies of water is still under debate. An understanding of these anomalous properties of water is closely linked to an understanding of the phase diagram of the metastable non-crystalline states of ice. The process of pressure induced amorphization of ice was first observed by Mishima et al. [1]. The authors pressurized hexagonal ice at 77 K up to a pressure of 1.6 GPa to form high density amorphous ice (HDA). So far three distinct structural states of amorphous water are known [2], they are called low- (LDA), high- (HDA) and very high density amorphous ice (VHDA). Since the discovery of multiple distinct amorphous states it is controversy discussed whether this phenomenon of polyamorphism at high pressures is connected to the occurrence of more than one supercooled liquid phase [3]. Alternatively, amorphous ices have been suggested to be of nanocrystalline nature, unrelated to liquids. Indeed inelastic X-ray scattering measurements indicate sharp crystal-like phonons in the amorphous ices [4]. In case of LDA the connection to the low-density liquid (LDL) was inferred from several experiments including the observation of a calorimetric glass-to-liquid transition at 136 K and ambient pressure [5]. Recently also the glass transition in HDA was observed at 116 K at ambient pressure [6] and at 140 K at elevated pressure of 1 GPa [7], using calorimetric measurements as well as dielectric spectroscopy. We discuss here the general importance of amorphous ices and their liquid counterparts and present calorimetric and dielectric measurements on LDA and HDA. The good agreement between dielectric and calorimetric results convey for a clearer picture of water's vitrification phenomenon. [1] O. Mishima, L. D. Calvert, and E. Whalley, Nature 314, 76, 1985 [2] D.T. Bowron, J. L. Finney, A. Hallbrucker, et al., J. Chem

Glassy carbon supercapacitor: 100,000 cycles demonstrated

Energy Technology Data Exchange (ETDEWEB)

Baertsch, M; Braun, A; Schnyder, B; Koetz, R [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

A 5 V glassy carbon capacitor stack was built consisting of four bipolar and two end-plate electrodes. More than 100,000 charging/discharging cycles were applied to test the stability of the double-layer capacitor. Low and high frequency resistances were measured as a function of the number of cycles. (author) 2 figs., 1 ref.

Iron(II) tris(3-bromo-1,10-phenanthroline) complex:synthesis, crystal structure and electropolymerization

CERN Document Server

Lee, K J; Lee, S S; Lee, B Y

2002-01-01

The complex of iron(II) tris(3-Br-phen)(3-Br-phen; 3-bromo-1,10-phenanthroline) was prepared as a precursor of electropolymerization and the crystal structure of [Fe(3-Br-phen) sub 3](PF sub 6) sub 2 centre dot CH sub 3 CN with a distorted octahedral geometry has been investigated. The reductive electropolymerization of [Fe(3-Br-phen) sub 3] sup 2 sup + complex onto the surface of a glassy carbon electrode and indium tin oxide (ITO) optically transparent electrode were performed in acetonitrile at room temperature. Thin film of poly-[Fe(3-Br-phen) sub 3] sup 2 sup + formed was adherent, electroactive and stably deposited on a glassy carbon disk electrode. The thin metallopolymeric film formed was also confirmed by absorption spectroscopy.

Ultrafast state detection and 2D ion crystals in a Paul trap

Science.gov (United States)

Ip, Michael; Ransford, Anthony; Campbell, Wesley

2016-05-01

Projective readout of quantum information stored in atomic qubits typically uses state-dependent CW laser-induced fluorescence. This method requires an often sophisticated imaging system to spatially filter out the background CW laser light. We present an alternative approach that instead uses simple pulse sequences from a mode-locked laser to affect the same state-dependent excitations in less than 1 ns. The resulting atomic fluorescence occurs in the dark, allowing the placement of non-imaging detectors right next to the atom to improve the qubit state detection efficiency and speed. We also study 2D Coulomb crystals of atomic ions in an oblate Paul trap. We find that crystals with hundreds of ions can be held in the trap, potentially offering an alternative to the use of Penning traps for the quantum simulation of 2D lattice spin models. We discuss the classical physics of these crystals and the metastable states that are supported in 2D. This work is supported by the US Army Research Office.

SUPERNOVA SHOCK-WAVE-INDUCED CO-FORMATION OF GLASSY CARBON AND NANODIAMOND

Energy Technology Data Exchange (ETDEWEB)

Stroud, Rhonda [Naval Research Laboratory, Washington, D.C.; Chisholm, Matthew F [ORNL; Heck, Phillipp [The Field Museum, Chicago, IL; Alexander, Conel [Carnegie Institution of Washington; Nittler, Larry [Carnegie Institution of Washington

2011-01-01

Nanodiamond (ND) was the first extrasolar dust phase to be identified in meteorites. However, the 2 nm average size of the NDs precludes isotopic analysis of individual particles, and thus their origin(s) remains controversial. Using electron microscopy with subnanometer resolution, we show that ND separates from the Allende and Murchison meteorites are actually a two-phase mixture of ND and glassy carbon. This phase mixture is likely the product of supernova shock-wave transformation of pre-formed organics in the interstellar medium (ISM). The glassy carbon ND mixture is also a plausible contributor to the 2175 extinction feature in the diffuse ISM.

A wrinkling-based method for investigating glassy polymer film relaxation as a function of film thickness and temperature.

Science.gov (United States)

Chung, Jun Young; Douglas, Jack F; Stafford, Christopher M

2017-10-21

We investigate the relaxation dynamics of thin polymer films at temperatures below the bulk glass transition T g by first compressing polystyrene films supported on a polydimethylsiloxane substrate to create wrinkling patterns and then observing the slow relaxation of the wrinkled films back to their final equilibrium flat state by small angle light scattering. As with recent relaxation measurements on thin glassy films reported by Fakhraai and co-workers, we find the relaxation time of our wrinkled films to be strongly dependent on film thickness below an onset thickness on the order of 100 nm. By varying the temperature between room temperature and T g (≈100 °C), we find that the relaxation time follows an Arrhenius-type temperature dependence to a good approximation at all film thicknesses investigated, where both the activation energy and the relaxation time pre-factor depend appreciably on film thickness. The wrinkling relaxation curves tend to cross at a common temperature somewhat below T g , indicating an entropy-enthalpy compensation relation between the activation free energy parameters. This compensation effect has also been observed recently in simulated supported polymer films in the high temperature Arrhenius relaxation regime rather than the glassy state. In addition, we find that the film stress relaxation function, as well as the height of the wrinkle ridges, follows a stretched exponential time dependence and the short-time effective Young's modulus derived from our modeling decreases sigmoidally with increasing temperature-both characteristic features of glassy materials. The relatively facile nature of the wrinkling-based measurements in comparison to other film relaxation measurements makes our method attractive for practical materials development, as well as fundamental studies of glass formation.

Glassy and Metastable Crystalline BaTi2O5 by Containerless Processing

Science.gov (United States)

Yoda, Shinichi; Kentei Yu, Yu; Kumar, Vijaya; Kameko, Masashi

Many efforts have been devoted to forming bulk glass from the melt of ferroelectric crystalline materials without adding any network-forming oxides such as SiO2 due to the potential for producing transparent glass ceramics with high dielectric constant and enhanced piezoelectric, pyroelectric and electro-optic use. The containerless processing is an attractive synthesis tech-nique as it can prevent melt contamination, minimize heterogeneous nucleation, and allow melt to achieve deep undercooling for forming metastable and glassy materials. We have fabricated a new ferroelectric materiel BaTi2 O5 [1] as bulk glass from melt by us-ing containerless processing and studied the phase relationship between microstructure and ferroelectric properties of BaTi2 O5 [2]. The structures of glassy and metastable crystalline BaTi2 O5 fabricated by the containerless pro-cessing were comprehensively investigated by combined X-ray and neutron diffractions, XANES analyses and computer simulations [3]. The 3-dimensional atomic structure of glassy BaTi2 O5 (g-BaTi2 O5 ), simulated by Reverse Monte Carlo (RMC) modelling on diffraction data, shows that extremely distorted TiO5 polyhedra interconnected with both corner-and edge-shared oxy-gen, formed a higher packing density structure than that of conventional silicate glass linked with only corner-sharing of SiO4 polyhedra. In addition, XANES measurement reveales that five-coordinated TiO5 polyhedra were formable in the crystallized metastable a-and b-BaTi2 O5 phases. The structure of metastable b-BaTi2 O5 was solved by ab initio calculation, and refined by Rietveld refinement as group Pnma with unit lattices a = 10.23784 ˚, b = 3.92715 ˚, c A A = 10.92757 A ˚. Our results show that the glass-forming ability enhanced by containerless pro-cessing, not by `strong glass former', fabricated new bulk oxide glasses with peculiar structures and properties. The intermediate-range structure of g-BaTi2 O5 and the crystalline structure of

Solvated electron structure in glassy matrices

International Nuclear Information System (INIS)

Kevan, L.

1981-01-01

Current knowledge of the detailed geometrical structure of solvated electrons in aqueous and organic media is summarized. The geometry of solvated electrons in glassy methanol, ethanol, and 2-methyltetrahydrofuran is discussed. Advanced electron magnetic resonance methods and development of new methods of analysis of electron spin echo modulation patterns, second moment line shapes, and forbidden photon spin-flip transitions for paramagnetic species in these disordered systems are discussed. 66 references are cited

An all-silicon laser by coupling between electronic localized states and defect states of photonic crystal

Energy Technology Data Exchange (ETDEWEB)

Huang Weiqi, E-mail: WQHuang2001@yahoo.com [Institute of Nanophotonic Physics, Key Laboratory of Photoelectron Technology and Application, Guizhou University, Guiyang 550025 (China); Huang Zhongmei; Miao Xinjiang; Cai Chenlan; Liu Jiaxin; Lue Quan [Institute of Nanophotonic Physics, Key Laboratory of Photoelectron Technology and Application, Guizhou University, Guiyang 550025 (China); Liu Shirong, E-mail: Shirong@yahoo.com [State Key Laboratory of Ore Deposit Geochemistry Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550003 (China); Qin Chaojian [State Key Laboratory of Ore Deposit Geochemistry Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550003 (China)

2012-01-15

In a nano-laser of Si quantum dots (QD), the smaller QD fabricated by nanosecond pulse laser can form the pumping level tuned by the quantum confinement (QC) effect. Coupling between the active centers formed by localized states of surface bonds and the two-dimensional (2D) photonic crystal is used to select model in the nano-laser. The experimental demonstration is reported in which the peaks of stimulated emission at about 600 nm and 700 nm were observed on the Si QD prepared in oxygen after annealing which improves the stimulated emission. It is interesting to make a comparison between the localized electronic states in gap due to defect formed by surface bonds and the localized photonic states in gap of photonic band due to defect of 2D photonic crystal.

Self-Assembly and Crystallization of Conjugated Block Copolymers

Science.gov (United States)

Davidson, Emily Catherine

This dissertation demonstrates the utility of molecular design in conjugated polymers to create diblock copolymers that robustly self-assemble in the melt and confine crystallization upon cooling. This work leverages the model conjugated polymer poly(3-(2'-ethyl)hexylthiophene) (P3EHT), which features a branched side chain, resulting in a dramatically reduced melting temperature (Tm 80°C) relative to the widely-studied poly(3-hexylthiophene) (P3HT) (Tm 200°C). This reduced melting temperature permits an accessible melt phase, without requiring that the segregation strength (chiN) be dramatically increased. Thus, diblock copolymers containing P3EHT demonstrate robust diblock copolymer self-assembly in the melt over a range of compositions and morphologies. Furthermore, confined crystallization in the case of both glassy (polystyrene (PS) matrix block) and soft (polymethylacrylate (PMA) matrix block) confinement is studied, with the finding that even in soft confinement, crystallization is constrained within the diblock microdomains. This success demonstrates the strategy of leveraging molecular design to decrease the driving force for crystallization as a means to achieving robust self-assembly and confined crystallization in conjugated block copolymers. Importantly, despite the relatively flexible nature of P3EHT in the melt, the diblock copolymer phase behavior appears to be significantly impacted by the stiffness (persistence length of 3 nm) of the P3EHT chain compared to the coupled amorphous blocks (persistence length 0.7 nm). In particular, it is shown that the synthesized morphologies are dominated by a very large composition window for lamellar geometries (favored at high P3EHT volume fractions); cylindrical geometries are favored when P3EHT is the minority fraction. This asymmetry of the composition window is attributed to impact of conformational asymmetry (the difference in chain stiffness, as opposed to shape) between conjugated and amorphous blocks

FTIR and Mössbauer spectroscopic study of sodium–aluminum–iron phosphate glassy materials for high level waste immobilization

Energy Technology Data Exchange (ETDEWEB)

Stefanovsky, S.V., E-mail: serge.stefanovsky@yandex.ru [Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Laboratory of Radioecology and Radiation Problems, Moscow (Russian Federation); Stefanovsky, O.I. [Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Laboratory of Radioecology and Radiation Problems, Moscow (Russian Federation); Remizov, M.B.; Belanova, E.A.; Kozlov, P.V. [FSUE PA Mayak, Central Plant Laboratory, Ozersk, Chelyabinsk Reg. (Russian Federation); Glazkova, Ya.S.; Sobolev, A.V.; Presniakov, I.A. [Lomonosov Moscow State University, Department of Radiochemistry (Russian Federation); Kalmykov, S.N. [Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Laboratory of Radioecology and Radiation Problems, Moscow (Russian Federation); Lomonosov Moscow State University, Department of Radiochemistry (Russian Federation); Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences, Laboratory of Radiochemistry, Moscow (Russian Federation); Myasoedov, B.F. [Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences, Laboratory of Radioecology and Radiation Problems, Moscow (Russian Federation); Vernadsky Institute of Geochemistry and Analytical Chemistry of the Russian Academy of Sciences, Laboratory of Radiochemistry, Moscow (Russian Federation)

2015-11-15

Complex sodium-aluminum-iron phosphate glassy materials with various Al{sub 2}O{sub 3} to Fe{sub 2}O{sub 3} ratio containing high level waste (HLW) surrogate were characterized by X-ray diffraction and scanning electron microscopy and studied in details by Fourier transform infrared (FTIR) spectroscopy. The samples with high Al{sub 2}O{sub 3} content and not containing Fe{sub 2}O{sub 3} were predominantly amorphous but subjected to devitrification under annealing. Addition of B{sub 2}O{sub 3} and partial Fe{sub 2}O{sub 3} substitution for Al{sub 2}O{sub 3} in the materials increases their resistance to devitrification whereas further substitution and NiO incorporation significantly increase the tendency to devitrification. FTIR spectra demonstrate changes in the structure of glassy materials caused by both structural variations in the anionic motif and occurrence of crystalline phases in the materials. According to Mössbauer spectroscopy data, iron in the glassy samples is present as octahedrally coordinated Fe{sup 3+} ions while in the partly devitrified samples iron is partitioned among vitreous and crystalline phases entering the vitreous phase mainly as Fe{sup 3+}O{sub 6} units and crystalline phases as major Fe{sup 3+} and minor Fe{sup 2+} ions in a magnetically ordered state and participating in a “fast” electronic exchange.

Graphene oxide-mediated electrochemistry of glucose oxidase on glassy carbon electrodes.

Science.gov (United States)

Castrignanò, Silvia; Valetti, Francesca; Gilardi, Gianfranco; Sadeghi, Sheila J

2016-01-01

Glucose oxidase (GOD) was immobilized on glassy carbon electrodes in the presence of graphene oxide (GO) as a model system for the interaction between GO and biological molecules. Lyotropic properties of didodecyldimethylammonium bromide (DDAB) were used to stabilize the enzymatic layer on the electrode surface resulting in a markedly improved electrochemical response of the immobilized GOD. Transmission electron microscopy images of the GO with DDAB confirmed the distribution of the GO in a two-dimensional manner as a foil-like material. Although it is known that glassy carbon surfaces are not ideal for hydrogen peroxide detection, successful chronoamperometric titrations of the GOD in the presence of GO with β-d-glucose were performed on glassy carbon electrodes, whereas no current response was detected upon β-d-glucose addition in the absence of GO. The GOD-DDAB-GO system displayed a high turnover efficiency and substrate affinity as a glucose biosensor. The simplicity and ease of the electrode preparation procedure of this GO/DDAB system make it a good candidate for immobilizing other biomolecules for fabrication of amperometric biosensors. © 2015 International Union of Biochemistry and Molecular Biology, Inc.

Comparing the mechanism of water condensation and evaporation in glassy aerosol.

Science.gov (United States)

Bones, David L; Reid, Jonathan P; Lienhard, Daniel M; Krieger, Ulrich K

2012-07-17

Atmospheric models generally assume that aerosol particles are in equilibrium with the surrounding gas phase. However, recent observations that secondary organic aerosols can exist in a glassy state have highlighted the need to more fully understand the kinetic limitations that may control water partitioning in ambient particles. Here, we explore the influence of slow water diffusion in the condensed aerosol phase on the rates of both condensation and evaporation, demonstrating that significant inhibition in mass transfer occurs for ultraviscous aerosol, not just for glassy aerosol. Using coarse mode (3-4 um radius) ternary sucrose/sodium chloride/aqueous droplets as a proxy for multicomponent ambient aerosol, we demonstrate that the timescale for particle equilibration correlates with bulk viscosity and can be ≫10(3) s. Extrapolation of these timescales to particle sizes in the accumulation mode (e.g., approximately 100 nm) by applying the Stokes-Einstein equation suggests that the kinetic limitations imposed on mass transfer of water by slow bulk phase diffusion must be more fully investigated for atmospheric aerosol. Measurements have been made on particles covering a range in dynamic viscosity from  10(13) Pa s. We also retrieve the radial inhomogeneities apparent in particle composition during condensation and evaporation and contrast the dynamics of slow dissolution of a viscous core into a labile shell during condensation with the slow percolation of water during evaporation through a more homogeneous viscous particle bulk.

SUPERNOVA SHOCK-WAVE-INDUCED CO-FORMATION OF GLASSY CARBON AND NANODIAMOND

International Nuclear Information System (INIS)

Stroud, Rhonda M.; Chisholm, Matthew F.; Heck, Philipp R.; Alexander, Conel M. O'D.; Nittler, Larry R.

2011-01-01

Nanodiamond (ND) was the first extrasolar dust phase to be identified in meteorites. However, the 2 nm average size of the NDs precludes isotopic analysis of individual particles, and thus their origin(s) remains controversial. Using electron microscopy with subnanometer resolution, we show that ND separates from the Allende and Murchison meteorites are actually a two-phase mixture of ND and glassy carbon. This phase mixture is likely the product of supernova shock-wave transformation of pre-formed organics in the interstellar medium (ISM). The glassy carbon-ND mixture is also a plausible contributor to the 2175 A extinction feature in the diffuse ISM.

Formation, thermal stability and mechanical properties of bulk glassy alloys with a diameter of 20 mm in Zr-(Ti,Nb)-Al-Ni-Cu system

International Nuclear Information System (INIS)

Inoue, A.; Zhang, Q.S.; Zhang, W.; Yubuta, K.; Son, K.S.; Wang, X.M.

2009-01-01

Bulk glassy alloy rods with a diameter of 20 mm were produced for Zr 61 Ti 2 Nb 2 Al 7.5 Ni 10 Cu 17.5 and Zr 60 Ti 2 Nb 2 Al 7.5 Ni 10 Cu 18.5 by a tilt casting method. The replacement of Zr by a small amount of Ti and Nb caused a distinct increase in the maximum diameter from 16 mm for Zr 65 Al 7.5 Ni 10 Cu 17.5 to 20 mm, accompanying the decrease in liquidus temperature and the increase in reduced glass transition temperature. The primary precipitation phase from supercooled liquid also shows a distinct change, i.e., from coexistent Zr 2 Cu, Zr 2 Ni and Zr 6 NiAl 2 phases for the 65%Zr alloy to an icosahedral phase for the 61%Zr and 60%Zr alloys. These results allow us to presume that the enhancement of the glass-forming ability is due to an increase in the stability of supercooled liquid against crystallization caused by the development of icosahedral short-range ordered atomic configurations. The 60%Zr specimens taken from the central and near-surface regions in the transverse cross section at the site which is 15 mm away from the bottom surface of the cast glassy rod with a diameter of 20 mm exhibit good mechanical properties under a compressive deformation mode, i.e., Young's modulus of 81 GPa, large elastic strain of 0.02, high yield strength of 1610 MPa and distinct plastic strain of 0.012. Besides, a number of shear bands are observed along the maximum shear stress plane on the peripheral surface near the final fracture site. The finding of producing the large scale Zr-based bulk glassy alloys exhibiting reliable mechanical properties is encouraging for future advancement of bulk glassy alloys as a new type of functional material. (author)

Electrochemical pre anodization of glassy carbon electrode and application to determine chloramphenicol

International Nuclear Information System (INIS)

Truc, Nguyen Minh; Mortensen, John; Anh, Nguyen Ba Hoai

2008-01-01

This paper suggested a method to enhance the performance of carbon electrodes for the determination of chloramphenicol (CAP). The sensitivity and the reproducibility of the carbon electrodes could be enhanced easily by electrochemical pretreatment. Some kinds of carbon material were studied including glassy carbon, graphite carbon and pyrolytic carbon. Numerous kinds of supporting electrolyte have been tried. For glassy carbon electrode, the acidic solution, H 2 SO 4 5 mM, resulted in best performance at pretreated voltage of +2.1V (vs. Ag/ AgCl) in duration of 250 second. However, for graphite and pyrolytic carbon electrodes, the phosphate buffer solution pH 6.0 gave the best performance at +1.7V (vs. Ag/ AgCl) in duration of 20 seconds. The detection limit could be at very low concentration of CAP: 0.8 ng/ ml for glassy carbon electrode, 3.5 ng/ ml for graphite carbon electrode. The method was successful applied to aqua-agriculture water sample and milk sample with simple extraction as well as direct ointment sample analysis. (author)

Engineering topological edge states in two dimensional magnetic photonic crystal

Science.gov (United States)

Yang, Bing; Wu, Tong; Zhang, Xiangdong

2017-01-01

Based on a perturbative approach, we propose a simple and efficient method to engineer the topological edge states in two dimensional magnetic photonic crystals. The topological edge states in the microstructures can be constructed and varied by altering the parameters of the microstructure according to the field-energy distributions of the Bloch states at the related Bloch wave vectors. The validity of the proposed method has been demonstrated by exact numerical calculations through three concrete examples. Our method makes the topological edge states "designable."

Emergence of Griffiths phase and glassy mixed phase in Sm0.5Ca0.5MnO3 nanomanganites

International Nuclear Information System (INIS)

Giri, S.K.; Yusuf, S.M.; Mukadam, M.D.; Nath, T.K.

2014-01-01

Graphical abstract: A detailed investigation on the effect of grain size on formation of Griffiths phase, and glassy mixed phase in CE-type antiferromagnetic Sm 0.5 Ca 0.5 MnO 3 manganite are carried out. A rigorous measurement of linear and non-linear ac magnetic susceptibilities, time dependent relaxation and aging phenomena in Sm 0.5 Ca 0.5 MnO 3 nanomanganite confirm the existence of a glassy mixed phase in the low temperature regime. The signature of Griffiths phase in nanosized manganite has been confirmed from the detailed ac and dc magnetization studies. The existence of Griffiths phase is verified through the anomalous behavior of the low field temperature dependent an inverse ac and dc magnetic susceptibility. Based on experimental results, the glassy phase of nanomanganites has been attributed to the phase separation effect and interaction between the ferromagnetic clusters. A phenomenological core/shell model has also been proposed based on the surface disorder to explain the observed Griffiths phase in these nanosized manganites. Fig. 1: (Left) The plot of inverse of ac susceptibility χ ac -1 measured at f = 1 Hz and H ac = 2 Oe as a function of temperature for S750 sample. Inset shows the same for S550 sample. (Right) A schematic of the proposed model to describe the magnetic state of the Sm 0.5 Ca 0.5 MnO 3 system at different average sizes. Highlights: • Effect of grain size on Griffiths phase and glassy mixed phase is discussed. • GP is confirmed by dc, linear and non-linear ac magnetization in nanomanganites. • Glassy mixed phase is discussed by time dependent relaxation and aging phenomena. • The existence of GP is verified through an inverse ac and dc magnetic susceptibility. • A phenomenological core/shell model has been proposed based on surface disorder. -- Abstract: A detailed investigation on the effect of grain size on formation of Griffiths phase (GP), and glassy mixed phase in CE-type antiferromagnetic Sm 0.5 Ca 0.5 MnO 3

Effects of nymphal diet and adult feeding on allocation of resources to glassy-winged sharpshooter egg production

Science.gov (United States)

The glassy-winged sharpshooter is an invasive insect capable of transmitting the bacterial pathogen Xylella fastidiosa. Pre-oviposition periods of laboratory reared glassy-winged sharpshooters are variable. Here, two questions were addressed: does nymphal diet affect pre-oviposition period and how d...

Formation of glassy carbon structure and its change under neutron irradiation

Energy Technology Data Exchange (ETDEWEB)

Kurolenkin, E.I.; Lopato, Yu.S.; Virgil' ev, Yu.S.; Khakimova, D.K.; Aksenov, S.I.

1981-01-01

The changes of glassy carbon structure, which is prepared of phenol-formaldehyde and furfurol-phenol-formaldehyde resins in the process of irradiation with 5.3x10/sup 20/ cm/sup -2/ neutron fluence with the energy E>0.18 MeV in the temperature range of 90-540 deg C are studied. It is established the irradiation results in the shrinkage of the samples. The compression of the samples increases with the irradiation temperature and neutron fluence. The thermal annealing does not result in the restoration of the volume of samples. The sample shrinkage, caused by more compact package of globular structures and the destruction of film structures, decrease gas permeability of glassy carbon.

Protein crystal growth results from the United States Microgravity Laboratory-1 mission

Science.gov (United States)

Delucas, Lawrence J.; Moore, K. M.; Vanderwoerd, M.; Bray, T. L.; Smith, C.; Carson, M.; Narayana, S. V. L.; Rosenblum, W. M.; Carter, D.; Clark, A. D, Jr.

1994-01-01

Protein crystal growth experiments have been performed by this laboratory on 18 Space Shuttle missions since April, 1985. In addition, a number of microgravity experiments also have been performed and reported by other investigators. These Space Shuttle missions have been used to grow crystals of a variety of proteins using vapor diffusion, liquid diffusion, and temperature-induced crystallization techniques. The United States Microgravity Laboratory - 1 mission (USML-1, June 25 - July 9, 1992) was a Spacelab mission dedicated to experiments involved in materials processing. New protein crystal growth hardware was developed to allow in orbit examination of initial crystal growth results, the knowledge from which was used on subsequent days to prepare new crystal growth experiments. In addition, new seeding hardware and techniques were tested as well as techniques that would prepare crystals for analysis by x-ray diffraction, a capability projected for the planned Space Station. Hardware that was specifically developed for the USML-1 mission will be discussed along with the experimental results from this mission.

Pseudo-time-reversal symmetry and topological edge states in two-dimensional acoustic crystals

KAUST Repository

Mei, Jun

2016-09-02

We propose a simple two-dimensional acoustic crystal to realize topologically protected edge states for acoustic waves. The acoustic crystal is composed of a triangular array of core-shell cylinders embedded in a water host. By utilizing the point group symmetry of two doubly degenerate eigenstates at the Î

Pseudo-time-reversal symmetry and topological edge states in two-dimensional acoustic crystals

KAUST Repository

Mei, Jun; Chen, Zeguo; Wu, Ying

2016-01-01

We propose a simple two-dimensional acoustic crystal to realize topologically protected edge states for acoustic waves. The acoustic crystal is composed of a triangular array of core-shell cylinders embedded in a water host. By utilizing the point group symmetry of two doubly degenerate eigenstates at the Î

Temperature effect on phase states of quartz nano-crystals in silicon single crystal

International Nuclear Information System (INIS)

Kalanov, M.U.; Ibragimova, E.M.; Khamraeva, R.N.; Rustamova, V.M.; Ummatov, Kh.D.

2006-01-01

Full text: Oxygen penetrates into the silicon lattice up to the concentration of 2·10 18 cm -3 in the course of growing [1]. By the author's opinion at a low oxygen content the formation of solid solution is possible in the local defect places of the silicon single crystal lattice due to the difference in effective ion radius of oxygen and silicon (r O 0.176 and r Si = 0.065 nm). Upon reaching some critical content (∼ 10 17 cm -3 ), it becomes favorable energetically for oxygen ions to form precipitates (SiO x ) and finally a dielectric layer (stoichiometric inclusions of SiO 2 ). It was shown later that depending on the growth conditions, indeed the quartz crystal inclusions are formed in the silicon single crystals at an amount of 0.3 /0.5 wt. % [2]. However the authors did not study a phase state of the quartz inclusions. Therefore the aim of this work was to study a phase state of the quartz inclusions in silicon crystal at various temperatures. We examined the silicon single crystals grown by Czochralski technique, which were cut in (111) plane in the form of disk of 20 mm diameter and 1.5 thickness and had hole conductivity with the specific resistance ρ o ≅ 1/10 Ohm cm. The dislocation density was N D ≅ 10 1 /10 3 cm -2 , the concentrations of oxygen and boron were N 0 ≅ 2/ 4·10 17 cm -3 and N B ≅ 3*10 15 cm -3 . Structure was analyzed at the set-up DRON-UM1 with high temperature supply UVD-2000 ( CuK = 0.1542 nm) at the temperatures of 300, 1173 and 1573 K measured with platinum-platinum-rhodium thermocouple. The high temperature diffraction spectrum measured at 1573 K in the angle range (2Θ≅10/70 d egree ) there is only one main structure reflection (111) with a high intensity and d/n ≅ 0.3136 nm (2 Θ≅ 28.5 d egree ) from the matrix lattice of silicon single crystal. The weak line at 2 Θ≅ 25.5 d egree ( d/n≅0.3136 nm) is β component of the main reflection (111), and the weak structure peak at 2Θ≅59 d egree ( d/n≅ 0.1568 nm

Fabrication of folic acid sensor based on the Cu doped SnO2 nanoparticles modified glassy carbon electrode

International Nuclear Information System (INIS)

Lavanya, N; Radhakrishnan, S; Sudhan, N; Sekar, C; Leonardi, S G; Neri, G; Cannilla, C

2014-01-01

A novel folic acid biosensor has been fabricated using Cu doped SnO 2 nanoparticles (NPs) synthesized by a simple microwave irradiation method. Powder XRD and TEM studies confirmed that both the pure and Cu doped SnO 2 (Cu: 0, 10, 20wt%) crystallized in tetragonal rutile-type structure with spherical morphology. The average crystallite size of pure SnO 2 was estimated to be around 16 nm. Upon doping, the crystallite sizes decreased to 9 nm and 5 nm for 10 and 20wt% Cu doped SnO 2 respectively. XPS studies confirmed the electronic state of Sn and Cu to be 4+ and 2+ respectively. Cu (20wt%) doped SnO 2 NPs are proved to be a good sensing element for the determination of folic acid (FA). Cu-SnO 2 NPs (20wt%) modified glassy carbon electrode (GCE) exhibited the lowest detection limit of 0.024 nM over a wide folic acid concentration range of 1.0 × 10 −10 to 6.7 × 10 −5 M at physiological pH of 7.0. The fabricated sensor is highly selective towards the determination of FA even in the presence of a 100 fold excess of common interferent ascorbic acid. The sensor proved to be useful for the estimation of FA content in pharmaceutical sample with satisfactory recovery. (paper)

Neutron single crystal diffraction studies of orientational glass state in the [Rbx(NH4)1-x]3H(SO4)2 mixed crystals

International Nuclear Information System (INIS)

Smirnov, L.S.; Reehuis, M.; Loose, A.; Hohlwein, D.; Hoffmann, J.U.; Wozniak, K.; Dominiak, P.; Baranov, A.I.; Dolbinina, V.V.

2005-01-01

The [Rb x (NH 4 ) 1-x ] 3 H(SO 4 ) 2 mixed crystal with the concentration x=0.0 at room temperature crystallizes in a monoclinic C2/c with sp.gr. (space group), which is stabilized for x>0.09 down to low temperatures. This system is transformed in the orientational glass state below the freezing temperature T g =30 K. The differential Fourier maps for the [Rb x (NH 4 ) 1-x ] 3 H(SO 4 ) 2 mixed crystals show that if for x=0.0 and 0.11 at 293 K the obtained maps reflect different orientational positions of crystallographically independent NH 4 (1) and NH 4 (2) groups, then the differential Fourier maps for x=0.20 at 9 K in the orientational glass state are similar for both ammonium groups reflecting their static disorder. The existence of the modulated structure in the [Rb x (NH 4 ) 1-x ] 3 H(SO 4 ) 2 mixed crystals with x=0.11 at 2 K is discovered, while the modulated structure for x=0.20 at 2 K is absent. This observation supposes that there should be two different regions of the orientational glass state on x-T phase diagram of the [Rb x (NH 4 ) 1-x ] 3 H(SO 4 ) 2 mixed crystals

Novel Transrotational Solid State Order Discovered by TEM in Crystallizing Amorphous Films

Science.gov (United States)

Kolosov, Vladimir

Exotic thin crystals with unexpected transrotational microstructures have been discovered by transmission electron microscopy (TEM) for crystal growth in thin (10-100 nm) amorphous films of different chemical nature (oxides, chalcogenides, metals and alloys) prepared by various methods. Primarily we use our TEM bend contour technique. The unusual phenomenon can be traced in situ in TEM column: dislocation independent regular internal bending of crystal lattice planes in a growing crystal. Such transrotation (unit cell trans lation is complicated by small rotationrealized round an axis lying in the film plane) can result in strong regular lattice orientation gradients (up to 300 degrees per micrometer) of different geometries: cylindrical, ellipsoidal, toroidal, saddle, etc. Transrotation is increasing as the film gets thinner. Transrotational crystal resembles ideal single crystal enclosed in a curved space. Transrotational micro crystals have been eventually recognized by other authors in some vital thin film materials, i.e. PCMs for memory, silicides, SrTiO3. Atomic model and possible mechanisms of the phenomenon are discussed. New transrotational nanocrystalline model of amorphous state is also proposed Support of RF Ministry of Education and Science is acknowledged.

Mechanical properties of Fe-Ni-Cr-Si-B bulk glassy alloy

International Nuclear Information System (INIS)

Lee, Kee Ahn; Kim, Yong Chan; Kim, Jung Han; Lee, Chong Soo; Namkung, Jung; Kim, Moon Chul

2007-01-01

The mechanical properties and crystallization behavior of new Fe-Ni-Cr-Si-B-based bulk glassy alloys were investigated. The suitability of the continuous roll casting method for the production of bulk metallic glass (BMG) sheets in such alloy systems was also examined. BMG samples (Fe-Ni-Cr-Si-B, Fe-Ni-Zr-Cr-Si-B, Fe-Ni-Zr-Cr-W-Si-B) in amorphous strip, cylindrical, and sheet forms were prepared through melt spinning, copper mold casting, and twin roll strip casting, respectively. Fe-Ni-Cr-Si-B alloy exhibited compressive strength of up to 2.93 GPa and plastic strain of about 1.51%. On the other hand, the Fe-Ni-Zr-Cr-Si-B, composite-type bulk sample with diameter of 2.0 mm showed remarkable compressive plastic strain of about 4.03%. The addition of zirconium was found to enhance the homogeneous precipitation of nanocrystalline less than 7 nm and to develop a hybrid-composite microstructure with increasing sample thickness. Twin roll strip casting was successfully applied to the fabrication of sheets in Fe-Ni-Cr-Si-B-based BMGs. The combined characteristics of high mechanical properties and ease of microstructure control proved to be promising in terms of the future progress of structural bulk amorphous alloys

Mechanical properties of Fe-Ni-Cr-Si-B bulk glassy alloy

Energy Technology Data Exchange (ETDEWEB)

Lee, Kee Ahn [School of Advanced Materials Engineering, Andong National University, Andong 760-749 (Korea, Republic of)]. E-mail: keeahn@andong.ac.kr; Kim, Yong Chan [New Metals Research Team, RIST, Pohang 790-330 (Korea, Republic of); Kim, Jung Han [Center for Advanced Aerospace materials, POSTECH, Pohang 790-784 (Korea, Republic of); Lee, Chong Soo [Center for Advanced Aerospace materials, POSTECH, Pohang 790-784 (Korea, Republic of); Namkung, Jung [New Metals Research Team, RIST, Pohang 790-330 (Korea, Republic of); Kim, Moon Chul [New Metals Research Team, RIST, Pohang 790-330 (Korea, Republic of)

2007-03-25

The mechanical properties and crystallization behavior of new Fe-Ni-Cr-Si-B-based bulk glassy alloys were investigated. The suitability of the continuous roll casting method for the production of bulk metallic glass (BMG) sheets in such alloy systems was also examined. BMG samples (Fe-Ni-Cr-Si-B, Fe-Ni-Zr-Cr-Si-B, Fe-Ni-Zr-Cr-W-Si-B) in amorphous strip, cylindrical, and sheet forms were prepared through melt spinning, copper mold casting, and twin roll strip casting, respectively. Fe-Ni-Cr-Si-B alloy exhibited compressive strength of up to 2.93 GPa and plastic strain of about 1.51%. On the other hand, the Fe-Ni-Zr-Cr-Si-B, composite-type bulk sample with diameter of 2.0 mm showed remarkable compressive plastic strain of about 4.03%. The addition of zirconium was found to enhance the homogeneous precipitation of nanocrystalline less than 7 nm and to develop a hybrid-composite microstructure with increasing sample thickness. Twin roll strip casting was successfully applied to the fabrication of sheets in Fe-Ni-Cr-Si-B-based BMGs. The combined characteristics of high mechanical properties and ease of microstructure control proved to be promising in terms of the future progress of structural bulk amorphous alloys.

Glassy slags as novel waste forms for remediating mixed wastes with high metal contents

International Nuclear Information System (INIS)

Feng, X.; Wronkiewicz, D.J.; Bates, J.K.; Brown, N.R.; Buck, E.C.; Gong, M.; Ebert, W.L.

1994-01-01

Argonne National Laboratory (ANL) is developing a glassy slag final waste form for the remediation of low-level radioactive and mixed wastes with high metal contents. This waste form is composed of various crystalline and metal oxide phases embedded in a silicate glass phase. This work indicates that glassy slag shows promise as final waste form because (1) it has similar or better chemical durability than high-level nuclear waste (HLW) glasses, (2) it can incorporate large amounts of metal wastes, (3) it can incorporate waste streams having low contents of flux components (boron and alkalis), (4) it has less stringent processing requirements (e.g., viscosity and electric conductivity) than glass waste forms, (5) its production can require little or no purchased additives, which can result in greater reduction in waste volume and overall treatment costs. By using glassy slag waste forms, minimum additive waste stabilization approach can be applied to a much wider range of waste streams than those amenable only to glass waste forms

An anomalous X-ray scattering study on glassy superionic conductor (As2Se3)1-x(CuI) x using a third-generation synchrotron radiation facility

International Nuclear Information System (INIS)

Usuki, T.; Hosokawa, S.; Berar, J.-F.

2005-01-01

Anomalous X-ray scattering experiments on glassy superionic conductor (As 2 Se 3 ) 0.4 (CuI) 0.6 were performed at energies close to the As, Se, and Cu K edges using a new detecting system and a third-generation synchrotron radiation facility. The detecting system was composed of a graphite-crystal energy-analyzer and a NaI(Tl) detector on a 40-cm-long arm. The overall energy resolution was about 60 eV, which can discriminate the elastic signal from the fluorescence and Compton contributions, and a sufficient number of scattered X-ray photons were acquired within a reasonable data collection time. The differential structure factors, Δ i S(Q), were obtained from the detailed analyses, indicating that Δ As S(Q) and Δ Se S(Q) are similar to those of glassy As 2 Se 3 except at the prepeak position, and Δ Cu S(Q) that in liquid CuI. From these findings, it can be concluded that a pseudo-binary mixture of the As 2 Se 3 network matrix and CuI-related conduction pathways would be a good structural model for this superionic glass

Homogeneous nucleation limit on the bulk formation of metallic glasses

International Nuclear Information System (INIS)

Drehman, A.J.

1983-01-01

Glassy Pd 82 Si 18 spheres, of up to 1 mm diameter, were formed in a drop tube filled with He gas. The largest spheres were successfully cooled to a glass using a cooling rate of less than 800 K/sec. Even at this low cooling rate, crystallization (complete or partial) was the result of heterogeneous nucleation at a high temperature, relative to the temperature at which copious homogeneous nucleation would commence. Bulk underscoring experiments demonstrated that this alloy could be cooled to 385 K below its eutectic melting temperature (1083 K) without the occurrence of crystallization. If heterogeneous nucleation can be avoided, it is estimated that a cooling rate of at most 100 K/sec would be required to form this alloy in the glassy state. Ingots of glassy Pd 40 Ni 40 P 20 were formed from the liquid by cooling at a rate of only 1 K/sec. It was found that glassy samples of this alloy could be heated well above the glass transition temperature without the occurrence of rapid divitrification. This is a result due, in part of the low density of pre-existing nuclei, but, more importantly, due to the low homogeneous nucleation rate and the slow crystal growth kinetics. Based on the observed devitrification kinetics, the steady-state homogeneous nucleation rate is approximately 1 nuclei/cm 3 sec at 590 K (the temperature at which the homogeneous nucleation rate is estimated to be a maximum). Two iron-nickel based glass-forming alloys (Fe 40 Ni 40 P 14 B 6 and Fe 40 Ni 40 B 20 , were not successfully formed into glassy spheres, however, microstructural examination indicates that crystallization was not the result of copious homogeneous nucleation. In contrast, glass forming iron based alloys (Fe 80 B 20 and Fe/sub 79.3/B/sub 16.4/Si/sub 4.0/C/sub 0.3/) exhibit copious homogeneous nucleation when cooled at approximately the same rate

One-way propagation of bulk states and robust edge states in photonic crystals with broken inversion and time-reversal symmetries

Science.gov (United States)

Lu, Jin-Cheng; Chen, Xiao-Dong; Deng, Wei-Min; Chen, Min; Dong, Jian-Wen

2018-07-01

The valley is a flexible degree of freedom for light manipulation in photonic systems. In this work, we introduce the valley concept in magnetic photonic crystals with broken inversion symmetry. One-way propagation of bulk states is demonstrated by exploiting the pseudo-gap where bulk states only exist at one single valley. In addition, the transition between Hall and valley-Hall nontrivial topological phases is also studied in terms of the competition between the broken inversion and time-reversal symmetries. At the photonic boundary between two topologically distinct photonic crystals, we illustrate the one-way propagation of edge states and demonstrate their robustness against defects.

Photoswitchable molecular dipole antennas with tailored coherent coupling in glassy composite

DEFF Research Database (Denmark)

Elbahri, Mady; Zillohu, Ahnaf Usman; Gothe, Bastian

2015-01-01

. We also introduce the concept of 'tailored molecular photonic coupling' while highlighting the role of interferences for the design of optically active media by adjusting the photonic response of the medium with the real and imaginary refractive index of photoswitchable molecules in the 'ON' state...... alteration of photochromic molecular dipole antennas. We successfully demonstrate the concept of Brewster wavelength, which is based on the dipolar interaction between radiating dipoles and the surrounding matrix possessing a net dipole moment, as a key tool for highly localized sensing of matrix polarity....... Our results enhance our fundamental understanding of coherent dipole radiation and open a new vein of research based on glassy disordered dipolar composites that act as macroscopic antenna with cooperative action; furthermore, these results have important implications for new design rules of tailored...

Superionic state and interionic potential of α-AgI crystals

International Nuclear Information System (INIS)

Polyakov, V.I.

1999-01-01

The nature of α-AgI crystal superionic state is condensed using a model of delayed rotational diffusion, in which α-AgI curvilinear conductivity channels are explained processing from the character of silver ions motion. The superionic state nature is explained using periodic equipotential surfaces of spatial interionic potential constructed of monomeric effective coupled potential by the EXAFS method. The physical character of periodic minimal surfaces for analysis of dynamic processes is substantiated [ru

Dielectric relaxation and AC conductivity studies of Se90Cd10−xInx glassy alloys

Directory of Open Access Journals (Sweden)

Nitesh Shukla

2016-06-01

Full Text Available Chalcogenide glassy alloys of Se90Cd10−xInx (x = 2, 4, 6, 8 are synthesized by melt quench technique. The prepared glassy alloys have been characterized by techniques such as differential scanning calorimetry (DSC, scanning electron microscopy (SEM and energy dispersive X-ray (EDAX. Dielectric properties of Se90Cd10−xInx (x = 2, 4, 6, 8 chalcogenide glassy system have been studied using impedance spectroscopic technique in the frequency range 42 Hz to 5 MHz at room temperature. It is found that the dielectric constants ɛ′, dielectric loss factor ɛ″ and loss angle Tan δ depend on frequency. ɛ′, ɛ″ and loss angle Tan δ are found to be decreasing with the In content in Se90Cd10−xInx glassy system. AC conductivity of the prepared sample has also been studied. It is found that AC conductivity increases with frequency where as it has decreasing trend with increasing In content in Se–Cd matrix. The semicircles observed in the Cole–Cole plots indicate a single relaxation process.

Effect of glassy carbon properties on the electrochemical deposition of platinum nano-catalyst and its activity for methanol oxidation

Directory of Open Access Journals (Sweden)

SANJA TERZIC

2007-02-01

Full Text Available The effects of the properties of glassy carbon on the deposition of platinum particles and the electrocatalytic activity of platinum supported on glassy carbon (GC/Pt for methanol oxidation in alkaline and acidic solutions were studied. Platinum was potentiostatically deposited on two glassy carbon samples, thermally treated at different temperatures, which were either polished or anodicaly polarised in acid (GCOX-AC/Pt and in alkali (GCOX-AL/Pt. Anodic polarisation of glassy carbon, either in alkaline or acidic solution, enhances the activity of both types of GC/Pt electrodes for methanol oxidation. The activity of the catalysts follows the change in the properties of the glassy carbon support upon anodic treatment. The specific activity of the GCOX-AL/Pt electrode for this reaction in alkali is increased only a few times in comparison with the activity of the GC/Pt one. On the other hand, the specific activity of the GCOX-AC/Pt electrode for methanol oxidation in acid is about one order of magnitude higher than that of the GC/Pt electrode. The role of the substrate on the properties of catalyst is discussed in detail.

Connection between NMR and electrical conductivity in glassy chalcogenide fast ionic conductors

International Nuclear Information System (INIS)

Kim, K.H.

1995-01-01

The work documented in this thesis follows the traditional order. In this chapter a general discussion of ionic conduction and of glassy materials are followed by a brief outline of the experimental techniques for the investigation of fast ionic conduction in glassy materials, including NMR and impedance spectroscopy techniques. A summary of the previous and present studies is presented in the last section of this introductory chapter. The details of the background theory and models are found in the Chapter II, followed by the description of the experimental details in Chapter III. Chapter IV of the thesis describes the experimental results and the analysis of the experimental observations followed by the conclusions in chapter V

Glass-crystal transformation under non-isothermal conditions: Kinetic analysis of the Ag{sub 0.16}As{sub 0.38}Se{sub 0.46} glassy alloy by using a new theoretical method based on nucleation and growth processes, which depend on time as a power law

Energy Technology Data Exchange (ETDEWEB)

Vazquez, J., E-mail: jose.vazquez@uca.e [Departamento de Fisica de la Materia Condensada, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, 11510, Puerto Real (Cadiz) (Spain); Cardenas-Leal, J.L.; Garcia-G Barreda, D.; Gonzalez-Palma, R.; Lopez-Alemany, P.L.; Villares, P. [Departamento de Fisica de la Materia Condensada, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, 11510, Puerto Real (Cadiz) (Spain)

2010-11-01

A theoretical method, which we have published in two previous works, has been applied to the study of the glass-crystal transformation of the Ag{sub 0.16}As{sub 0.38}Se{sub 0.46} semiconductor glass under non-isothermal conditions. This method allows one to obtain an evolution equation with temperature for the actual volume fraction, to calculate the kinetic parameters of the quoted transformation, to establish the thermal process type, to determine the dimensionality of the crystal growth and to evaluate the exponents of the power laws of the time-dependence both for the nucleation frequency and for the crystal growth rate in non-isothermal transformations. The quoted method assumes the concept of extended volume of the transformed material, the condition of randomly located nuclei and the supposition of mutual interference of regions growing from separated nuclei, considering moreover the case presented in the practice of a kinetic exponent with a value larger than 4. To study the quoted case it is proposed that both the nucleation frequency and the crystal growth rate depend on time as a power law. The above-mentioned Ag{sub 0.16}As{sub 0.38}Se{sub 0.46} glassy alloy presents two exothermic peaks. The second peak gives for the kinetic exponent a value large enough than 4 and it is necessary to resort to the hypotheses of the considered method to justify the unexpectedly high value of the kinetic exponent. Following the quoted method it has been found that the thermal process type is continuous nucleation with three-dimensional growth for the two peaks of crystallization of the studied alloy. Moreover, the experimental curve of the transformed fraction shows a satisfactory agreement with the theoretical curve corresponding to the considered method, confirming the reliability of the quoted method in order to analyze the transformation kinetics of the above-mentioned alloy.

Glassy slag from rotary hearth vitrification

International Nuclear Information System (INIS)

Eschenbach, R.C.; Simpson, M.D.; Paulson, W.S.; Whitworth, C.G.

1995-01-01

Use of a Plasma Arc Centrifugal Treatment (PACT) system for treating mixed wastes containing significant quantities of soil results in formation of a glassy slag which melts at significantly higher temperatures than the borosilicate glasses. The slag typically contains mostly crystalline material, frequently in an amorphous matrix, thus the appellation open-quotes glassy slag.close quotes Details of the PACT process are given. The process will be used for treating buried wastes from Pit 9 at the Idaho National Engineering Laboratory and low-level mixed wastes from nuclear power plants in Switzerland. Properties of the slag after cooling to room temperature are reported, in particular the Product Consistency Test, for a number of different feedstocks. In almost all cases, the results compare favorably with conventional borosilicate glasses. In the PACT system, a transferred arc carries current from the plasma torch to a rotating molten bed of slag, which is the material being heated. Thus this transferred arc adds energy where it is needed - at and near the surface of the molten bath. Material is fed into the furnace through a sealed feeder, and falls into a rotating tub which is heated by the arc. Any organic material is quickly vaporized into the space above the slag bed and burned by the oxygen in the furnace. Metal oxides in the charge are melted into the slag. Metal in the feed tends to melt and collect as a separate phase underneath the slag, but can be oxidized if desired. When oxidized, it unites with other constituents forming a homogeneous slag

Generation of fine hydromagmatic ash by growth and disintegration of glassy rinds

Science.gov (United States)

Mastin, L.G.

2007-01-01

The deposits of mafic hydromagmatic eruptions are more fine grained and variable in vesicularity than dry magmatic deposits. Blocky, equant shapes of many hydromagmatic clasts also contrast with droplet, thread, and bubble wall morphology of dry magmatic fragments. Small (disintegration of glassy rinds on pyroclast surfaces as they deform within turbulent flows. This process, termed "turbulent shedding", may occur during the expansion phase of vapor explosions or during turbulent but nonexplosive mixing of magma with water, steam, or water sprays. The occurrence of turbulent shedding and the resulting fragment sizes depend on the timescale for rind growth and the timescale between disturbances that remove or disintegrate glassy rinds. Turbulent shedding is directly observable in some small littoral jets at Kilauea. Calculations suggest that, in the presence of liquid water or water sprays, glassy rinds having a thickness of microns to millimeters should form in milliseconds to seconds. This is similar to the timescale between turbulent velocity fluctuations that can shred lava globules and remove such rinds. The fraction of a deposit consisting of fine ash should increase with the duration of this process: Large-scale Surtseyan jets generate hundreds or thousands of shedding events; bubble bursts or tephra jets at Kilauea's coast may produce only a few.

Protection of nuclear graphite toward fluoride molten salt by glassy carbon deposit

International Nuclear Information System (INIS)

Bernardet, V.; Gomes, S.; Delpeux, S.; Dubois, M.; Guerin, K.; Avignant, D.; Renaudin, G.; Duclaux, L.

2009-01-01

Molten salt reactor represents one of the promising future Generation IV nuclear reactors families where the fuel, a liquid molten fluoride salt, is circulating through the graphite reactor core. The interactions between nuclear graphite and fluoride molten salt and also the graphite surface protection were investigated in this paper by powder X-ray diffraction, micro-Raman spectroscopy and scanning electron microscopy coupled with X-ray microanalysis. Nuclear graphite discs were covered by two kinds of protection deposit: a glassy carbon coating and a double coating of pyrolitic carbon/glassy carbon. Different behaviours have been highlighted according to the presence and the nature of the coated protection film. Intercalation of molten salt between the graphite layers did not occur. Nevertheless the molten salt adhered more or less to the surface of the graphite disc, filled more or less the graphite surface porosity and perturbed more or less the graphite stacking order at the disc surface. The behaviour of unprotected graphite was far to be satisfactory after two days of immersion of graphite in molten salt at 500 deg. C. The best protection of the graphite disc surface, with the maximum of inertness towards molten salt, has been obtained with the double coating of pyrolitic carbon/glassy carbon

Electrocatalytic Determination of Isoniazid by a Glassy Carbon Electrode Modified with Poly (Eriochrome Black T)

OpenAIRE

Karim Asadpour-Zeynali; Venus Baghalabadi

2017-01-01

In this work poly eriochrome black T (EBT) was electrochemically synthesized on the glassy carbon electrode as electrode modifier. On the modified electrode, voltammetric behavior of isoniazid (INH) was investigated. The poly (EBT)-modified glassy carbon electrode has excellent electrocatalytic ability for the electrooxidation of isoniazid. This fact was appeared as a reduced overpotential of INH oxidation in a wide operational pH range from 2 to 13. It has been found that the catalytic peak ...

Electrochemical Determination of Caffeine Content in Ethiopian Coffee Samples Using Lignin Modified Glassy Carbon Electrode

OpenAIRE

Amare, Meareg; Aklog, Senait

2017-01-01

Lignin film was deposited at the surface of glassy carbon electrode potentiostatically. In contrast to the unmodified glassy carbon electrode, an oxidative peak with an improved current and overpotential for caffeine at modified electrode showed catalytic activity of the modifier towards oxidation of caffeine. Linear dependence of peak current on caffeine concentration in the range 6 ? 10?6 to 100 ? 10?6?mol?L?1 with determination coefficient and method detection limit (LoD = 3?s/slope) of 0....

Phase separation, crystallization and polyamorphism in the Y{sub 2}O{sub 3}-Al{sub 2}O{sub 3} system

Energy Technology Data Exchange (ETDEWEB)

Skinner, Lawrie B; Barnes, Adrian C [H H Wills Physics Laboratory, Royal Fort, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Salmon, Philip S [Department of Physics, University of Bath, Bath BA2 7AY (United Kingdom); Crichton, Wilson A [European Synchrotron Radiation Facility, 6 rue Jules Horowitz, BP 220, Grenoble Cedex, F-38043 (France)], E-mail: a.c.barnes@bristol.ac.uk

2008-05-21

A detailed study of glass formation from aerodynamically levitated liquids in the (Y{sub 2}O{sub 3}){sub x}(Al{sub 2}O{sub 3}){sub 1-x} system for the composition range 0.21{<=}x{<=}0.41 was undertaken by using pyrometric, optical imaging and x-ray diffraction methods. Homogeneous and clear single-phase glasses were produced over the composition range 0.27{<=}x{<=}0.33. For Y{sub 2}O{sub 3}-rich compositions (0.33{<=}x{<=}0.375), cloudy materials were produced which contain inclusions of crystalline yttrium aluminium garnet (YAG) of diameter up to 40 {mu}m in a glassy matrix. For Y{sub 2}O{sub 3}-poor compositions around x = 0.24, cloudy materials were also produced, but it was not possible to deduce whether this resulted from (i) sub-micron inclusions of a nano-crystalline or glassy material in a glassy matrix or (ii) a glass formed by spinodal decomposition. For x = 0.21, however, the sample cloudiness results from crystallization into at least two phases comprising yttrium aluminium perovskite and alumina. The associated pyrometric cooling curve shows slow recalescence events with a continuous and slow evolution of excess heat which contrasts with the sharp recalescence events observed for the crystallization of YAG at compositions near x = 0.375. The materials that are the most likely candidates for demonstrating homogeneous nucleation of a second liquid phase occur around x = 0.25, which corresponds to the limit for formation of a continuous random network of corner-shared AlO{sub 4} tetrahedra.

Directory of crystal growth and solid state materials production and research

International Nuclear Information System (INIS)

Connolly, T.F.; Battle, G.C.; Keesee, A.M.

1979-03-01

This directory lists only those who returned questionnaires distributed by the Research Materials Information Center during 1978. The directory includes, in addition to crystal growers, those preparing starting materials for crystal growth and ultrapure noncrystalline research specimens. It also includes responses from those characterizing, or otherwise studying, the properties of materials provided by others. The international coverage of the directory is limited to the United States, Argentina, Australia, Bulgaria, Canada, Czechoslovakia, Egypt, Finland, East Germany, Hungary, India, Israel, Japan, Mexico, Poland, Romania, South Africa, Taiwan, Yugoslavia, and Zaire

Directory of crystal growth and solid state materials production and research

Energy Technology Data Exchange (ETDEWEB)

Connolly, T.F.; Battle, G.C.; Keesee, A.M. (comps.)

1979-03-01

This directory lists only those who returned questionnaires distributed by the Research Materials Information Center during 1978. The directory includes, in addition to crystal growers, those preparing starting materials for crystal growth and ultrapure noncrystalline research specimens. It also includes responses from those characterizing, or otherwise studying, the properties of materials provided by others. The international coverage of the directory is limited to the United States, Argentina, Australia, Bulgaria, Canada, Czechoslovakia, Egypt, Finland, East Germany, Hungary, India, Israel, Japan, Mexico, Poland, Romania, South Africa, Taiwan, Yugoslavia, and Zaire.

Transparent phosphosilicate glasses containing crystals formed during cooling of melts

DEFF Research Database (Denmark)

Liu, S. J.; Zhang, Yanfei; He, W.

2011-01-01

The effect of P2O5-SiO2 substitution on spontaneous crystallization of SiO2-Al2O3-P2O5- Na2O-MgO melts during cooling was studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and rotation viscometry. Results show that addition of P2O5 leads...... to amorphous phase separation (APS), i.e., phosphate- and silicate-rich phases. It is due to the tendency of Mg2+ to form [MgO4] linking with [SiO4]. Molar substitution of P2O5 for SiO2 enhances the network polymerization of silicate-rich phase in the melts, and thereby the spontaneous crystallization of cubic...... Na2MgSiO4 is also enhanced during cooling of the melts. In addition, the sizes of the local crystalline and separated glassy domains are smaller than the wavelength of the visible light, and this leads to the transparency of the obtained glasses containing crystals....

Steady-State Crack Growth in Rate-Sensitive Single Crystals

DEFF Research Database (Denmark)

Juul, Kristian Jørgensen; Nielsen, Kim Lau; Niordson, Christian Frithiof

2016-01-01

The characteristics of the active plastic zone surrounding a crack growingin a single crystal (FCC, BCC, and HCP) at constant velocity is investigated for ModeI loading under plane strain assumptions. The framework builds upon a steady-state relation bringing the desired solution out in a frame...... translating with the crack tip. In the study, the shielding of the crack tip that follows from plastic slip is investigated by adopting the SSV-model. High resolution plots of the plastic zones are obtained and a detailed study confirms the existence of analytically determined velocity discontinuities from...... the literature. The plastic zone is found to be smallest for the FCC structure andlargest for the HCP structure, which is also reected in the shielding ratio, where FCC crystals show the smallest shielding and HCP the largest shielding....

Relook on fitting of viscosity with undercooling of glassy liquids

Indian Academy of Sciences (India)

Department of Materials Science and Engineering, Indian Institute of Technology, Kanpur ... The present approach is on the modification of viscosity fitting of undercooled liquid as a function of ... behaviour of glassy alloys and organic and ionic compounds ...... the present method is applied to calculate the analytical solu-.

Ultrasound-induced crystallization around the glass transition temperature for Pd40Ni40P20 metallic glass

International Nuclear Information System (INIS)

Ichitsubo, Tetsu; Matsubara, Eiichiro; Kai, Satoshi; Hirao, Masahiko

2004-01-01

We have found that crystallization of a Pd 40 Ni 40 P 20 bulk metallic glass is accelerated in the vicinity of the glass transition temperature T g when it is subjected to sub/low-MHz frequency ultrasonic vibration. Resonance frequencies and internal frictions have been measured with the electromagnetic acoustic resonance (EMAR) technique. In the initial heating process of an as-cast glassy sample, the resonance frequencies jump up just above T g under ultrasonic excitation, which is attributed to nano-crystallization that is confirmed by the X-ray diffraction profile. However, such a notable change is not observed without ultrasonic vibration. The irregular Λ-shaped internal-friction peaks are also observed prior to the abrupt crystallization. This rapid crystallization is considered to be caused by a stochastic resonance, in which the jump frequency of atoms matches the frequency of the interatomic-potential change by the ultrasonic vibration

Electrochemical functionalization of glassy carbon electrode by reduction of diazonium cations in protic ionic liquid

International Nuclear Information System (INIS)

Shul, Galyna; Ruiz, Carlos Alberto Castro; Rochefort, Dominic; Brooksby, Paula A.; Bélanger, Daniel

2013-01-01

Protic ionic liquid based on 2-methoxypyridine and trifluoroacetic acid was used as electrolyte for the functionalization of a glassy carbon electrode surface by electrochemical reduction of in situ generated 4-chlorobenzene diazonium and 4-nitrobenzene diazonium cations. The diazonium cations were synthesized in an electrochemical cell by reaction of the corresponding amines with NaNO 2 dissolved in protic ionic liquid. The resulting electrografted organic layers exhibit similar properties to those layers obtained by the derivatization from isolated diazonium salts dissolved in protic ionic liquid. Functionalized glassy carbon electrode surfaces were characterized by cyclic voltammetry, Fourier transform infrared and X-ray photoelectron spectroscopies. Atomic force microscopy thickness measurements revealed that, in our experimental conditions, the use of protic ionic liquid led to the formation of film with a thickness of about 1.5 nm. It is also demonstrated that the nitrobenzene chemisorbed on glassy carbon electrode or dissolved in protic ionic liquid undergoes electrochemical conversion to hydroxyaminobenzene

State of the art in crystal oscillators - Present and future

Science.gov (United States)

Rosati, V. J.; Filler, R. L.; Schodowski, S. S.; Vig, J. R.

It is pointed out that most military communication, navigation, surveillance and IFF systems which are currently under development require stable oscillators for frequency control and/or timing. Examples of such systems are the Single Channel Ground and Airborne Radio System (SINCGARS), MILSTAR, the Global Positioning System (GPS), the Combat Identification System (CIS), and several radar systems. In 1981, a survey and evaluation program was initiated with the aim to determine the state-of-the-art of both TCXOs (temperature compensated crystal oscillators) and OCXOs (oven controlled crystal oscillators). This program is continuing. The results obtained to date are considered because they can provide useful guidance to system users on the availability of stable oscillators.

Analysis of diffuse scattering in neutron powder diagrams. Application to glassy carbon

International Nuclear Information System (INIS)

Boysen, H.

1985-01-01

From the quantitative analysis of the diffuse scattered intensity in powder diagrams valuable information about the disorder in crystals may be obtained. According to the dimensionality of this disorder (0D, 1D, 2D or 3D corresponding to diffuse peaks, streaks, planes or volume in reciprocal space) a characteristic modulation of the background is observed, which is described by specific functions. These are derived by averaging the appropriate cross sections over all crystallite orientations in the powder and folding with the resolution function of the instrument. If proper account is taken of all proportionality factors different components of the background can be put on one relative scale. The results are applied to two samples of glassy carbon differing in their degree of disorder. The neutron powder patterns contain contributions from 0D (00l peaks due to the stacking of graphitic layers), 1D (hkzeta streaks caused by the random orientation of these layers) and 3D (incoherent scattering, averaged thermal diffuse scattering, multiple scattering). From the fit to the observed data various parameters of the disorder like domain sizes, strains, interlayer distances, amount of incorporated hydrogen, pore sizes etc. are determined. It is shown that the omission of resolution corrections leads to false parameters. (orig.)

Effects of the sintering temperature on the diffused phase transition and the spin-glassy behavior in Pb0.95La0.05(Fe2/3W1/3)0.65Ti0.35O3 ceramics

International Nuclear Information System (INIS)

Hong, Cheng-Shong; Chu, Sheng-Yuan; Hsu, Chi-Cheng

2010-01-01

In this paper, the effect of the sintering temperature on the low-field dielectric behavior of nonstoichiometric Pb 0.95 La 0.05 (Fe 2/3 W 1/3 ) 0.65 Ti 0.35 O 3 relaxor ferroelectrics is investigated. The x-ray patterns and the scanning electron microscope images are used to detect the pyrochlore phase and the perovskite structure. The electric properties of the resistivity, the space charge polarization, the temperature-dependent dielectric constant and dielectric loss are discussed. The diffused phase transition and the ordering state are fitted and discussed by using the empirical law and two ordering models. Furthermore, the glassy behavior is determined by using the Curie-Weiss law and the spin-glass model. According to the experimental data and fitting results, the dielectric picture is changed from the short range order relaxorlike behavior to the long range order normal ferroelectric state as increasing the sintering temperature and the glassy behavior is weakened at the lowest and highest sintering temperature at which the pyrochlore phase PWO 4 is induced. Therefore, it is suggested that the 1:1 ordered domain is enhanced by increasing the sintering temperature and the glassy behavior is related to not only the ordering degree also the polar defect pairs. For more ordering degree and polar defect pairs, the glassy is weakened and the correlation of neighboring polar microregions is enhanced.

Density of states controls Anderson localization in disordered photonic crystal waveguides

DEFF Research Database (Denmark)

Garcia-Fernández, David; Smolka, Stephan; Stobbe, Søren

2010-01-01

We prove Anderson localization in a disordered photonic crystal waveguide by measuring the ensemble-averaged extinction mean-free path, ℓe, which is controlled by the dispersion in the photon density of states (DOS) of the photonic crystal waveguide. Except for the very low DOS case, where out......-of-plane losses are non-negligible, ℓe can be approximated to be the localization length ξ. The extinction mean-free path shows a fivefold variation between the low- and the high-DOS regime, and it becomes shorter than the sample length thus giving rise to strongly confined modes. The dispersive behavior of ℓe...

Method for solid state crystal growth

Science.gov (United States)

Nolas, George S.; Beekman, Matthew K.

2013-04-09

A novel method for high quality crystal growth of intermetallic clathrates is presented. The synthesis of high quality pure phase crystals has been complicated by the simultaneous formation of both clathrate type-I and clathrate type-II structures. It was found that selective, phase pure, single-crystal growth of type-I and type-II clathrates can be achieved by maintaining sufficient partial pressure of a chemical constituent during slow, controlled deprivation of the chemical constituent from the primary reactant. The chemical constituent is slowly removed from the primary reactant by the reaction of the chemical constituent vapor with a secondary reactant, spatially separated from the primary reactant, in a closed volume under uniaxial pressure and heat to form the single phase pure crystals.

Equation-free dynamic renormalization in a glassy compaction model

International Nuclear Information System (INIS)

Chen, L.; Kevrekidis, I. G.; Kevrekidis, P. G.

2006-01-01

Combining dynamic renormalization with equation-free computational tools, we study the apparently asymptotically self-similar evolution of void distribution dynamics in the diffusion-deposition problem proposed by Stinchcombe and Depken [Phys. Rev. Lett. 88, 125701 (2002)]. We illustrate fixed point and dynamic approaches, forward as well as backward in time; these can be used to accelerate simulators of glassy dynamic phenomena

Equation-free dynamic renormalization in a glassy compaction model

Science.gov (United States)

Chen, L.; Kevrekidis, I. G.; Kevrekidis, P. G.

2006-07-01

Combining dynamic renormalization with equation-free computational tools, we study the apparently asymptotically self-similar evolution of void distribution dynamics in the diffusion-deposition problem proposed by Stinchcombe and Depken [Phys. Rev. Lett. 88, 125701 (2002)]. We illustrate fixed point and dynamic approaches, forward as well as backward in time; these can be used to accelerate simulators of glassy dynamic phenomena.

Solid-state dynamics and single-crystal to single-crystal structural transformations in octakis(3-chloropropyl)octasilsesquioxane and octavinyloctasilsesquioxane.

Science.gov (United States)

Kowalewska, A; Nowacka, M; Włodarska, M; Zgardzińska, B; Zaleski, R; Oszajca, M; Krajenta, J; Kaźmierski, S

2017-10-18

Reactive octahedral silsesquioxanes of rod-like [octakis(3-chloropropyl)octasilsesquioxane - T 8 (CH 2 CH 2 CH 2 Cl) 8 ] and spherical [octavinyloctasilsesquioxane - T 8 (CH[double bond, length as m-dash]CH 2 ) 8 ] structure can undergo reversible thermally induced phase transitions in the solid state. The phase behaviour has been studied with differential scanning calorimetry (DSC, including temperature modulated DSC), X-ray diffraction, dielectric relaxation spectroscopy (DRS), and nuclear magnetic resonance spectroscopy in the solid state (SS NMR), as well as positron annihilation lifetime spectroscopy (PALS) and polarized optical microscopy (POM). The mechanisms involving fitting the molecules into most symmetrical crystal lattices vary for species of different structure. Thermal energy can be used to expand the crystal lattice leading to thermochromism in the case of T 8 (CH[double bond, length as m-dash]CH 2 ) 8 or conversely to an unusual negative thermal expansion of crystals of T 8 (CH 2 CH 2 CH 2 Cl) 8 that results in their self-actuation. The complex behaviour is reflected in unusual changes in the capacitance and fractional free volume of the material. These phenomena can be used for molecular design of advanced well-defined hybrid materials capable of reversible thermally induced structural transformations. The findings present a new perspective for POSS-based flexible metal-organic frameworks (MOF) of cooperative structural transformability via entropy-based translational sub-net sliding.

Modification of glassy carbon electrode with a polymer/mediator composite and its application for the electrochemical detection of iodate

International Nuclear Information System (INIS)

Li, Ta-Jen; Lin, Chia-Yu; Balamurugan, A.; Kung, Chung-Wei; Wang, Jen-Yuan; Hu, Chih-Wei; Wang, Chun-Chieh; Chen, Po-Yen; Vittal, R.; Ho, Kuo-Chuan

2012-01-01

Highlights: ► FAD and PEDOT are combined to modify the glassy carbon electrode for IO 3 − sensing. ► The doping of FAD into PEDOT matrix can almost be viewed as an irreversible process. ► The optimal cycle number for preparing the GCE/PEDOT/FAD electrode is found to be 9. ► The detection limit of the GCE/PEDOT/FAD electrode for IO 3 − is found to be 0.16 μM. ► The GCE/PEDOT/FAD electrode possesses enough selectivity toward IO 3 − . - Abstract: A modified glassy carbon electrode was prepared by depositing a composite of polymer and mediator on a glassy carbon electrode (GCE). The mediator, flavin adenine dinucleotide (FAD) and the polymer, poly(3,4-ethylenedioxythiophene) (PEDOT) were electrochemically deposited as a composite on the GCE by applying cyclic voltammetry (CV). This modified electrode is hereafter designated as GCE/PEDOT/FAD. FAD was found to significantly enhance the growth of PEDOT. Electrochemical quartz crystal microbalance (EQCM) analysis was performed to study the mass changes in the electrode during the electrodeposition of PEDOT, with and without the addition of FAD. The optimal cycle number for preparing the modified electrode was determined to be 9, and the corresponding surface coverage of FAD (Γ FAD ) was ca. 5.11 × 10 −10 mol cm −2 . The amperometric detection of iodate was performed in a 100 mM buffer solution (pH 1.5). The GCE/PEDOT/FAD showed a sensitivity of 0.78 μA μM −1 cm −2 , a linear range of 4–140 μM, and a limit of detection of 0.16 μM for iodate. The interference effects of 250-fold Na + , Mg 2+ , Ca 2+ , Zn 2+ , Fe 2+ , Cl − , NO 3 − , I − , SO 4 2− and SO 3 2− , with reference to the concentration of iodate were negligible. The long-term stability of GCE/PEDOT/FAD was also investigated. The GCE/PEDOT/FAD electrode retained 82% of its initial amperometric response to iodate after 7 days. The GCE/PEDOT/FAD was also applied to determine iodate in a commercial salt.

Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

Energy Technology Data Exchange (ETDEWEB)

Yamaura, Kazunari, E-mail: YAMAURA.Kazunari@nims.go.jp [Superconducting Properties Unit, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, North 10 West 8, Kita-ku, Sapporo, Hokkaido 060-0810 (Japan)

2016-04-15

High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO{sub 3}, LiOsO{sub 3}, and Na{sub 2}OsO{sub 4}, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal–insulator transition in NaOsO{sub 3}, a ferroelectric-like transition in LiOsO{sub 3}, and high-temperature ferrimagnetism driven by a local structural distortion in Ca{sub 2}FeOsO{sub 6} may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices. - Graphical Abstract: Flux-grown crystals of NaOsO{sub 3} under high-pressure and high-temperature conditions in a belt-type apparatus. The crystal shows a magnetically driven metal–insulator transition at a temperature of 410 K. - Highlights: • Short review of high-pressure crystal growth of solid-state osmium oxides. • Wide variety of magnetic properties of solid-state osmium oxides. • Perovskite and related dense structures stabilized at 3–17 GPa.

Achieving dynamic behaviour and thermal expansion in the organic solid state via co-crystallization.

Science.gov (United States)

Hutchins, Kristin M; Groeneman, Ryan H; Reinheimer, Eric W; Swenson, Dale C; MacGillivray, Leonard R

2015-08-01

Thermal expansion involves a response of a material to an external stimulus that typically involves an increase in a crystallographic axis (positive thermal expansion (PTE)), although shrinking with applied heat (negative thermal expansion (NTE)) is known in rarer cases. Here, we demonstrate a means to achieve dynamic molecular motion and thermal expansions in organic solids via co-crystallizations. One co-crystal component is known to exhibit dynamic behaviour in the solid state while the second, when varied systematically, affords co-crystals with linear thermal expansion coefficients that range from colossal to nearly zero. Two co-crystals exhibit rare NTE. We expect the approach to guide the design of molecular solids that enable predesigned motion related to thermal expansion processes.

A study of nanostructured gold modified glassy carbon electrode for ...

Indian Academy of Sciences (India)

A nanostructured gold modified glassy carbon electrode (Aunano/GCE) was employed for the determination of trace chromium(VI). To prepare Aunano/GCE, the GCE was immersed into KAuCl4 solution and electrodeposition was conducted at the potential of -0.4 V (vs Ag/AgCl) for 600 s. Scanning electron microscopy ...

Gold nanoparticles directly modified glassy carbon electrode for non-enzymatic detection of glucose

Energy Technology Data Exchange (ETDEWEB)

Chang, Gang; Shu, Honghui; Ji, Kai [Ministry-of-Education Key Laboratory for the Green Preparation and Application of Functional Materials, Faculty of Materials Science and Engineering, Hubei University, No. 368 Youyi Avenue, Wuchang, Wuhan 430062 (China); Oyama, Munetaka [Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8520 (Japan); Liu, Xiong [Ministry-of-Education Key Laboratory for the Green Preparation and Application of Functional Materials, Faculty of Materials Science and Engineering, Hubei University, No. 368 Youyi Avenue, Wuchang, Wuhan 430062 (China); He, Yunbin, E-mail: ybhe@hubu.edu.cn [Ministry-of-Education Key Laboratory for the Green Preparation and Application of Functional Materials, Faculty of Materials Science and Engineering, Hubei University, No. 368 Youyi Avenue, Wuchang, Wuhan 430062 (China)

2014-01-01

This work describes controllable preparation of gold nanoparticles on glassy carbon electrodes by using the seed mediated growth method, which contains two steps, namely, nanoseeds attachment and nanocrystals growth. The size and the dispersion of gold nanoparticles grown on glassy carbon electrodes could be easily tuned through the growth time based on results of field-emission scanning electron microscopy. Excellent electrochemical catalytic characteristics for glucose oxidation were observed for the gold nanoparticles modified glassy carbon electrodes (AuNPs/GC), resulting from the extended active surface area provided by the dense gold nanoparticles attached. It exhibited a wide linear range from 0.1 mM to 25 mM with the sensitivity of 87.5 μA cm{sup −2} mM{sup −1} and low detection limit down to 0.05 mM for the sensing of glucose. The common interfering species such as chloride ion, ascorbic acid, uric acid and 4-acetamidophenol were verified having no interference effect on the detection of glucose. It is demonstrated that the seed mediated method is one of the facile approaches for fabricating Au nanoparticles modified substrates, which could work as one kind of promising electrode materials for the glucose nonenzymatic sensing.

Forming a three-dimensional porous organic network via solid-state explosion of organic single crystals.

Science.gov (United States)

Bae, Seo-Yoon; Kim, Dongwook; Shin, Dongbin; Mahmood, Javeed; Jeon, In-Yup; Jung, Sun-Min; Shin, Sun-Hee; Kim, Seok-Jin; Park, Noejung; Lah, Myoung Soo; Baek, Jong-Beom

2017-11-17

Solid-state reaction of organic molecules holds a considerable advantage over liquid-phase processes in the manufacturing industry. However, the research progress in exploring this benefit is largely staggering, which leaves few liquid-phase systems to work with. Here, we show a synthetic protocol for the formation of a three-dimensional porous organic network via solid-state explosion of organic single crystals. The explosive reaction is realized by the Bergman reaction (cycloaromatization) of three enediyne groups on 2,3,6,7,14,15-hexaethynyl-9,10-dihydro-9,10-[1,2]benzenoanthracene. The origin of the explosion is systematically studied using single-crystal X-ray diffraction and differential scanning calorimetry, along with high-speed camera and density functional theory calculations. The results suggest that the solid-state explosion is triggered by an abrupt change in lattice energy induced by release of primer molecules in the 2,3,6,7,14,15-hexaethynyl-9,10-dihydro-9,10-[1,2]benzenoanthracene crystal lattice.

Angular dependences of the luminescence and density of photon states in a chiral liquid crystal

Energy Technology Data Exchange (ETDEWEB)

Umanskii, B A; Blinov, L M; Palto, S P [A.V. Shubnikov Institute of Crystallography, Russian Academy of Sciences, Moscow, Russian Federaion (Russian Federation)

2013-11-30

Luminescence spectra of a laser dye-doped chiral liquid crystal have been studied in a wide range of angles (up to 60°) to the axis of its helical structure using a semicylindrical quartz prism, which made it possible to observe the shift and evolution of the photonic band gap in response to changes in angle. Using measured spectra and numerical simulation, we calculated the spectral distributions of the density of photon states in such a cholesteric crystal for polarised and unpolarised light, which characterise its structure as that of a chiral one-dimensional photonic crystal. (optics of liquid crystals)

Electric resistivity and thermoelectricity of Ni-Nb-Zr and Ni-Nb-Zr-H glassy alloys

Science.gov (United States)

Fukuhara, Mikio; Inoue, Akihisa

2010-09-01

Electric resistivity ρ and thermoelectric power S of Ni 36Nb 24Zr 40 and (Ni 0.36Nb 0.24Zr 0.4) 90H 10 glassy alloys were investigated in temperature region between 1.5 and 300 K. After resistivity curves of both alloys increase gradually with decreasing temperature down to around 6 K, they dropped suddenly and then reached zero resistivity at 2.1 K, leading to superconductivity. Linear curve with negative TCR of ρ vs T2 and slight increase of S/ T in temperature region down to around 6 K clearly reveal Fermi-liquid phenomenon in electronic state for both alloys independent of hydrogen content.

Electric resistivity and thermoelectricity of Ni-Nb-Zr and Ni-Nb-Zr-H glassy alloys

International Nuclear Information System (INIS)

Fukuhara, Mikio; Inoue, Akihisa

2010-01-01

Electric resistivity ρ and thermoelectric power S of Ni 36 Nb 24 Zr 40 and (Ni 0.36 Nb 0.24 Zr 0.4 ) 90 H 10 glassy alloys were investigated in temperature region between 1.5 and 300 K. After resistivity curves of both alloys increase gradually with decreasing temperature down to around 6 K, they dropped suddenly and then reached zero resistivity at 2.1 K, leading to superconductivity. Linear curve with negative TCR of ρ vs T 2 and slight increase of S/T in temperature region down to around 6 K clearly reveal Fermi-liquid phenomenon in electronic state for both alloys independent of hydrogen content.

Solid-state syntheses and single-crystal characterizations of three tetravalent thorium and uranium silicates

International Nuclear Information System (INIS)

Jin, Geng Bang; Soderholm, L.

2015-01-01

Colorless crystals of ThSiO 4 (huttonite) (1) and (Ca 0.5 Na 0.5 ) 2 NaThSi 8 O 20 (2) have been synthesized by the solid-state reactions of ThO 2 , CaSiO 3 , and Na 2 WO 4 at 1073 K. Green crystals of (Ca 0.5 Na 0.5 ) 2 NaUSi 8 O 20 (3) have been synthesized by the solid-state reactions of UO 2 , CaSiO 3 , and Na 2 WO 4 at 1003 K. All three compounds have been characterized by single-crystal X-ray diffraction. Compound 1 adopts a monazite-type three-dimensional condensed structure, which is built from edge- and corner-shared ThO 9 polyhedra and SiO 4 tetrahedra. Compounds 2 and 3 are isostructural and they crystallize in a steacyite-type structure. The structure consists of discrete pseudocubic [Si 8 O 20 ] 8− polyanions, which are connected by An 4+ cations into a three-dimensional framework. Each An atom coordinates to eight monodentate [Si 8 O 20 ] 8− moieties in a square antiprismatic geometry. Na + and Ca 2+ ions reside in the void within the framework. Raman spectra of 1, 2, and 3 were collected on single crystal samples. 1 displays more complex vibrational bands than thorite. Raman spectra of 2 and 3 are analogous with most of vibrational bands located at almost the same regions. - Graphical abstract: A Raman spectrum and crystal structures of (Ca 0.5 Na 0.5 ) 2 NaAnSi 8 O 20 (An=Th, U), which contain pseudocubic [Si 8 O 20 ] 8− polyanions and eight-coordinate An 4+ cations. - Highlights: • Single crystal growth of three tetravalent actinide silicates from melts. • Single-crystal structures and Raman spectra of (Ca 0.5 Na 0.5 ) 2 NaAnSi 8 O 20 (An=Th, U). • First report of Raman spectrum of huttonite on single crystal samples

Free volume and elastic properties changes in Cu-Zr-Ti-Pd bulk glassy alloy on heating

International Nuclear Information System (INIS)

Louzguine-Luzgin, Dmitri V.; Yavari, Alain Reza; Fukuhara, Mikio; Ota, Katsumi; Xie, Guoqiang; Vaughan, Gavin; Inoue, Akihisa

2007-01-01

The variation of free volume and elastic properties of the Cu 55 Zr 30 Ti 10 Pd 5 glassy alloy on heating was studied. The structure changes on heating were studied by synchrotron X-ray diffraction, differential scanning and isothermal calorimetries. The studied glassy alloy shows a rather high Poisson's ratio exceeding 0.42 which is maintained after the structure relaxation and primary devitrification. Young's and Shear modules decrease upon primary devitrification while Bulk modulus exhibits a maximum after structural relaxation

Occurrence of particle debris field during focused Ga ion beam milling of glassy carbon

Energy Technology Data Exchange (ETDEWEB)

Hu Qin [Centre for Industrial Photonics, Institute for Manufacturing, Department of Engineering, University of Cambridge, Alan Reece Building, 17 Charles Babbage Road, Cambridge, CB3 0FS (United Kingdom); O' Neill, William, E-mail: wo207@eng.cam.ac.uk [Centre for Industrial Photonics, Institute for Manufacturing, Department of Engineering, University of Cambridge, Alan Reece Building, 17 Charles Babbage Road, Cambridge, CB3 0FS (United Kingdom)

2010-08-01

To explore the machining characteristics of glassy carbon by focused ion beam (FIB), particles induced by FIB milling on glassy carbon have been studied in the current work. Nano-sized particles in the range of tens of nanometers up to 400 nm can often be found around the area subject to FIB milling. Two ion beam scanning modes - slow single scan and fast repetitive scan - have been tested. Fewer particles are found in single patterns milled in fast repetitive scan mode. For a group of test patterns milled in a sequence, it was found that a greater number of particles were deposited around sites machined early in the sequence. In situ EDX analysis of the particles showed that they were composed of C and Ga. The formation of particles is related to the debris generated at the surrounding areas, the low melting point of gallium used as FIB ion source and the high contact angle of gallium on glassy carbon induces de-wetting of Ga and the subsequent formation of Ga particles. Ultrasonic cleaning can remove over 98% of visible particles. The surface roughness (R{sub a}) of FIB milled areas after cleaning is less than 2 nm.

Occurrence of particle debris field during focused Ga ion beam milling of glassy carbon

International Nuclear Information System (INIS)

Hu Qin; O'Neill, William

2010-01-01

To explore the machining characteristics of glassy carbon by focused ion beam (FIB), particles induced by FIB milling on glassy carbon have been studied in the current work. Nano-sized particles in the range of tens of nanometers up to 400 nm can often be found around the area subject to FIB milling. Two ion beam scanning modes - slow single scan and fast repetitive scan - have been tested. Fewer particles are found in single patterns milled in fast repetitive scan mode. For a group of test patterns milled in a sequence, it was found that a greater number of particles were deposited around sites machined early in the sequence. In situ EDX analysis of the particles showed that they were composed of C and Ga. The formation of particles is related to the debris generated at the surrounding areas, the low melting point of gallium used as FIB ion source and the high contact angle of gallium on glassy carbon induces de-wetting of Ga and the subsequent formation of Ga particles. Ultrasonic cleaning can remove over 98% of visible particles. The surface roughness (R a ) of FIB milled areas after cleaning is less than 2 nm.

Electrochemical investigations of Pu(IV)/Pu(III) redox reaction using graphene modified glassy carbon electrodes and a comparison to the performance of SWCNTs modified glassy carbon electrodes

International Nuclear Information System (INIS)

Gupta, Ruma; Gamare, Jayashree; Sharma, Manoj K.; Kamat, J.V.

2016-01-01

Highlights: • First report of aqueous electrochemistry of Plutonium on graphene modified electrode. • Graphene is best electrocatalytic material for Pu(IV)/Pu(III) redox couple among the reported modifiers viz. reduced graphene oxide (rGO) and SWCNT’s. • The electrochemical reversibility of Pu(IV)/Pu(III) redox couple improves significantly on graphene modified electrode compared to previously reported rGO & SWCNTs modified electrodes • Donnan interaction between plutonium species and graphene surface offers a possibility for designing a highly sensitive sensor for plutonium • Graphene modified electrode shows higher sensitivity for the determination of plutonium compared to glassy carbon and single walled carbon nanotube modified electrode - Abstract: The work reported in this paper demonstrates for the first time that graphene modified glassy carbon electrode (Gr/GC) show remarkable electrocatalysis towards Pu(IV)/Pu(III) redox reaction and the results were compared with that of single-walled carbon nanotubes modified GC (SWCNTs/GC) and glassy carbon (GC) electrodes. Graphene catalyzes the exchange of current of the Pu(IV)/Pu(III) couple by reducing both the anodic and cathodic overpotentials. The Gr/GC electrode shows higher peak currents (i p ) and smaller peak potential separation (ΔE p ) values than the SWCNTs/GC and GC electrodes. The heterogeneous electron transfer rate constants (k s ), charge transfer coefficients (α) and the diffusion coefficients (D) involved in the electrocatalytic redox reaction were determined. Our observations show that graphene is best electrocatalytic material among both the SWCNTs and GC to study Pu(IV)/Pu(III) redox reaction.

Determination of Volatility and Element Fractionation in Glassy Fallout Debris by SIMS

Energy Technology Data Exchange (ETDEWEB)

Williamson, Todd L. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Tenner, Travis Jay [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Bonamici, Chloe Elizabeth [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Kinman, William Scott [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Pollington, Anthony Douglas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Steiner, Robert Ernest [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-05-10

The purpose of this report is to characterize glassy fallout debris using the Trinity Test and then characterize the U-isotopes of U₃O₈ reference materials that contain weaponized debris.

Physical ageing in the above-bandgap photoexposured glassy arsenic selenides

Energy Technology Data Exchange (ETDEWEB)

Kozdras, A [Faculty of Physics of Opole University of Technology, 75, Ozimska str., Opole, PL-45370 (Poland); Golovchak, R [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202, Stryjska str., Lviv, UA-79031 (Ukraine); Shpotyuk, O [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202, Stryjska str., Lviv, UA-79031 (Ukraine)

2007-08-15

Physical ageing induced by above-bandgap light illumination is studied in glassy As-Se using differential scanning calorimetry. It is shown that measurable effect like to known short-term physical ageing is observed only in Se-rich glasses. The kinetics of this effect is compared with that caused by natural storage in a dark.

Physical ageing in the above-bandgap photoexposured glassy arsenic selenides

International Nuclear Information System (INIS)

Kozdras, A; Golovchak, R; Shpotyuk, O

2007-01-01

Physical ageing induced by above-bandgap light illumination is studied in glassy As-Se using differential scanning calorimetry. It is shown that measurable effect like to known short-term physical ageing is observed only in Se-rich glasses. The kinetics of this effect is compared with that caused by natural storage in a dark

Co-based soft magnetic bulk glassy alloys optimized for glass ...

Indian Academy of Sciences (India)

diameter of 5 mm by conventional copper mould casting method. It reveals ... For example, Co43Fe20Ta5.5B31.5 glassy alloy with a ... coercive force (Hc) of 0.25 A m. −1 ..... [7] Lu Z P, Liu C T, Thompson J R and Porter W D 2004 Phys. Rev.

Gigantic spin splitting of exciton states in CdSe:Mn hexagonal crystal

International Nuclear Information System (INIS)

Komarov, A.V.; Ryabchenko, S.M.; Semenov, Yu.G.; Shanina, B.D.; Vitrikhovskij, N.I.; AN Ukrainskoj SSR, Kiev. Inst. Poluprovodnikov)

1980-01-01

Gigantic spin splitting of exciton states in magneto-doped semiconductors is observed for the first time in the CdSe: Mn hexagonal crystal. A theoretical interpretation of some features of the effect due to the anisotropy of the crystal is presented. The parameters of the band structure are determined by comparing with the experiments: Δ 1 =46+-3, Δ 2 =137+-1, Δ 3 =140.6+-0.3 meV. It is shown that in CdSe:Mn just as in cubic semiconductors, exchange interaction with magnetic impurities is ferromagnetic for electrons of the conductivity band and antiferromagnetic for electrons of the valence band. The exchange constants are of the same order of magnetude as those for the CdTe:Mn, ZnTe:Mn and ZnSe:Mn crystals

Definition and preparation of glassy matrices by innovating processes to confine radioactive wastes and industrial toxic materials

International Nuclear Information System (INIS)

Moncouyoux, J.P.

1995-01-01

The confinement by vitrification of high-level radioactive wastes is studied in the CEA for fifteen years. These studies have lead to the preparation of glassy matrices by innovating processes. These processes can be applied to non-radioactive toxic materials treatment too. In this work are more particularly described the glassy matrix long-dated behaviour and the different vitrification processes used (by direct induction in cold crucible, by transferred arc plasma). (O.L.). 1 tab

Effect of Slag Composition on the Crystallization Kinetics of Synthetic CaO-SiO2-Al2O3-MgO Slags

Science.gov (United States)

Esfahani, Shaghayegh; Barati, Mansoor

2018-04-01

The crystallization kinetics of CaO-SiO2-Al2O3-MgO (CSAM) slags was studied with the aid of single hot thermocouple technique (SHTT). Kinetic parameters such as the Avrami exponent ( n), rate coefficient ( K), and effective activation energy of crystallization ( E A ) were obtained by kinetic analysis of data obtained from in situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In an attempt to predict crystallization rate under non-isothermal conditions, a mathematical model was developed that employs the rate data of isothermal transformation. The model was validated by reproducing an experimental continuous cooling transformation diagram purely from isothermal data.

Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals

KAUST Repository

Shi, Dong

2015-01-29

The fundamental properties and ultimate performance limits of organolead trihalide MAPbX3(MA = CH3NH3 +; X = Br- or I- ) perovskites remain obscured by extensive disorder in polycrystalline MAPbX3 films. We report an antisolvent vapor-assisted crystallization approach that enables us to create sizable crack-free MAPbX3 single crystals with volumes exceeding 100 cubic millimeters. These large single crystals enabled a detailed characterization of their optical and charge transport characteristics.We observed exceptionally low trap-state densities on the order of 109 to 1010 per cubic centimeter in MAPbX3 single crystals (comparable to the best photovoltaic-quality silicon) and charge carrier diffusion lengths exceeding 10 micrometers. These results were validated with density functional theory calculations.

Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals

KAUST Repository

Shi, Dong; Adinolfi, Valerio; Comin, Riccardo; Yuan, Mingjian; Alarousu, Erkki; Buin, Andrei K.; Chen, Yin; Hoogland, Sjoerd H.; Rothenberger, Alexander; Katsiev, Khabiboulakh; Losovyj, Yaroslav B.; Zhang, Xin; Dowben, Peter A.; Mohammed, Omar F.; Sargent, E. H.; Bakr, Osman

2015-01-01

The fundamental properties and ultimate performance limits of organolead trihalide MAPbX3(MA = CH3NH3 +; X = Br- or I- ) perovskites remain obscured by extensive disorder in polycrystalline MAPbX3 films. We report an antisolvent vapor-assisted crystallization approach that enables us to create sizable crack-free MAPbX3 single crystals with volumes exceeding 100 cubic millimeters. These large single crystals enabled a detailed characterization of their optical and charge transport characteristics.We observed exceptionally low trap-state densities on the order of 109 to 1010 per cubic centimeter in MAPbX3 single crystals (comparable to the best photovoltaic-quality silicon) and charge carrier diffusion lengths exceeding 10 micrometers. These results were validated with density functional theory calculations.

Mapping the Local Density of Optical States of a Photonic Crystal with Single Quantum Dots

DEFF Research Database (Denmark)

Wang, Qin; Stobbe, Søren; Lodahl, Peter

2011-01-01

We use single self-assembled InGaAs quantum dots as internal probes to map the local density of optical states of photonic crystal membranes. The employed technique separates contributions from nonradiative recombination and spin-flip processes by properly accounting for the role of the exciton...... fine structure. We observe inhibition factors as high as 70 and compare our results to local density of optical states calculations available from the literature, thereby establishing a quantitative understanding of photon emission in photonic crystal membranes. © 2011 American Physical Society....

Electrocatalytic oxidation of hydrazine at overoxidized polypyrrole film modified glassy carbon electrode

Energy Technology Data Exchange (ETDEWEB)

Majidi, Mir Reza [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51664 (Iran, Islamic Republic of); Jouyban, Abolghasem [Faculty of Pharmacy and Drug Applied Research Center, Tabriz University of Medical Sciences, Tabriz 51664 (Iran, Islamic Republic of); Asadpour-Zeynali, Karim [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51664 (Iran, Islamic Republic of)]. E-mail: asadpour@tabrizu.ac.ir

2007-06-20

Electrocatalytic oxidation of hydrazine (HZ) was studied on an overoxidized polypyrrole (OPPy) modified glassy carbon electrode using cyclic voltammetry and chronoamperometry techniques. The OPPy-modified glassy carbon electrode has very high catalytic ability for electrooxidation of HZ, which appeared as a reduced overpotential in a wide operational pH range of 5-10. The overall numbers of electrons involved in the catalytic oxidation of HZ, the number of electrons involved in the rate-determining and diffusion coefficient of HZ were estimated using cyclic voltammetry and chronoamperometry. It has been shown that using the OPPy-modified electrode, HZ can be determined by cyclic voltammetry and amperometry with limit of detection 36 and 3.7 {mu}M, respectively. The results of the analysis suggest that the proposed method promises accurate results and could be employed for the routine determination of HZ.

Study of electrical properties of glassy Se100–xTex alloys

Indian Academy of Sciences (India)

Unknown

can be successfully explained by correlated barrier hopping (CBH) model. ... The results show that bipolaron hopping dominates over single-polaron hopping in this glassy system. This .... where ∆E is the activation energy and σ0 is called the.

Density of photonic states in cholesteric liquid crystals

Science.gov (United States)

Dolganov, P. V.

2015-04-01

Density of photonic states ρ (ω ) , group vg, and phase vph velocity of light, and the dispersion relation between wave vector k , and frequency ω (k ) were determined in a cholesteric photonic crystal. A highly sensitive method (measurement of rotation of the plane of polarization of light) was used to determine ρ (ω ) in samples of different quality. In high-quality samples a drastic increase in ρ (ω ) near the boundaries of the stop band and oscillations related to Pendellösung beatings are observed. In low-quality samples photonic properties are strongly modified. The maximal value of ρ (ω ) is substantially smaller, and density of photonic states increases near the selective reflection band without oscillations in ρ (ω ) . Peculiarities of ρ (ω ) , vg, and ω (k ) are discussed. Comparison of the experimental results with theory was performed.

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...

Cooperative strings and glassy interfaces.

Science.gov (United States)

Salez, Thomas; Salez, Justin; Dalnoki-Veress, Kari; Raphaël, Elie; Forrest, James A

2015-07-07

We introduce a minimal theory of glass formation based on the ideas of molecular crowding and resultant string-like cooperative rearrangement, and address the effects of free interfaces. In the bulk case, we obtain a scaling expression for the number of particles taking part in cooperative strings, and we recover the Adam-Gibbs description of glassy dynamics. Then, by including thermal dilatation, the Vogel-Fulcher-Tammann relation is derived. Moreover, the random and string-like characters of the cooperative rearrangement allow us to predict a temperature-dependent expression for the cooperative length ξ of bulk relaxation. Finally, we explore the influence of sample boundaries when the system size becomes comparable to ξ. The theory is in agreement with measurements of the glass-transition temperature of thin polymer films, and allows quantification of the temperature-dependent thickness hm of the interfacial mobile layer.

Asphaltene-laden interfaces form soft glassy layers in contraction experiments: a mechanism for coalescence blocking.

Science.gov (United States)

Pauchard, Vincent; Rane, Jayant P; Banerjee, Sanjoy

2014-11-04

In previous studies, the adsorption kinetics of asphaltenes at the water-oil interface were interpreted utilizing a Langmuir equation of state (EOS) based on droplet expansion experiments.1-3 Long-term adsorption kinetics followed random sequential adsorption (RSA) theory predictions, asymptotically reaching ∼85% limiting surface coverage, which is similar to limiting random 2D close packing of disks. To extend this work beyond this slow adsorption process, we performed rapid contractions and contraction-expansions of asphaltene-laden interfaces using the pendant drop experiment to emulate a Langmuir trough. This simulates the rapid increase in interfacial asphaltene concentration that occurs during coalescence events. For the contraction of droplets aged in asphaltene solutions, deviation from the EOS consistently occurs at a surface pressure value ∼21 mN/m corresponding to a surface coverage ∼80%. At this point droplets lose the shape required for validity of the Laplace-Young equation, indicating solidlike surface behavior. On further contraction wrinkles appear, which disappear when the droplet is held at constant volume. Surface pressure also decreases down to an equilibrium value near that measured for slow adsorption experiments. This behavior appears to be due to a transition to a glassy interface on contraction past the packing limit, followed by relaxation toward equilibrium by desorption at constant volume. This hypothesis is supported by cycling experiments around the close-packed limit where the transition to and from a solidlike state appears to be both fast and reversible, with little hysteresis. Also, the soft glass rheology model of Sollich is shown to capture previously reported shear behavior during adsorption. The results suggest that the mechanism by which asphaltenes stabilize water-in-oil emulsions is by blocking coalescence due to rapid formation of a glassy interface, in turn caused by interfacial asphaltenes rapidly increasing in

Glassy slag: A complementary waste form to homogeneous glass for the implementation of MAWS in treating DOE low level/mixed wastes

International Nuclear Information System (INIS)

Feng, X.; Ordaz, G.; Krumrine, P.

1994-01-01

Glassy slag waste forms are being developed to complement glass waste forms in implementing the Minimum Additive Waste Stabilization (MAWS) Program for supporting DOE's environmental restoration efforts. These glassy slags are composed of various metal oxide crystalline phases embedded in an alumino-silicate glass phase. The slags are appropriate final waste forms for waste streams that contain large amounts of scrap metals and elements with low solubilities in glass, and that have low-flux contents. Homogeneous glass waste forms are appropriate for wastes with sufficient fluxes and low metal contents. Therefore, utilization of both glass and glassy slag waste forms will make vitrification technology applicable to the treatment of a much larger range of radioactive and mixed wastes. The MAWS approach was a plied to glassy slags by blending multiple waste streams to produce the final waste form, minimizing overall waste form volume and reducing costs. The crystalline oxide phases formed in the glassy slags can be specially formulated so that they are very durable and contain hazardous and radioactive elements in their lattice structures. The Structural Bond Strength (SBS) Model was used to predict the chemical durability of the product from the slag composition so that optimized slag compositions could be obtain with a limited number of crucible melts and testing

Electric-field-induced flow-aligning state in a nematic liquid crystal.

Science.gov (United States)

Fatriansyah, Jaka Fajar; Orihara, Hiroshi

2015-04-01

The response of shear stress to a weak ac electric field as a probe is measured in a nematic liquid crystal under shear flow and dc electric fields. Two states with different responses are clearly observed when the dc electric field is changed at a constant shear rate: the flow aligning and non-flow aligning states. The director lies in the shear plane in the flow aligning state and out of the plane in the non-flow aligning state. Through application of dc electric field, the non-flow aligning state can be changed to the flow aligning state. In the transition from the flow aligning state to the non-flow aligning state, it is found that the response increases and the relaxation time becomes longer. Here, the experimental results in the flow aligning state are discussed on the basis of the Ericksen-Leslie theory.

Characterization of glassy phase at the surface of alumina ceramics substrate and its effect on laser cutting

Energy Technology Data Exchange (ETDEWEB)

Fu Renli [School of Mechanical-Electronic and Materials Engineering, China Univ. of Mining and Technology, Xuzhou, JS (China); Dept. of Ceramics and Glass Engineering, CICECO, Univ. of Aveiro, Aveiro (Portugal); Li Yanbo [School of Mechanical-Electronic and Materials Engineering, China Univ. of Mining and Technology, Xuzhou, JS (China); Xu Xin; Ferreira, J.M.F. [Dept. of Ceramics and Glass Engineering, CICECO, Univ. of Aveiro, Aveiro (Portugal)

2004-07-01

Nowadays alumina ceramic substrates are widely used for high precision applications in electronic devices, such as hybrid integrated circuits (HIC). Usually, the alumina ceramic substrates are shaped through tape casting method and sintered in continuous slab kilns. The sintering aids used to enhance densification during sintering give rise to the formation of an alumino-silicate liquid phase, which is of crucial importance in pressureless and low-temperature sintering (<1600 C) of alumina ceramics. The preferential migration of liquid phase to the surface of alumina substrates under the capillary action and its transformation into glassy phase during cooling affects the subsequent processing steps of HIC. A smoothening effect on surface with its enrichment in glassy phase is accompanied by a decrease of the surface toughness. On the other hand, the accumulated glassy phase onto the surface has a great effect on laser cutting. The high temperatures developed during laser cutting turn the superficial glassy phase into liquid again, while rapid solidification will occur after removing laser beam. The fast cooling of the liquid phase causes formation of extensive network of cracks on the surface of alumina substrate. Apparently, the presence of such faults degrades mechanical strength and thermal shock resistance of alumina substrates. Meanwhile, the recast layers and spatter deposits at the periphery of the hole has been observed. (orig.)

Isothermal equation of state of a lithium fluoride single crystal

Energy Technology Data Exchange (ETDEWEB)

Kim, K.Y.

1975-01-01

An isothermal equation of state of a LiF single crystal was determined from length change measurements of the specimen as a function of hydrostatic pressure up to approximately 7 kbars at 28 to 41/sup 0/C. The length change was measured with an accuracy of approximately 500 A by using a Fabry Perot type He--Ne laser interferometer for a 1-m long specimen at temperatures constant to less than 0.002/sup 0/C. Several two- and three-parameter equations of state were used in analyzing the measured pressure-volume data. The computer fit for each equation of state determines not only the value of its parameters but also the standard deviations associated with them and one dependent variable, either pressure or volume. With the parameters determined, the equations of state are extrapolated to approximately 5 megabars in order to see discrepancies. Using the Born model of ionic solids, two equations of state were derived both from a power law potential and from an exponential form for the repulsive energy of alkali metal halides and used to fit the pressure-volume data of a LiF single crystal. They are also extrapolated to approximately 5 megabars. The Birch's two-parameter equation and the Grover, Getting, and Kennedy equation are indistinguishable from the two equations of state derived from the Born model for pressures approximately equal to or less than 800 kbars within +-20 kbars. The above four equations of state also fit closely the Pagannone and Drickamer static compression data, the Christian shock wave data, and the Kormer et al. shock wave data. The isothermal bulk modulus and its first pressure derivative at atmospheric pressure and 28.83/sup 0/C are 664.5 +- 0.5 kbars and 5.40 +- 0.18, respectively, in close agreement with those values ultrasonically measured by R. A. Miller and C. S. Smith. (auth)

Modification of glassy carbon surfaces by atmospheric pressure cold plasma torch

DEFF Research Database (Denmark)

Mortensen, Henrik Junge; Kusano, Yukihiro; Leipold, Frank

2006-01-01

The effect of plasma treatment on glassy carbon (GC) surfaces was studied with adhesion improvement in mind. A newly constructed remote plasma source was used to treat GC plates. Pure He and a dilute NH3/He mixture were used as feed gases. Optical emission spectroscopy was performed for plasma to...

Direct electron transfer from glucose oxidase immobilized on a nano-porous glassy carbon electrode

International Nuclear Information System (INIS)

Haghighi, Behzad; Tabrizi, Mahmoud Amouzadeh

2011-01-01

Highlights: → A direct electron transfer reaction of glucose oxidase was observed on the surface of a nano-porous glassy carbon electrode. → A pair of well-defined and reversible redox peaks was observed at the formal potential of approximately -0.439 V. → The apparent electron transfer rate constant was measured to be 5.27 s -1 . → A mechanism for the observed direct electron transfer reaction was proposed, which consists of a two-electron and a two-proton transfer. - Abstract: A pair of well-defined and reversible redox peaks was observed for the direct electron transfer (DET) reaction of an immobilized glucose oxidase (GOx) on the surface of a nano-porous glassy carbon electrode at the formal potential (E o ') of -0.439 V versus Ag/AgCl/saturated KCl. The electron transfer rate constant (k s ) was calculated to be 5.27 s -1 . The dependence of E o ' on pH indicated that the direct electron transfer of the GOx was a two-electron transfer process, coupled with two-proton transfer. The results clearly demonstrate that the nano-porous glassy carbon electrode is a cost-effective and ready-to-use scaffold for the fabrication of a glucose biosensor.

Direct electron transfer from glucose oxidase immobilized on a nano-porous glassy carbon electrode

Energy Technology Data Exchange (ETDEWEB)

Haghighi, Behzad, E-mail: haghighi@iasbs.ac.ir [Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, Gava Zang, Zanjan (Iran, Islamic Republic of); Tabrizi, Mahmoud Amouzadeh [Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, Gava Zang, Zanjan (Iran, Islamic Republic of)

2011-11-30

Highlights: > A direct electron transfer reaction of glucose oxidase was observed on the surface of a nano-porous glassy carbon electrode. > A pair of well-defined and reversible redox peaks was observed at the formal potential of approximately -0.439 V. > The apparent electron transfer rate constant was measured to be 5.27 s{sup -1}. > A mechanism for the observed direct electron transfer reaction was proposed, which consists of a two-electron and a two-proton transfer. - Abstract: A pair of well-defined and reversible redox peaks was observed for the direct electron transfer (DET) reaction of an immobilized glucose oxidase (GOx) on the surface of a nano-porous glassy carbon electrode at the formal potential (E{sup o}') of -0.439 V versus Ag/AgCl/saturated KCl. The electron transfer rate constant (k{sub s}) was calculated to be 5.27 s{sup -1}. The dependence of E{sup o}' on pH indicated that the direct electron transfer of the GOx was a two-electron transfer process, coupled with two-proton transfer. The results clearly demonstrate that the nano-porous glassy carbon electrode is a cost-effective and ready-to-use scaffold for the fabrication of a glucose biosensor.

Voltammetric behavior of sedative drug midazolam at glassy carbon electrode in solubilized systems

Directory of Open Access Journals (Sweden)

Rajeev Jain

2012-04-01

Full Text Available Redox behavior of midazolam was studied at a glassy carbon electrode in various buffer systems, supporting electrolytes and pH using differential pulse, square-wave and cyclic voltammetry. Based on its reduction behavior, a direct differential pulse voltammetric method has been developed and validated for the determination of midazolam in parenteral dosage. Three well-defined peaks were observed in 0.1% SLS, Britton–Robinson (BR buffer of pH 2.5. The effect of surfactants like sodium lauryl sulfate (SLS, cetyl trimethyl ammonium bromide (CTAB and Tween 20 was studied. Among these surfactants SLS showed significant enhancement in reduction peak. The cathodic peak currents were directly proportional to the concentration of midazolam with correlation coefficient of 0.99. Keywords: Midazolam, Voltammetry, Surfactant, Glassy carbon electrode, Parenteral dosage form

ELECTROCHEMICAL DETERMINATION OF ETHANOL, 2- PROPANOL AND 1-BUTANOL ON GLASSY CARBON ELECTRODE MODIFIED WITH NICKEL OXIDE FILM

Directory of Open Access Journals (Sweden)

A. Benchettara

2014-12-01

Full Text Available In this work, we present the modification of a glassy carbon electrode with nickel oxide film which is performed in two successive steps. In the first one, the electrochemical deposition of metallic nickel on the glassy carbon electrode (GCE is achieved in 0.1M boric acid; in the second step, the metallic deposit is anodically oxidized in 0.1M NaOH. These two operations were carried out in a three electrode cell with a filiform platinum auxiliary electrode, a SCE as potential reference and a working microelectrode of modified glassy carbon with nickel oxides. This electrode is characterized by several electrochemical techniques and is used for the catalytic determination of ethanol, 2-propanol and 1-butanol in 0.1 M NaOH. The proposed chemical mechanism shows that NiO2 acts as a mediator.

ELECTROCHEMICAL DETERMINATION OF ETHANOL, 2- PROPANOL AND 1-BUTANOL ON GLASSY CARBON ELECTRODE MODIFIED WITH NICKEL OXIDE FILM

Directory of Open Access Journals (Sweden)

A. Benchettara

2015-07-01

Full Text Available In this work, we present the modification of a glassy carbon electrode with nickel oxide film which is performed in two successive steps. In the first one, the electrochemical deposition of metallic nickel on the glassy carbon electrode (GCE is achieved in 0.1M boric acid; in the second step, the metallic deposit is anodically oxidized in 0.1M NaOH. These two operations were carried out in a three electrode cell with a filiform platinum auxiliary electrode, a SCE as potential reference and a working microelectrode of modified glassy carbon with nickel oxides. This electrode is characterized by several electrochemical techniques and is used for the catalytic determination of ethanol, 2-propanol and 1-butanol in 0.1 M NaOH. The proposed chemical mechanism shows that NiO2 acts as a mediator.

A crystal chemistry approach for high-power ytterbium doped solid-state lasers: diffusion-bonded crystals and new crystalline hosts

International Nuclear Information System (INIS)

Gaume, R.

2002-11-01

This work deals with ytterbium based crystals for high-power laser applications. In particular, we focus our interest in reducing crystal heating and its consequences during laser operation following two different ways. First, we review the specific properties of ytterbium doped solid-state lasers in order to define a figure-of-merit which gives the evaluation of laser performances, thermo-mechanical and thermo-optical properties. Bearing in mind this analysis, we propose a set of theoretical tools, based on the crystallographic structure of the crystal and its chemical composition, to predict thermo-mechanical and optical potentials. This approach, used for the seek of new Yb 3+ -doped materials for high-power laser applications, shows that simple oxides containing rare-earths are favorable. Therefore, the spectroscopic properties of six new materials Yb 3+ :GdVO 4 , Yb 3+ :GdAlO 3 , Yb 3+ :Gd 2 O 3 , Yb 3+ :Sc 2 SiO 5 , Yb 3+ :CaSc 2 O 4 and Yb 3+ :SrSc 2 O 4 are described. The second aspect developed in this work deals with thermal properties enhancement of already well characterized laser materials. Two different ways are explored: a) elaboration by diffusion bonding of end-caps lasers with undoped crystals (composite crystals). Thus, different composites were obtained and a fairly lowering of thermal lensing effect was observed during laser operation. b) strengthening of crystalline structures by ionic substitution of one of its constituents. We demonstrate how crystal growth ability can be improved by a cationic substitution in the case of Yb 3+ :BOYS, a largely-tunable laser material which is of great interest for femtosecond pulses generation. (author)

{sup 35}Cl NQR in glassy crystal, 3-chlorothiophene

Energy Technology Data Exchange (ETDEWEB)

Fujimori, H., E-mail: fujimori@chs.nihon-u.ac.jp; Kaneko, T.; Asaji, T. [Nihon University, Department of Chemistry, College of Humanities and Sciences (Japan)

2008-01-15

{sup 35}Cl NQR measurements were carried out between 77 and 209 K for 3-chlorothiophene, which has a glass transition in a stable crystalline state. An NQR signal with full widths of about 100 kHz at half maximum was observed in this temperature range. The spin-lattice relaxation time T{sub 1} was measured at the peak frequencies. The activation energy {Delta}{epsilon}{sub a} obtained from the results of the T{sub 1} measurements showed a good agreement with those estimated from calorimetric measurements.

Electrochemically modified sulfisoxazole nanofilm on glassy carbon for determination of cadmium(II) in water samples

International Nuclear Information System (INIS)

Gupta, Vinod Kumar; Yola, Mehmet Lütfi; Atar, Necip; Solak, Ali Osman; Uzun, Lokman; Üstündağ, Zafer

2013-01-01

Highlights: • Sulfisoxazole was grafted onto glassy carbon electrode. • The electrode was characterized by spectroscopic and electrochemical methods. • It has been used for the determination of Cd(II) ions in real samples in very low concentrations. -- Abstract: Sulfisoxazole (SO) was grafted to glassy carbon electrode (GCE) via the electrochemical oxidation of SO in acetonitrile solution containing 0.1 M tetrabutylammoniumtetra-fluoroborate (TBATFB). The prepared electrode was characterized by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), reflection–absorption infrared spectroscopy (RAIRS) and X-ray photoelectron spectroscopy (XPS). The ellipsometric thickness of SO nanofilm at the glassy carbon surface was obtained as 14.48 ± 0.11 nm. The stability of the SO modified GCE was studied. The SO modified GCE was also utilized for the determination of Cd(II) ions in water samples in the presence of Pb(II) and Fe(II) by adsorptive stripping voltammetry. The linearity range and the detection limit of Cd(II) ions were 1.0 × 10 −10 to 5.0 × 10 −8 M and 3.3 × 10 −11 M (S/N = 3), respectively

Optical Tamm states in one-dimensional superconducting photonic crystal

Energy Technology Data Exchange (ETDEWEB)

El Abouti, O. [LPMR, Département de Physique, Faculté des Sciences, Université Mohammed 1, 60000 Oujda (Morocco); El Boudouti, E. H. [LPMR, Département de Physique, Faculté des Sciences, Université Mohammed 1, 60000 Oujda (Morocco); IEMN, UMR-CNRS 8520, UFR de Physique, Université de Lille 1, 59655 Villeneuve d' Ascq (France); El Hassouani, Y. [ESIM, Département de Physique, Faculté des Sciences et Techniques, Université Moulay Ismail, Boutalamine BP 509, 52000 Errachidia (Morocco); Noual, A. [LPMR, Département de Physique, Faculté des Sciences, Université Mohammed 1, 60000 Oujda (Morocco); Ecole Normale Supérieur de Tétouan, Université Abdelmalek Essaadi, Tétouan (Morocco); Djafari-Rouhani, B. [IEMN, UMR-CNRS 8520, UFR de Physique, Université de Lille 1, 59655 Villeneuve d' Ascq (France)

2016-08-15

In this study, we investigate localized and resonant optical waves associated with a semi-infinite superlattice made out of superconductor-dielectric bilayers and terminated with a cap layer. Both transverse electric and transverse magnetic waves are considered. These surface modes are analogous to the so-called Tamm states associated with electronic states found at the surface of materials. The surface guided modes induced by the cap layer strongly depend on whether the superlattice ends with a superconductor or a dielectric layer, the thickness of the surface layer, the temperature of the superconductor layer as well as on the polarization of the waves. Different kinds of surface modes are found and their properties examined. These structures can be used to realize the highly sensitive photonic crystal sensors.

Electrochemical Glucose Oxidation Using Glassy Carbon Electrodes Modified with Au-Ag Nanoparticles: Influence of Ag Content

Directory of Open Access Journals (Sweden)

Nancy Gabriela García-Morales

2015-01-01

Full Text Available This paper describes the application of glassy carbon modified electrodes bearing Aux-Agy nanoparticles to catalyze the electrochemical oxidation of glucose. In particular, the paper shows the influence of the Ag content on this oxidation process. A simple method was applied to prepare the nanoparticles, which were characterized by transmission electron microscopy, Ultraviolet-Visible spectroscopy, X-ray diffraction spectroscopy, and cyclic voltammetry. These nanoparticles were used to modify glassy carbon electrodes. The effectiveness of these electrodes for electrochemical glucose oxidation was evaluated. The modified glassy carbon electrodes are highly sensitive to glucose oxidation in alkaline media, which could be attributed to the presence of Aux-Agy nanoparticles on the electrode surface. The voltammetric results suggest that the glucose oxidation speed is controlled by the glucose diffusion to the electrode surface. These results also show that the catalytic activity of the electrodes depends on the Ag content of the nanoparticles. Best results were obtained for the Au80-Ag20 nanoparticles modified electrode. This electrode could be used for Gluconic acid (GA production.

Microscopic origin of resistance drift in the amorphous state of the phase-change compound GeTe

Science.gov (United States)

Gabardi, S.; Caravati, S.; Sosso, G. C.; Behler, J.; Bernasconi, M.

2015-08-01

Aging is a common feature of the glassy state. In the case of phase-change chalcogenide alloys the aging of the amorphous state is responsible for an increase of the electrical resistance with time. This phenomenon called drift is detrimental in the application of these materials in phase-change nonvolatile memories, which are emerging as promising candidates for storage class memories. By means of combined molecular dynamics and electronic structure calculations based on density functional theory, we have unraveled the atomistic origin of the resistance drift in the prototypical phase-change compound GeTe. The drift results from a widening of the band gap and a reduction of Urbach tails due to structural relaxations leading to the removal of chains of Ge-Ge homopolar bonds. The same structural features are actually responsible for the high mobility above the glass transition which boosts the crystallization speed exploited in the device.

Magma heating by decompression-driven crystallization beneath andesite volcanoes.

Science.gov (United States)

Blundy, Jon; Cashman, Kathy; Humphreys, Madeleine

2006-09-07

Explosive volcanic eruptions are driven by exsolution of H2O-rich vapour from silicic magma. Eruption dynamics involve a complex interplay between nucleation and growth of vapour bubbles and crystallization, generating highly nonlinear variation in the physical properties of magma as it ascends beneath a volcano. This makes explosive volcanism difficult to model and, ultimately, to predict. A key unknown is the temperature variation in magma rising through the sub-volcanic system, as it loses gas and crystallizes en route. Thermodynamic modelling of magma that degasses, but does not crystallize, indicates that both cooling and heating are possible. Hitherto it has not been possible to evaluate such alternatives because of the difficulty of tracking temperature variations in moving magma several kilometres below the surface. Here we extend recent work on glassy melt inclusions trapped in plagioclase crystals to develop a method for tracking pressure-temperature-crystallinity paths in magma beneath two active andesite volcanoes. We use dissolved H2O in melt inclusions to constrain the pressure of H2O at the time an inclusion became sealed, incompatible trace element concentrations to calculate the corresponding magma crystallinity and plagioclase-melt geothermometry to determine the temperature. These data are allied to ilmenite-magnetite geothermometry to show that the temperature of ascending magma increases by up to 100 degrees C, owing to the release of latent heat of crystallization. This heating can account for several common textural features of andesitic magmas, which might otherwise be erroneously attributed to pre-eruptive magma mixing.

Glass formation and crystallization of Zr53Cu21Al10Ni8Ti8 alloy

International Nuclear Information System (INIS)

Neogy, S.; Tewari, R.; Srivastava, D.; Dey, G.K.; Banerjee, S.; Vaibhaw, K.; Ranganathan, S.

2010-01-01

In the present study, transmission electron microscopy techniques, like micro-diffraction, high resolution and fluctuation microscopy, have been employed to carry out detailed investigation of as-solidified and crystallized microstructures of the Zr 53 Cu 21 Al 10 Ni 8 Ti 8 alloy synthesized using melt spinning, suction casting and copper mould casting techniques. Samples produced by copper mould casting technique showed partially crystalline microstructure whereas the other techniques resulted in complete amorphous microstructures. High-resolution microscopy established that the dendrites of the big cube phase in partially crystalline glass grew by atomistic ledges. The other crystalline bct Zr 2 Ni phase, present in partially crystalline glass and also in all the crystallized microstructures, showed various types of internal faults depending upon the crystallite size. Fluctuation microscopy established that oxygen plays a major role in determining the degree of medium range order in glassy phases. In addition, variation in oxygen content changed the crystallization behaviour of glasses from a single to multiple events

Diazonium Chemistry for the Bio-Functionalization of Glassy Nanostring Resonator Arrays

Directory of Open Access Journals (Sweden)

Wei Zheng

2015-07-01

Full Text Available Resonant glassy nanostrings have been employed for the detection of biomolecules. These devices offer high sensitivity and amenability to large array integration and multiplexed assays. Such a concept has however been impaired by the lack of stable and biocompatible linker chemistries. Diazonium salt reduction-induced aryl grafting is an aqueous-based process providing strong chemical adhesion. In this work, diazonium-based linker chemistry was performed for the first time on glassy nanostrings, which enabled the bio-functionalization of such devices. Large arrays of nanostrings with ultra-narrow widths down to 10 nm were fabricated employing electron beam lithography. Diazonium modification was first developed on SiCN surfaces and validated by X-ray photoelectron spectroscopy. Similarly modified nanostrings were then covalently functionalized with anti-rabbit IgG as a molecular probe. Specific enumeration of rabbit IgG was successfully performed through observation of downshifts of resonant frequencies. The specificity of this enumeration was confirmed through proper negative control experiments. Helium ion microscopy further verified the successful functionalization of nanostrings.

Diazonium Chemistry for the Bio-Functionalization of Glassy Nanostring Resonator Arrays.

Science.gov (United States)

Zheng, Wei; Du, Rongbing; Cao, Yong; Mohammad, Mohammad A; Dew, Steven K; McDermott, Mark T; Evoy, Stephane

2015-07-30

Resonant glassy nanostrings have been employed for the detection of biomolecules. These devices offer high sensitivity and amenability to large array integration and multiplexed assays. Such a concept has however been impaired by the lack of stable and biocompatible linker chemistries. Diazonium salt reduction-induced aryl grafting is an aqueous-based process providing strong chemical adhesion. In this work, diazonium-based linker chemistry was performed for the first time on glassy nanostrings, which enabled the bio-functionalization of such devices. Large arrays of nanostrings with ultra-narrow widths down to 10 nm were fabricated employing electron beam lithography. Diazonium modification was first developed on SiCN surfaces and validated by X-ray photoelectron spectroscopy. Similarly modified nanostrings were then covalently functionalized with anti-rabbit IgG as a molecular probe. Specific enumeration of rabbit IgG was successfully performed through observation of downshifts of resonant frequencies. The specificity of this enumeration was confirmed through proper negative control experiments. Helium ion microscopy further verified the successful functionalization of nanostrings.

Force-free state in a superconducting single crystal and angle-dependent vortex helical instability

Science.gov (United States)

del Valle, J.; Gomez, A.; Gonzalez, E. M.; Manas-Valero, S.; Coronado, E.; Vicent, J. L.

2017-06-01

Superconducting 2 H -NbS e2 single crystals show intrinsic low pinning values. Therefore, they are ideal materials with which to explore fundamental properties of vortices. (V , I ) characteristics are the experimental data we have used to investigate the dissipation mechanisms in a rectangular-shaped 2 H -NbS e2 single crystal. Particularly, we have studied dissipation behavior with magnetic fields applied in the plane of the crystal and parallel to the injected currents, i.e., in the force-free state where the vortex helical instability governs the vortex dynamics. In this regime, the data follow the elliptic critical state model and the voltage dissipation shows an exponential dependence, V ∝eα (I -IC ∥ ) , IC ∥ being the critical current in the force-free configuration and α a linear temperature-dependent parameter. Moreover, this exponential dependence can be observed for in-plane applied magnetic fields up to 40° off the current direction, which implies that the vortex helical instability plays a role in dissipation even out of the force-free configuration.

Crystal structure and tautomerism of Pigment Yellow 138 determined by X-ray powder diffraction and solid-state NMR

DEFF Research Database (Denmark)

Gumbert, Silke D.; Körbitzer, Meike; Alig, Edith

2016-01-01

The crystal structure of C.I. Pigment Yellow 138 was determined from X-ray powder diffraction data using real-space methods with subsequent Rietveld refinements. The tautomeric state was investigated by solid-state 1D and 2D multinuclear NMR experiments. In the crystals, the compound exhibits...... the NH-tautomer with a hydrogen atom situated at the nitrogen of the quinoline moiety. Direct evidence of the presence of the NH-tautomer is provided by 1H–14N HMQC solid-state NMR at very fast MAS. Solid-state dispersion-corrected density functional theory calculations with BLYP-D3 confirm...

Stress-induced state transitions in flexible liquid-crystal devices

International Nuclear Information System (INIS)

Ho, I-Lin; Chang, Yia-Chung

2012-01-01

This work studies the stress-strain dynamics for the transient optoelectronic characteristics of flexible liquid-crystal (LC) devices. Due to the fast response of LC directors, the configuration of the LC is assumed to be in quasi-equilibrium during the process of elastic deformations of the flexible structures. The LC medium hence can be treated effectively as a thin-film layer and can approximately follow the strain-stress mechanism in the solids. Relevant theoretical algorithms are studied in this work, and numerical results present the stress-induced state transitions in the π cell.

Crystal structure and spin state of mixed-crystals of iron with NCS and NCBH3 for the assembled complexes bridged by 1,3-bis(4-pyridyl)propanes

International Nuclear Information System (INIS)

Haruka Dote; Hiroki Yasuhara

2015-01-01

New mixed crystals, Fe(NCS) x (NCBH 3 )( 2-x )(bpp) 2 , (bpp = 1,3-bis(4-pyridyl)propane) were synthesized. The formation of mixed crystals was confirmed by powder X-ray diffraction patterns and single crystal X-ray structural analysis. Elemental analyses showed that all Fe(NCS) x (NCBH 3 )( 2-x )(bpp) 2 samples had more Fe(NCS) 2 unit than the preparation fraction. 57 Fe Moessbauer spectroscopy revealed that all the spectra consist of only Fe(NCS) 2 unit and Fe(NCBH 3 ) 2 unit. And the fraction of low-spin state in the Fe(NCBH 3 ) 2 unit changed with the change of x. The results suggested that the high spin site of Fe(NCS) 2 unit affects the spin state of Fe(NCBH 3 ) 2 unit. (author)

Dynamics and Geometry of Icosahedral Order in Liquid and Glassy Phases of Metallic Glasses

Directory of Open Access Journals (Sweden)

Masato Shimono

2015-07-01

Full Text Available The geometrical properties of the icosahedral ordered structure formed in liquid and glassy phases of metallic glasses are investigated by using molecular dynamics simulations. We investigate the Zr-Cu alloy system as well as a simple model for binary alloys, in which we can change the atomic size ratio between alloying components. In both cases, we found the same nature of icosahedral order in liquid and glassy phases. The icosahedral clusters are observed in liquid phases as well as in glassy phases. As the temperature approaches to the glass transition point Tg, the density of the clusters rapidly grows and the icosahedral clusters begin to connect to each other and form a medium-range network structure. By investigating the geometry of connection between clusters in the icosahedral network, we found that the dominant connecting pattern is the one sharing seven atoms which forms a pentagonal bicap with five-fold symmetry. From a geometrical point of view, we can understand the mechanism of the formation and growth of the icosahedral order by using the Regge calculus, which is originally employed to formulate a theory of gravity. The Regge calculus tells us that the distortion energy of the pentagonal bicap could be decreased by introducing an atomic size difference between alloying elements and that the icosahedral network would be stabilized by a considerably large atomic size difference.

Steady-state hydrodynamic instabilities of active liquid crystals: hybrid lattice Boltzmann simulations.

Science.gov (United States)

Marenduzzo, D; Orlandini, E; Cates, M E; Yeomans, J M

2007-09-01

We report hybrid lattice Boltzmann (HLB) simulations of the hydrodynamics of an active nematic liquid crystal sandwiched between confining walls with various anchoring conditions. We confirm the existence of a transition between a passive phase and an active phase, in which there is spontaneous flow in the steady state. This transition is attained for sufficiently "extensile" rods, in the case of flow-aligning liquid crystals, and for sufficiently "contractile" ones for flow-tumbling materials. In a quasi-one-dimensional geometry, deep in the active phase of flow-aligning materials, our simulations give evidence of hysteresis and history-dependent steady states, as well as of spontaneous banded flow. Flow-tumbling materials, in contrast, rearrange themselves so that only the two boundary layers flow in steady state. Two-dimensional simulations, with periodic boundary conditions, show additional instabilities, with the spontaneous flow appearing as patterns made up of "convection rolls." These results demonstrate a remarkable richness (including dependence on anchoring conditions) in the steady-state phase behavior of active materials, even in the absence of external forcing; they have no counterpart for passive nematics. Our HLB methodology, which combines lattice Boltzmann for momentum transport with a finite difference scheme for the order parameter dynamics, offers a robust and efficient method for probing the complex hydrodynamic behavior of active nematics.

Supercooled and glassy water: Metastable liquid(s), amorphous solid(s), and a no-man's land

Science.gov (United States)

Handle, Philip H.; Loerting, Thomas; Sciortino, Francesco

2017-12-01

We review the recent research on supercooled and glassy water, focusing on the possible origins of its complex behavior. We stress the central role played by the strong directionality of the water-water interaction and by the competition between local energy, local entropy, and local density. In this context we discuss the phenomenon of polyamorphism (i.e., the existence of more than one disordered solid state), emphasizing both the role of the preparation protocols and the transformation between the different disordered ices. Finally, we present the ongoing debate on the possibility of linking polyamorphism with a liquid-liquid transition that could take place in the no-man's land, the temperature-pressure window in which homogeneous nucleation prevents the investigation of water in its metastable liquid form.

Violation of the fluctuation-dissipation theorem in glassy systems: basic notions and the numerical evidence

International Nuclear Information System (INIS)

Crisanti, A; Ritort, F

2003-01-01

This review reports on the research done during past years on violations of the fluctuation-dissipation theorem (FDT) in glassy systems. It is focused on the existence of a quasi-fluctuation-dissipation theorem (QFDT) in glassy systems and the current supporting knowledge gained from numerical simulation studies. It covers a broad range of non-stationary aging and stationary driven systems such as structural glasses, spin glasses, coarsening systems, ferromagnetic models at criticality, trap models, models with entropy barriers, kinetically constrained models, sheared systems and granular media. The review is divided into four main parts: (1) an introductory section explaining basic notions related to the existence of the FDT in equilibrium and its possible extension to the glassy regime (QFDT), (2) a description of the basic analytical tools and results derived in the framework of some exactly solvable models, (3) a detailed report of the current evidence in favour of the QFDT and (4) a brief digression on the experimental evidence in its favour. This review is intended for inexpert readers who want to learn about the basic notions and concepts related to the existence of the QFDT as well as for the more expert readers who may be interested in more specific results. (topical review)

A harmonic transition state theory model for defect initiation in crystals

International Nuclear Information System (INIS)

Delph, T J; Cao, P; Park, H S; Zimmerman, J A

2013-01-01

We outline here a model for the initiation of defects in crystals based upon harmonic transition state theory (hTST). This model combines a previously developed model for zero-temperature defect initiation with a multi-dimensional hTST model that is capable of accurately predicting the effects of temperature and loading rate upon defect initiation. The model has several features that set it apart from previous efforts along these lines, most notably a straightforward method of determining the energy barrier between adjacent equilibrium states that does not depend upon a priori information concerning the nature of the defect. We apply the model to two examples, triaxial stretching of a perfect fcc crystal and nanoindentation of a gold substrate. Very good agreement is found between the predictions of the model and independent molecular dynamics (MD) simulations. Among other things, the model predicts a strong dependence of the defect initiation behavior upon the loading parameter. A very attractive feature of this model is that it is valid for arbitrarily slow loading rates, in particular loading rates achievable in the laboratory, and suffers from none of the limitations in this regard inherent in MD simulations. (paper)

Topological structure and mechanics of glassy polymer networks.

Science.gov (United States)

Elder, Robert M; Sirk, Timothy W

2017-11-22

The influence of chain-level network architecture (i.e., topology) on mechanics was explored for unentangled polymer networks using a blend of coarse-grained molecular simulations and graph-theoretic concepts. A simple extension of the Watts-Strogatz model is proposed to control the graph properties of the network such that the corresponding physical properties can be studied with simulations. The architecture of polymer networks assembled with a dynamic curing approach were compared with the extended Watts-Strogatz model, and found to agree surprisingly well. The final cured structures of the dynamically-assembled networks were nearly an intermediate between lattice and random connections due to restrictions imposed by the finite length of the chains. Further, the uni-axial stress response, character of the bond breaking, and non-affine displacements of fully-cured glassy networks were analyzed as a function of the degree of disorder in the network architecture. It is shown that the architecture strongly affects the network stability, flow stress, onset of bond breaking, and ultimate stress while leaving the modulus and yield point nearly unchanged. The results show that internal restrictions imposed by the network architecture alter the chain-level response through changes to the crosslink dynamics in the flow regime and through the degree of coordinated chain failure at the ultimate stress. The properties considered here are shown to be sensitive to even incremental changes to the architecture and, therefore, the overall network architecture, beyond simple defects, is predicted to be a meaningful physical parameter in the mechanics of glassy polymer networks.

Read/write characteristics of a new type of bit-patterned-media using nano-patterned glassy alloy

International Nuclear Information System (INIS)

Takenaka, Kana; Saidoh, Noriko; Nishiyama, Nobuyuki; Ishimaru, Manabu; Futamoto, Masaaki; Inoue, Akihisa

2012-01-01

The paper reports a feasibility study of new type bit-patterned-media using a nano-patterned glassy alloy template for ultra-high density hard disk applications. The prototype bit-patterned-media was prepared using a nano-hole array pattern fabricated on a Pd-based glassy alloy thin film and a Co/Pd multilayered film filled in the nano-holes. The prepared prototype bit-patterned-media had a smooth surface and isolated Co/Pd multilayer magnetic dots, where the average dot diameter, the average dot pitch and the average dot height were 30, 60 and 19 nm, respectively. MFM (magnetic force microscope) observation revealed that each dot was magnetized in a perpendicular direction and the magnetization could reverse when an opposite magnetic field was applied. Static read/write tester measurements showed that repeated writing and reading on isolated magnetic dots were possible in combination with conventional magnetic heads and high-accuracy positioning technologies. The present study indicates that the new type of bit-patterned-media composed of nano-hole arrays fabricated on glassy alloy film template and Co/Pd multilayer magnetic dots are promising for applications to next generation ultra-high density hard disk drives. - Highlights: ► Prototype BPM using a nano-hole array pattern of imprinted Pd-based glassy alloy thin film and Co/Pd multilayered film was set. ► The prototype BPM has smooth surface and isolated Co/Pd multilayer magnetic dots with an average dot diameter of 30 nm. ► Dots acted as perpendicular magnetic dot and were able to read, erase and write in a row by a usual perpendicular magnetic head.

In situ Spectroscopy of Solid-State Chemical Reaction in PbBr2-Deposited CsBr Crystals

Science.gov (United States)

Kondo, Shin-ichi; Matsunaga, Toshihiro; Saito, Tadaaki; Asada, Hiroshi

2003-09-01

It is possible to measure the fundamental optical absorption spectra of CsPbBr3 and Cs4PbBr6, whose stability is predicted by the study of phase diagram in the binary system CsBr-PbBr2, by means of in situ optical absorption and reflection spectroscopy of thermally induced solid-state chemical reaction in PbBr2-deposited CsBr crystals. On heavy annealing of the crystals, the Pb2+ ions are uniformly dispersed in the crystal matrix. The present experiment provides a novel method for measuring intrinsic optical absorption of ternary metal halides and also for in situ monitoring of doping metal halide crystal with impurities (metal ions or halogen ions).

Crystallization mechanisms of acicular crystals

Science.gov (United States)

Puel, François; Verdurand, Elodie; Taulelle, Pascal; Bebon, Christine; Colson, Didier; Klein, Jean-Paul; Veesler, Stéphane

2008-01-01

In this contribution, we present an experimental investigation of the growth of four different organic molecules produced at industrial scale with a view to understand the crystallization mechanism of acicular or needle-like crystals. For all organic crystals studied in this article, layer-by-layer growth of the lateral faces is very slow and clear, as soon as the supersaturation is high enough, there is competition between growth and surface-activated secondary nucleation. This gives rise to pseudo-twinned crystals composed of several needle individuals aligned along a crystallographic axis; this is explained by regular over- and inter-growths as in the case of twinning. And when supersaturation is even higher, nucleation is fast and random. In an industrial continuous crystallization, the rapid growth of needle-like crystals is to be avoided as it leads to fragile crystals or needles, which can be partly broken or totally detached from the parent crystals especially along structural anisotropic axis corresponding to weaker chemical bonds, thus leading to slower growing faces. When an activated mechanism is involved such as a secondary surface nucleation, it is no longer possible to obtain a steady state. Therefore, the crystal number, size and habit vary significantly with time, leading to troubles in the downstream processing operations and to modifications of the final solid-specific properties. These results provide valuable information on the unique crystallization mechanisms of acicular crystals, and show that it is important to know these threshold and critical values when running a crystallizer in order to obtain easy-to-handle crystals.

Cap casting and enveloped casting techniques for Zr55Cu30Ni5Al10 glassy alloy rod with 32 mm in diameter

International Nuclear Information System (INIS)

Yokoyama, Yoshihiko; Inoue, Akihisa; Mund, Enrico; Schultz, Ludwig

2009-01-01

In order to produce centimetre-sized bulk glassy alloys (BMGs), various cast techniques have been developed. We succeed in the development of cap casting and enveloped casting technique to accomplish the fabrication of centimetre sized BMGs. The former has an advantage to increase cooling rate and the later has an advantage to joint another materials instead of welding. This paper presents the production of a glassy Zr 55 Cu 30 Ni 5 Al 10 alloy rod with a diameter of 32 mm and joined glassy Zr 55 Cu 30 Ni 5 Al 10 alloy parts with another materials for industrial applications.

Electrical studies on silver based fast ion conducting glassy materials

International Nuclear Information System (INIS)

Rao, B. Appa; Kumar, E. Ramesh; Kumari, K. Rajani; Bhikshamaiah, G.

2014-01-01

Among all the available fast ion conductors, silver based glasses exhibit high conductivity. Further, glasses containing silver iodide enhances fast ion conducting behavior at room temperature. Glasses of various compositions of silver based fast ion conductors in the AgI−Ag 2 O−[(1−x)B 2 O 3 −xTeO 2 ] (x=0 to1 mol% in steps of 0.2) glassy system have been prepared by melt quenching method. The glassy nature of the compounds has been confirmed by X-ray diffraction. The electrical conductivity (AC) measurements have been carried out in the frequency range of 1 KHz–3MHz by Impedance Analyzer in the temperature range 303–423K. The DC conductivity measurements were also carried out in the temperature range 300–523K. From both AC and DC conductivity studies, it is found that the conductivity increases and activation energy decreases with increasing the concentration of TeO 2 as well as with temperature. The conductivity of the present glass system is found to be of the order of 10 −2 S/cm at room temperature. The ionic transport number of these glasses is found to be 0.999 indicating that these glasses can be used as electrolyte in batteries

Photonic crystals possessing multiple Weyl points and the experimental observation of robust surface states

Science.gov (United States)

Chen, Wen-Jie; Xiao, Meng; Chan, C. T.

2016-01-01

Weyl points, as monopoles of Berry curvature in momentum space, have captured much attention recently in various branches of physics. Realizing topological materials that exhibit such nodal points is challenging and indeed, Weyl points have been found experimentally in transition metal arsenide and phosphide and gyroid photonic crystal whose structure is complex. If realizing even the simplest type of single Weyl nodes with a topological charge of 1 is difficult, then making a real crystal carrying higher topological charges may seem more challenging. Here we design, and fabricate using planar fabrication technology, a photonic crystal possessing single Weyl points (including type-II nodes) and multiple Weyl points with topological charges of 2 and 3. We characterize this photonic crystal and find nontrivial 2D bulk band gaps for a fixed kz and the associated surface modes. The robustness of these surface states against kz-preserving scattering is experimentally observed for the first time. PMID:27703140

Nonlinear spectroscopy of the bound exciton states in CdSe single crystals

International Nuclear Information System (INIS)

Lisitsa, M.P.; Onishchenko, N.A.; Stolyarenko, A.V.; Ananchenko, V.V.; Polishchuk, S.V.

1989-01-01

The study is devoted to the pulsed laser radiation effect on the time-resolved variations of free and bound exciton bands region at the helium temperature. A gradual disappearance of the bound I 2 exciton state is observed with increase of the excitation intensity I in CdSe transmission spectra. This phenomenon is explained by the fact that despite of the shorter life of I 2 excitons as compared to the free ones, the concentration of the centres on which they localize is rather low (≤10 16 cm -3 ) while the evolution of the light-generated electron-hole pairs is such as the most probable recombination through the bound excitons. The transmission spectrum kinetics is studied. The intensity limitation of the laser pulse transmitted through the crystal in the region of the exciton ground state region is shown to be related with two-photon absorption (TPA) in which the exciton state is an intermediate level. The calculation results are in good agreement with the experiment. The estimations show the giant TPA coefficient of ∼10 3 cm/MW. The evolution of photoexcited nonequilibrium electron-hole pairs is studied. The possibility of using CdSe single crystals as spectrum-selective limiters of the laser pulses is shown. (author)

Thermal analysis of cryoprotective solutions for red blood cells.

Science.gov (United States)

Iijima, T

1998-05-01

A differential scanning calorimeter was used to study the thermal behavior of glycerol-water solutions (binary system) and the more complex glycerol-based cryoprotective solutions that are used clinically in order to examine the cryoprotective role of glycerol in preserving frozen red blood cells. The melting and glass transition temperatures for the clinically used cryoprotective solutions were as expected, based on the nonequilibriumphase diagram for cryoprotective solutions incorporating isotonic phosphate-buffered saline. Two zones were identified in which solidification occurred without the formation of ice crystals: a glassy state that is crystallographically amorphous was found for glycerol concentrations between 40 and 55% in the binary system and between 45 and 60% in the complex system; a glassy state in the complete absence of ice was found at glycerol concentrations greater than 55% for the binary system or 60% for the complex system. In clinical practice, cryoprotectants are used at initial concentrations lower than those at which these two glassy states occur but there is an increase in the effective glycerol concentration inside and outside the cells as ice forms during the freezing process.

Unidirectional edge states in topological honeycomb-lattice membrane photonic crystals.

Science.gov (United States)

Anderson, P Duke; Subramania, Ganapathi

2017-09-18

Photonic analogs of electronic systems with topologically non-trivial behavior such as unidirectional scatter-free propagation has tremendous potential for transforming photonic systems. Like in electronics topological behavior can be observed in photonics for systems either preserving time-reversal (TR) symmetry or explicitly breaking it. TR symmetry breaking requires magneto-optic photonics crystals (PC) or generation of synthetic gauge fields. For on-chip photonics that operate at optical frequencies both are quite challenging because of poor magneto-optic response of materials or substantial nanofabrication challenges in generating synthetic gauge fields. A recent work by Ma, et al. [Phys. Rev. Lett.114, 223901 (2015)] based on preserving pseudo TR symmetry offers a promising design scheme for observing unidirectional edge states in a modified honeycomb photonic crystal (PC) lattice of circular rods that offers encouraging alternatives. Here we propose through bandstructure calculations the inverse system of modified honeycomb PC of circular holes in a dielectric membrane which is more attractive from fabrication standpoint for on-chip applications. We observe trivial and non-trivial bandgaps as well as unidirectional edge states of opposite helicity propagating in opposite directions at the interface of a trivial and non-trivial PC structures. Around 1550nm operating wavelength ~55nm of bandwidth is possible for practicable values of design parameters (lattice constant, hole radii, membrane thickness, scaling factor etc.) and robust to reasonable variations in those parameters.

Highly efficient red-emitting BaMgBO3F:Eu3+,R+ (R: Li, Na, K, Rb) phosphor for near-UV excitation synthesized via glass precursor solid-state reaction

Science.gov (United States)

Shinozaki, Kenji; Akai, Tomoko

2017-09-01

Eu3+-doped fluoroborate crystals of BaMgBO3F were synthesized by a solid-state reaction using a glassy precursor material, and their photoluminescence (PL) was investigated. To compensate for the incorporation of Eu3+ into Ba2+ sites, samples codoped with alkali ions (Li+, Na+, K+, Rb+) were also prepared. The Eu3+-doped sample showed red PL with a quantum yield (QY) of 65% caused by near-UV excitation (λ = 393 nm), and PL intensity and QY increased with the codoping of Eu3+ and alkali ions. It was found that the Eu3+,Li+-codoped sample showed the highest PL intensity and a QY of 83%.

Dielectric relaxation in glassy Se75In25−xPbx alloys

Indian Academy of Sciences (India)

to their atomic percentages and were sealed in quartz ampoules (length ~5 cm and internal dia. ~8 mm) in vacuum ... samples were taken out by breaking the quartz ampoules. The glassy nature of the ... measured with the help of a calibrated copper–constantan thermocouple mounted very near to the sample, which could ...

Dynamical singularities of glassy systems in a quantum quench.

Science.gov (United States)

Obuchi, Tomoyuki; Takahashi, Kazutaka

2012-11-01

We present a prototype of behavior of glassy systems driven by quantum dynamics in a quenching protocol by analyzing the random energy model in a transverse field. We calculate several types of dynamical quantum amplitude and find a freezing transition at some critical time. The behavior is understood by the partition-function zeros in the complex temperature plane. We discuss the properties of the freezing phase as a dynamical chaotic phase, which are contrasted to those of the spin-glass phase in the static system.

Gas Permeation Related to the Moisture Sorption in Films of Glassy Hydrophilic Polymers

NARCIS (Netherlands)

Laksmana, F. L.; Kok, P. J. A. Hartman; Frijlink, H. W.; Vromans, H.; Maarschalk, K. Van Der Voort

2010-01-01

The purpose of this article is to elucidate the effect of integral sorption of moisture on gas permeation in glassy hydrophilic polymers. The oxygen and the simultaneous moisture sorption into various hydroxypropyl methylcellulose (HPMC) films were measured under a wide range of relative humidities

A TPD-MS study of glassy carbon surfaces oxidized by CO2 and O2

Directory of Open Access Journals (Sweden)

MILA D. LAUSEVIC

2002-11-01

Full Text Available The temperature-programmed desorption (TPD method combined with mass spectrometric (MS analysis has been applied to investigate the surface properties of carbon materials. The apparatus consisting of a temperature-programmed furnace and a quadrupole mass spectrometer was constructed in order to characterize the surface of differently treated glassy carbon samples. In this work, samples of glassy carbon exposed to air, CO2 and O2 were examined. The desorption of H2O, CO and CO2, as major products, indicated the presence of different oxide groups. The amount of these groups for all samples was calculated. It is concluded that oxidation affects the nature and the amount of the surface oxide groups and contributes to their increased stability.

Novel electroanalysis of hydroxyurea at glassy carbon and gold electrode surfaces

Directory of Open Access Journals (Sweden)

Keerti M. Naik

2014-09-01

Full Text Available A simple and a novel electroanalysis of hydroxyurea (HU drug at glassy carbon and gold electrode was investigated for the first time using cyclic, linear sweep and differential pulse voltammetric techniques. The oxidation of HU was irreversible and exhibited a diffusion controlled process on both electrodes. The oxidation mechanism was proposed. The dependence of the current on pH, the concentration, nature of buffer, and scan rate was investigated to optimize the experimental conditions for the determination of HU. It was found that the optimum buffer pH was 7.0, a physiological pH. In the range of 0.01 to 1.0 mM, the current measured by differential pulse voltammetry showed a linear relationship with HU concentration with limit of detection of 0.46 µM for glassy carbon electrode and 0.92 µM for gold electrode. In addition, reproducibility, precision and accuracy of the method were checked as well. The developed method was successfully applied to HU determination in pharmaceutical formulation and human biological fluids. The method finds its applications in quality control laboratories and pharmacokinetics.

Gold nanoparticle/multi-walled carbon nanotube modified glassy carbon electrode as a sensitive voltammetric sensor for the determination of diclofenac sodium.

Science.gov (United States)

Afkhami, Abbas; Bahiraei, Atousa; Madrakian, Tayyebeh

2016-02-01

A simple and highly sensitive sensor for the determination of diclofenac sodium based on gold nanoparticle/multi-walled carbon nanotube modified glassy carbon electrode is reported. Scanning electron microscopy along with energy dispersive X-ray spectroscopy, electrochemical impedance spectroscopy, cyclic voltammetry and square wave voltammetry was used to characterize the nanostructure and performance of the sensor and the results were compared with those obtained at the multi-walled carbon nanotube modified glassy carbon electrode and bare glassy carbon electrode. Under the optimized experimental conditions diclofenac sodium gave linear response over the range of 0.03-200μmolL(-1). The lower detection limits were found to be 0.02μmolL(-1). The effect of common interferences on the current response of DS was investigated. The practical application of the modified electrode was demonstrated by measuring the concentration of diclofenac sodium in urine and pharmaceutical samples. This revealed that the gold nanoparticle/multiwalled carbon nanotube modified glassy carbon electrode shows excellent analytical performance for the determination of diclofenac sodium in terms of a very low detection limit, high sensitivity, very good accuracy, repeatability and reproducibility. Copyright © 2015 Elsevier B.V. All rights reserved.

Preface: Proceedings of the ESF Exploratory Workshop on Glassy Liquids under Pressure: Fundamentals and Applications (Ustroń, Poland, 10-12 October 2007) Proceedings of the ESF Exploratory Workshop on Glassy Liquids under Pressure: Fundamentals and Applications (Ustroń, Poland, 10-12 October 2007)

Science.gov (United States)

Drozd-Rzoska, Aleksandra; Rzoska, Sylwester J.; Tamarit, Josep Ll

2008-06-01

that the dynamics of (canonical) glasses is almost completely controlled by orientational degrees of freedom 34 and thus, vitrifying orientationally disordered crystals can yield materials with a reduction of complexity. This can be important for reaching a better insight into the glass state and vitrification in general. The European Science Foundation Exploratory Workshop (ESF EW) is a brainstorming panel for the best specialists in the given field of science. Participants of the ESF EW 'Glassy Liquids Under Pressure' arrived at the Institute of Physics, the Silesian University, Katowice, Poland on 10 October 2007. Katowice is the capital of Upper Silesia and of the metropolitan area of Silesia (population ≈ 4 000 000)—the most industrial area of Poland. The conference coach took participants to the Jaskółka Hotel in Ustroń, a tourist resort situated in the beautiful valley at the foot of the Beskidy mountains (a part of West Carpaty), 80 km south from Katowice. The picturesque surroundings together with the delicious local cuisine created a stimulating atmosphere for the three days of lectures and discussions. References [1] Turnbull D 1969 Under what criterion the glass can be formed Contemp. Phys.10 3473 [2] Drozd-Rzoska A, Rzoska S J and Imre A R 2007 On the pressure evolution of the melting temperature and the glass transition temperature J. Non-Cryst. Solids 353 3915 [3]Donth E 1998 The Glass Transition. Relaxation Dynamics in Liquids and Disordered Materials(Springer Series in Materials Science II vol 48) (Berlin: Springer) [4] Johari G P and Goldstein M 1971 Viscous liquids and the glass transition in aliphatic alcohols and other norigid molecules J. Chem. Phys. 55 4245 [5] Roland C M and Casalini R 2004 Viscosity crossover in 0-therphenyl and salol under high pressure Phys. Rev. Lett.92 245702 [6] Novikov V N and Sokolov A P 2003 Universality of the dynamic crossover in glass-forming liquids: A 'magic' relaxation time Phys. Rev. E 67 031507 [7

Dynamically tunable interface states in 1D graphene-embedded photonic crystal heterostructure

Science.gov (United States)

Huang, Zhao; Li, Shuaifeng; Liu, Xin; Zhao, Degang; Ye, Lei; Zhu, Xuefeng; Zang, Jianfeng

2018-03-01

Optical interface states exhibit promising applications in nonlinear photonics, low-threshold lasing, and surface-wave assisted sensing. However, the further application of interface states in configurable optics is hindered by their limited tunability. Here, we demonstrate a new approach to generate dynamically tunable and angle-resolved interface states using graphene-embedded photonic crystal (GPC) heterostructure device. By combining the GPC structure design with in situ electric doping of graphene, a continuously tunable interface state can be obtained and its tuning range is as wide as the full bandgap. Moreover, the exhibited tunable interface states offer a possibility to study the correspondence between space and time characteristics of light, which is beyond normal incident conditions. Our strategy provides a new way to design configurable devices with tunable optical states for various advanced optical applications such as beam splitter and dynamically tunable laser.

Nanostructured sodium lithium niobate and lithium niobium tantalate solid solutions obtained by controlled crystallization of glass

International Nuclear Information System (INIS)

Radonjic, L.; Todorovic, M.; Miladinovic, J.

2005-01-01

Transparent, nanostructured glass ceramics based on ferroelectric solid solutions of the type Na 1-x Li x NbO 3 (in very narrow composition regions for x = 0.12 and 0.93) and LiNb 1-y Ta y O 3 (y = 0.5 unlimited solid solubility), can be obtained by controlled crystallization of glass. The parent glass samples were prepared by conventional melt-quenching technique. Heat-treatment of the parent glasses was performed at the various temperatures, for the same time. The glass structure evolution during the controlled crystallization was examined by FT-IR spectroscopy analysis. Crystalline phases were identified by X-ray diffraction analysis and SEM was used for microstructure characterization. Densities of the crystallized glasses were measured by Archimedean principle. The capacitance and dielectric loss tangent were measured at a frequency of 1 kHz, at the room temperature. It was found that in the all investigated systems crystallize solid solutions Na 1-x Li x NbO 3 and LiNb 1-y Ta y O 3 in the glassy matrix, have crystal size on nanoscale (less than 100 nm), which is one of requirements to get a transparent glass ceramic that could be a good ferroelectric material regarding to the measured properties

The influence of the bulk reduction state on the surface structure and morphology of rutile TiO{sub 2}(110) single crystals

Energy Technology Data Exchange (ETDEWEB)

Li, M.; Hebenstreit, W.; Diebold, U.; Tyryshkin, A.M.; Bowman, M.K.; Dunham, G.G.; Henderson, M.A.

2000-05-25

The authors have investigated the relationship between different types and amounts of bulk defects and the surface morphology of TiO{sub 2}(110) single crystals prepared by annealing in ultrahigh vacuum and in oxygen. Rutile TiO{sub 2}(110) specimens were cut from the same crystal and were heated in a furnace to different temperatures which resulted in different states of reduction (colors of the crystals). After characterization of the bulk defects with electron paramagnetic resonance (EPR), the specimens were studied with scanning tunneling microscopy (STM), low-energy He{sup +} ion scattering (LEIS), and work function measurements. EPR reveals that darker rutile crystals exhibit higher concentrations of extended Ti{sup 3+} related bulk defects such as crystallographic shear planes (CSP), with a decrease in substitutional and interstitial defects as compared to lighter crystals. Surface structures with (1 x 2) features are preferably formed upon UHV annealing on these darker crystals. LEIS measurements show that all of the crystals' (110) surfaces are reoxidized upon annealing in {sup 18}O{sub 2} (573 K, 1 x 10{sup {minus}6} mbar, 10 min) and that the {sup 18}O surface content is proportional to the bulk reduction state. UV-visible adsorption spectra and resistivity measurements also scale with the reduction states of crystals. Only the (1 x 1) structure is observed on the surface of slightly reduced crystals. Annealing in oxygen induces additional metastable structures, i.e., TiO{sub 2} clusters on blue crystals and rosette networks on dark blue crystals.

Studies on Photodarkening Effect in Glassy As2S3 Using High Field NMR

Science.gov (United States)

Hari, Parameswar; Su, Tining; Taylor, Craig; Reyes, Arneil; Kuhns, Phil; Moulton, William; Sullivan, N. S.

2001-03-01

Photodarkening, or the shift of the optical absorption edge to smaller energies after excitation with light whose energy is near that of the optical band edge, has been studied in many chalcogenide glasses for many years. Recently we have conducted nuclear magnetic resonance (NMR) studies of 75As in glassy As2S3 at 17T . We compared the 75As NMR lineshape in glassy As2S3 before and after irradiation at 77K. After irradiation at 514.5 nm for 230 hours with 170 mW/cm2 there is a subtle change in the NMR lineshape. This change is reversible on annealing at 200 C for 1.75 hours. We will discuss the implications of this result based on NMR lineshape analysis using an exact solution of the spin 3/2 Hamiltonian

Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates.

Science.gov (United States)

Chadwick, F Mark; McKay, Alasdair I; Martinez-Martinez, Antonio J; Rees, Nicholas H; Krämer, Tobias; Macgregor, Stuart A; Weller, Andrew S

2017-08-01

Single-crystal to single-crystal solid/gas reactivity and catalysis starting from the precursor sigma-alkane complex [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(η 2 η 2 -NBA)][BAr F 4 ] (NBA = norbornane; Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) is reported. By adding ethene, propene and 1-butene to this precursor in solid/gas reactions the resulting alkene complexes [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(alkene) x ][BAr F 4 ] are formed. The ethene ( x = 2) complex, [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(ethene) 2 ][BAr F 4 ]-Oct , has been characterized in the solid-state (single-crystal X-ray diffraction) and by solution and solid-state NMR spectroscopy. Rapid, low temperature recrystallization using solution methods results in a different crystalline modification, [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(ethene) 2 ][BAr F 4 ]-Hex , that has a hexagonal microporous structure ( P 6 3 22). The propene complex ( x = 1) [Rh(Cy 2 PCH 2 CH 2 PCy 2 )(propene)][BAr F 4 ] is characterized as having a π-bound alkene with a supporting γ-agostic Rh···H 3 C interaction at low temperature by single-crystal X-ray diffraction, variable temperature solution and solid-state NMR spectroscopy, as well as periodic density functional theory (DFT) calculations. A fluxional process occurs in both the solid-state and solution that is proposed to proceed via a tautomeric allyl-hydride. Gas/solid catalytic isomerization of d 3 -propene, H 2 C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111

Nitric Oxide Detection with Glassy Carbon Electrodes Coated with Charge-different Polymer Films

Directory of Open Access Journals (Sweden)

Jianping Lei

2005-04-01

Full Text Available Trace amounts of nitric oxide (NO have been determined in aqueous phosphate buffersolutions (pH=7.4 by using a glassy carbon electrode coated with three charge-different polymerfilms. The glassy carbon electrode was coated first with negatively charged Nafion film containingtetrakis(pentafluorophenylporphyrin iron(III chloride (Fe(IIITPFPP as the NO oxidation catalyst,and then with positively charged poly(acrylamide-co-diallyldimethylammonium chloride (PADDAand with neutral poly(dimethylsiloxane (silicone at the outermost layer. This polymer-coatedelectrode showed an excellent selectivity towards NO against possible concomitants in blood such asnitrite, ascorbic acid, uric acid, and dopamine. All current ratios between each concomitant and NOat the cyclic voltammogram was in 10-3 ~ 10-4. This type of electrode showed a detection limit of80 nM for NO. It was speculated from the electrochemical study in methanol that high-valent oxoiron(IV of Fe(TPFPP participated in the catalytic oxidation of NO.

Calix[6]arene mono-diazonium salt synthesis and covalent immobilization onto glassy carbon electrodes

International Nuclear Information System (INIS)

Cannizzo, Caroline; Jasmin, Jean-Philippe; Vautrin-Ul, Christine; Chausse, Annie; Wagner, Mathieu; Doizi, Denis; Lamouroux, Christine

2014-01-01

This Letter describes the fast synthesis of a mono-aminated calix[6]arene. The immobilization of this macrocycle onto glassy carbon electrodes via diazonium salt chemistry and the electrochemical characterization of the grafted organic layer are also reported. (authors)

Nonreciprocal optical tunnelling through evanescently coupled Tamm states in magnetophotonic crystals

Energy Technology Data Exchange (ETDEWEB)

Fang, Yun-Tuan [Jiangsu Univ., Zhenjiang (China). School of Computer Science and Telecommunication Engineering; Han, Ling [The Second Military Medical Univ., Shanghai (China). Dept. of Radiation Medicine; Gao, Yong-Feng [Jiangsu Univ., Zhenjiang (China). School of Mechanical Engineering

2015-07-01

Evanescently coupled Tamm states are achieved through two magnetophotonic crystals (MPCs) with a pair of coupling prisms. At the wavelengths of coupled Tamm states, a double of nonreciprocal optical tunnelling channels is found through the transmission spectra obtained from a developed transfer matrix method. The nonreciprocal tunnelling wavelength and the interval between two nonreciprocal channels can be adjusted depending on the width of the air gap between two MPCs or the scale invariant of a PC. The nonreciprocal tunnelling is demonstrated through electromagnetic field distribution simulations based on finite element software. Such theoretical results may provide a new method to design tunable optical isolators with a double of channels.

Positronics of radiation-induced effects in chalcogenide glassy semiconductors

International Nuclear Information System (INIS)

Shpotyuk, O.; Kozyukhin, S. A.; Shpotyuk, M.; Ingram, A.; Szatanik, R.

2015-01-01

Using As 2 S 3 and AsS 2 glasses as an example, the principal possibility of using positron annihilation spectroscopy methods for studying the evolution of the free volume of hollow nanoobjects in chalcogenide glassy semiconductors exposed to radiation is shown. The results obtained by measurements of the positron annihilation lifetime and Doppler broadening of the annihilation line in reverse chronological order are in full agreement with the optical spectroscopy data in the region of the fundamental absorption edge, being adequately described within coordination defect-formation and physical-aging models

Positronics of radiation-induced effects in chalcogenide glassy semiconductors

Energy Technology Data Exchange (ETDEWEB)

Shpotyuk, O. [Scientific Research Company “Carat” (Ukraine); Kozyukhin, S. A., E-mail: sergkoz@igic.ras.ru [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation); Shpotyuk, M. [Scientific Research Company “Carat” (Ukraine); Ingram, A. [Opole Technical University (Poland); Szatanik, R. [Opole University (Poland)

2015-03-15

Using As{sub 2}S{sub 3} and AsS{sub 2} glasses as an example, the principal possibility of using positron annihilation spectroscopy methods for studying the evolution of the free volume of hollow nanoobjects in chalcogenide glassy semiconductors exposed to radiation is shown. The results obtained by measurements of the positron annihilation lifetime and Doppler broadening of the annihilation line in reverse chronological order are in full agreement with the optical spectroscopy data in the region of the fundamental absorption edge, being adequately described within coordination defect-formation and physical-aging models.

Unifying the crystallization behavior of hexagonal and square crystals with the phase-field-crystal model

International Nuclear Information System (INIS)

Yang Tao; Chen Zheng; Zhang Jing; Wang Yongxin; Lu Yanli

2016-01-01

By employing the phase-field-crystal models, the atomic crystallization process of hexagonal and square crystals is investigated with the emphasis on the growth mechanism and morphological change. A unified regime describing the crystallization behavior of both crystals is obtained with the thermodynamic driving force varying. By increasing the driving force, both crystals (in the steady-state) transform from a faceted polygon to an apex-bulged polygon, and then into a symmetric dendrite. For the faceted polygon, the interface advances by a layer-by-layer (LL) mode while for the apex-bulged polygonal and the dendritic crystals, it first adopts the LL mode and then transits into the multi-layer (ML) mode in the later stage. In particular, a shift of the nucleation sites from the face center to the area around the crystal tips is detected in the early growth stage of both crystals and is rationalized in terms of the relation between the crystal size and the driving force distribution. Finally, a parameter characterizing the complex shape change of square crystal is introduced. (paper)

Code Optimization, Frozen Glassy Phase and Improved Decoding Algorithms for Low-Density Parity-Check Codes

International Nuclear Information System (INIS)

Huang Hai-Ping

2015-01-01

The statistical physics properties of low-density parity-check codes for the binary symmetric channel are investigated as a spin glass problem with multi-spin interactions and quenched random fields by the cavity method. By evaluating the entropy function at the Nishimori temperature, we find that irregular constructions with heterogeneous degree distribution of check (bit) nodes have higher decoding thresholds compared to regular counterparts with homogeneous degree distribution. We also show that the instability of the mean-field calculation takes place only after the entropy crisis, suggesting the presence of a frozen glassy phase at low temperatures. When no prior knowledge of channel noise is assumed (searching for the ground state), we find that a reinforced strategy on normal belief propagation will boost the decoding threshold to a higher value than the normal belief propagation. This value is close to the dynamical transition where all local search heuristics fail to identify the true message (codeword or the ferromagnetic state). After the dynamical transition, the number of metastable states with larger energy density (than the ferromagnetic state) becomes exponentially numerous. When the noise level of the transmission channel approaches the static transition point, there starts to exist exponentially numerous codewords sharing the identical ferromagnetic energy. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Li ion transport in sputter deposited LiCoO{sub 2} thin films and glassy borate membranes

Energy Technology Data Exchange (ETDEWEB)

Stockhoff, Tobias; Gallasch, Tobias; Schmitz, Guido [Westfaelische Wilhelms-Universitaet Muenster, Institut fuer Materialphysik, Muenster (Germany)

2010-07-01

LiCoO{sub 2} membranes are key components of current battery technology. We investigate sputter-deposited thin films of these materials aiming at the application in all-solid-state thin film batteries. For this, LiCoO{sub 2} films (10-200 nm) were deposited onto ITO-coated glass substrates by ion beam sputtering. In addition, a part of these films are coated by an ion-conductive membrane of Li{sub 2}O-B{sub 2}O{sub 3} glasses in the thickness range of 50 to 300 nm. Structural, chemical and electrical properties of the layers are studied by means of TEM(EELS) and various electrical methods (cyclic voltammetry, chrono-amperometry/-potentiometry). Since the color of the LiCoO{sub 2} films changes from red-brown to grey during de-intercalation of Li and the substrate as well as the glassy membrane deposited on top are optical transparent, reversible Li de- and intercalation can be directly demonstrated and quantified by a measurement of light transmission through the layered system. Samples coated with an ion-conductive membrane reveal a characteristic delay in switching optical transparency which is due to the slower transport across the membrane. Varying the thickness of the glassy membrane, the d.c. ion-conductivity and permeation through the membrane is determined quantitatively. Using thin membranes in the range of a few tens of nanometers the critical current densities are way sufficient for battery applications.

Probing Properties of Glassy Water and Other Liquids with Site Selective Spectroscopies

Energy Technology Data Exchange (ETDEWEB)

Dang, Nhan Chuong [Iowa State Univ., Ames, IA (United States)

2005-01-01

The standard non-photochemical hole burning (NPHB) mechanism, which involves phonon-assisted tunneling in the electronically excited state, was originally proposed to explain the light-induced frequency change of chemically stable molecules in glassy solids at liquid helium temperatures by this research group more than two decades ago. The NPHB mechanism was then further elucidated and the concept of intrinsic to glass configurational relaxation processes as pre-mediating step to the hole burning process was introduced. The latter provided the theoretical basis for NPHB to evolve into a powerful tool probing the dynamics and nature of amorphous media, which aside from ''simple'' inorganic glasses may include also ''complex'' biological systems such as living cells and cancerous/normal tissues. Presented in this dissertation are the experimental and theoretical results of hole burning properties of aluminum phthalocyanine tetrasulphonate (APT) in several different matrices: (1) hyperquenched glassy water (HGW); (2) cubic ice (I_c); and (3) water confined into poly(2-hydroxyethylmethacrylate) (poly-HEMA). In addition, results of photochemical hole burning (PHB) studies obtained for phthalocyanine tetrasulphonate (P_cT) in HGW and free base phthalocyanine (P_c) in ortho-dichlorobenzene (DCB) glass are reported. The goal of this dissertation was to provide further evidence supporting the NPHB mechanism and to provide more insight that leads to a better understanding of the kinetic events (dynamics) in glasses, and various dynamical processes of different fluorescent chromorphores in various amorphous solids and the liquid that exist above the glass transition temperature (T_g). The following issues are addressed in detail: (1) time evolution of hole being burned under different conditions and in different hole burning systems; (2) temperature dependent hole profile; and (3) the structure

Mode coupling theory for nonequilibrium glassy dynamics of thermal self-propelled particles.

Science.gov (United States)

Feng, Mengkai; Hou, Zhonghuai

2017-06-28

We present a mode coupling theory study for the relaxation and glassy dynamics of a system of strongly interacting self-propelled particles, wherein the self-propulsion force is described by Ornstein-Uhlenbeck colored noise and thermal noises are included. Our starting point is an effective Smoluchowski equation governing the distribution function of particle positions, from which we derive a memory function equation for the time dependence of density fluctuations in nonequilibrium steady states. With the basic assumption of the absence of macroscopic currents and standard mode coupling approximation, we can obtain expressions for the irreducible memory function and other relevant dynamic terms, wherein the nonequilibrium character of the active system is manifested through an averaged diffusion coefficient D[combining macron] and a nontrivial structural function S 2 (q) with q being the magnitude of wave vector q. D[combining macron] and S 2 (q) enter the frequency term and the vertex term for the memory function, and thus influence both the short time and the long time dynamics of the system. With these equations obtained, we study the glassy dynamics of this thermal self-propelled particle system by investigating the Debye-Waller factor f q and relaxation time τ α as functions of the persistence time τ p of self-propulsion, the single particle effective temperature T eff as well as the number density ρ. Consequently, we find the critical density ρ c for given τ p shifts to larger values with increasing magnitude of propulsion force or effective temperature, in good accordance with previously reported simulation work. In addition, the theory facilitates us to study the critical effective temperature T for fixed ρ as well as its dependence on τ p . We find that T increases with τ p and in the limit τ p → 0, it approaches the value for a simple passive Brownian system as expected. Our theory also well recovers the results for passive systems and can be

Evidence of icosahedral short-range order in Zr70Cu30 and Zr70Cu29Pd1 metallic glasses

DEFF Research Database (Denmark)

Saksl, K.; Franz, H.; Jovari, P.

2003-01-01

Change in local atomic environment during crystallization of Zr-based glassy alloys was studied by extended x-ray absorption fine structure (EXAFS) spectroscopy. The formation of icosahedral quasicrystalline phase followed by crystallization of tetragonal CuZr2 has been observed in the Zr70Cu29Pd1...... glassy alloy during annealing up to 850 K. On the other hand, the binary Zr70Cu30 alloy shows a single glassy to crystalline CuZr2 phase transformation. The local atomic environment of as-quenched Zr70Cu30 alloy is matched to an icosahedral local atomic configuration, which is similar to that of the as......-quenched Zr70Cu29Pd1 alloy and the alloy annealed at 593 K containing icosahedral phase. Considering that the supercooled liquid region appears prior to crystallization in the Zr70Cu30 glassy alloy, the observed results support the theory claiming a strong correlation between the existence of local...

Heating-induced glass-glass and glass-liquid transformations in computer simulations of water

Science.gov (United States)

Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

2014-03-01

Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T "phase diagram" for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related

Heating-induced glass-glass and glass-liquid transformations in computer simulations of water

International Nuclear Information System (INIS)

Chiu, Janet; Giovambattista, Nicolas; Starr, Francis W.

2014-01-01

Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T “phase diagram” for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related

Heating-induced glass-glass and glass-liquid transformations in computer simulations of water

Energy Technology Data Exchange (ETDEWEB)

Chiu, Janet; Giovambattista, Nicolas [Department of Physics, Brooklyn College of the City University of New York, Brooklyn, New York 11210 (United States); Starr, Francis W. [Department of Physics, Wesleyan University, Middletown, Connecticut 06459 (United States)

2014-03-21

Water exists in at least two families of glassy states, broadly categorized as the low-density (LDA) and high-density amorphous ice (HDA). Remarkably, LDA and HDA can be reversibly interconverted via appropriate thermodynamic paths, such as isothermal compression and isobaric heating, exhibiting first-order-like phase transitions. We perform out-of-equilibrium molecular dynamics simulations of glassy water using the ST2 model to study the evolution of LDA and HDA upon isobaric heating. Depending on pressure, glass-to-glass, glass-to-crystal, glass-to-vapor, as well as glass-to-liquid transformations are found. Specifically, heating LDA results in the following transformations, with increasing heating pressures: (i) LDA-to-vapor (sublimation), (ii) LDA-to-liquid (glass transition), (iii) LDA-to-HDA-to-liquid, (iv) LDA-to-HDA-to-liquid-to-crystal, and (v) LDA-to-HDA-to-crystal. Similarly, heating HDA results in the following transformations, with decreasing heating pressures: (a) HDA-to-crystal, (b) HDA-to-liquid-to-crystal, (c) HDA-to-liquid (glass transition), (d) HDA-to-LDA-to-liquid, and (e) HDA-to-LDA-to-vapor. A more complex sequence may be possible using lower heating rates. For each of these transformations, we determine the corresponding transformation temperature as function of pressure, and provide a P-T “phase diagram” for glassy water based on isobaric heating. Our results for isobaric heating dovetail with the LDA-HDA transformations reported for ST2 glassy water based on isothermal compression/decompression processes [Chiu et al., J. Chem. Phys. 139, 184504 (2013)]. The resulting phase diagram is consistent with the liquid-liquid phase transition hypothesis. At the same time, the glass phase diagram is sensitive to sample preparation, such as heating or compression rates. Interestingly, at least for the rates explored, our results suggest that the LDA-to-liquid (HDA-to-liquid) and LDA-to-HDA (HDA-to-LDA) transformation lines on heating are related

Egg maturation by the glassy-winged sharpshooter (Hemiptera: Cicadellidae); a vector of Xylella fastidiosa

Science.gov (United States)

Rates of spread of insect-transmitted plant pathogens are a function of vector abundance. Despite this, factors affecting population growth rates of insects that transmit plant pathogens have received limited attention. The glassy-winged sharpshooter (Homalodisca vitripennis) feeds on xylem-sap and ...

Determining the critical relative humidity at which the glassy to rubbery transition occurs in polydextrose using an automatic water vapor sorption instrument.

Science.gov (United States)

Yuan, Xiaoda; Carter, Brady P; Schmidt, Shelly J

2011-01-01

Similar to an increase in temperature at constant moisture content, water vapor sorption by an amorphous glassy material at constant temperature causes the material to transition into the rubbery state. However, comparatively little research has investigated the measurement of the critical relative humidity (RHc) at which the glass transition occurs at constant temperature. Thus, the central objective of this study was to investigate the relationship between the glass transition temperature (Tg), determined using thermal methods, and the RHc obtained using an automatic water vapor sorption instrument. Dynamic dewpoint isotherms were obtained for amorphous polydextrose from 15 to 40 °C. RHc was determined using an optimized 2nd-derivative method; however, 2 simpler RHc determination methods were also tested as a secondary objective. No statistical difference was found between the 3 RHc methods. Differential scanning calorimetry (DSC) Tg values were determined using polydextrose equilibrated from 11.3% to 57.6% RH. Both standard DSC and modulated DSC (MDSC) methods were employed, since some of the polydextrose thermograms exhibited a physical aging peak. Thus, a tertiary objective was to compare Tg values obtained using 3 different methods (DSC first scan, DSC rescan, and MDSC), to determine which method(s) yielded the most accurate Tg values. In general, onset and midpoint DSC first scan and MDSC Tg values were similar, whereas onset and midpoint DSC rescan values were different. State diagrams of RHc and experimental temperature and Tg and %RH were compared. These state diagrams, though obtained via very different methods, showed relatively good agreement, confirming our hypothesis that water vapor sorption isotherms can be used to directly detect the glassy to rubbery transition. Practical Application: The food polymer science (FPS) approach, pioneered by Slade and Levine, is being successfully applied in the food industry for understanding, improving, and

Geochemical studies of abyssal lavas recovered by DSRV Alvin from Eastern Galapagos Rift, Inca Transform, and Ecuador Rift: 2. Phase chemistry and crystallization history

Science.gov (United States)

Perfit, Michael R.; Fornari, Daniel J.

1983-12-01

A diverse suite of lavas recovered by DSRV Alvin from the eastern Galapagos rift and Inca transform includes mid-ocean ridge tholeiitic basalts (MORB), iron- and titanium-enriched basalts (FeTi basalts), and abyssal andesites. Rock types transitional in character (ferrobasalts and basaltic andesites) were also recovered. The most mafic glassy basalts contain plagioclase, augite, and olivine as near-liquidus phases, whereas in more fractionated basalts, pigeonite replaces olivine and iron-titanium oxides crystallize. Plagioclase crystallizes after pyroxenes and iron-titanium oxides in andesites, possibly due to increased water contents or cooling rates. Apatite phenocrysts are present in some andesitic glasses. Ovoid sulfide globules are also common in many lavas. Compositional variations of phenocrysts in glassy lavas reflect changes in magma chemistry, temperature of crystallization, and cooling rate. The overall chemical variations parallel the chemical evolution of the lava suite and are similar to those in other fractionated tholeiitic complexes. Elemental partitioning between plagioclase-, pyroxene-, and olivine-glass pairs suggests that equilibration occurred at low pressure in a rather restricted temperature range. Various geothermometers indicate that the most primitive MORB began to crystallize between 1150° and 1200°C with fo2 PH 2 o could have been as high as 1 kbar during andesite crystallization. Compositions of the lavas from the Galapagos rift follow the experimentally determined (1 atm-QFM) liquid line of descent. Least squares calculations for the major elements indicate that the entire suite of lavas can be produced by fractional crystallization of successive residual liquids from a MORB parent magma. FeTi basalts represent 30-65 cumulative weight percent crystallization of plagioclase, augite, and olivine. An additional 30-50% fractionation of pyroxenes, plagioclase, titanomagnetite, and possible apatite is required to generate andesite from Fe

Coherent diffractive imaging of solid state reactions in zinc oxide crystals

Science.gov (United States)

Leake, Steven J.; Harder, Ross; Robinson, Ian K.

2011-11-01

We investigated the doping of zinc oxide (ZnO) microcrystals with iron and nickel via in situ coherent x-ray diffractive imaging (CXDI) in vacuum. Evaporated thin metal films were deposited onto the ZnO microcrystals. A single crystal was selected and tracked through annealing cycles. A solid state reaction was observed in both iron and nickel experiments using CXDI. A combination of the shrink wrap and guided hybrid-input-output phasing methods were applied to retrieve the electron density. The resolution was 33 nm (half order) determined via the phase retrieval transfer function. The resulting images are nevertheless sensitive to sub-angstrom displacements. The exterior of the microcrystal was found to degrade dramatically. The annealing of ZnO microcrystals coated with metal thin films proved an unsuitable doping method. In addition the observed defect structure of one crystal was attributed to the presence of an array of defects and was found to change upon annealing.

Modified positron annihilation model for glassy-like As2Se3

International Nuclear Information System (INIS)

Kozdras, A.; Shpotyuk, O.; Kovalskiy, A.; Filipecki, J.

2005-01-01

An approach to structural characterization of chalcogenide glasses based on the study of void distribution is discussed. The results of positron annihilation lifetime spectra measurements for glassy As 2 Se 3 are compared with nano-void distribution data obtained from Monte Carlo simulation. In this consideration perspectives to involve the parameters of nano-voids calculated from the first sharp diffraction peak in the frame work of known Elliott's model are analyzed. (author)

Crystal structure, magnetism, {sup 89}Y solid state NMR, and {sup 121}Sb Moessbauer spectroscopic investigations of YIrSb

Energy Technology Data Exchange (ETDEWEB)

Benndorf, Christopher [Institut fuer Physikalische Chemie, Universitaet Muenster (Germany); Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Heletta, Lukas; Block, Theresa; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Eckert, Hellmut [Institut fuer Physikalische Chemie, Universitaet Muenster (Germany); Institute of Physics in Sao Carlos, University of Sao Paulo, Sao Carlos (Brazil)

2017-02-15

The ternary antimonide YIrSb was synthesized from the binary precursor YIr and elemental antimony by a diffusion controlled solid-state reaction. Single crystals were obtained by a flux technique with elemental bismuth as an inert solvent. The YIrSb structure (TiNiSi type, space group Pnma) was refined from single-crystal X-ray diffractometer data: a = 711.06(9), b = 447.74(5), c = 784.20(8) pm, wR{sub 2} = 0.0455, 535 F{sup 2} values, 20 variables. {sup 89}Y solid state MAS NMR and {sup 121}Sb Moessbauer spectra show single resonance lines in agreement with single-crystal X-ray data. YIrSb is a Pauli paramagnet. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

The electrocatalytical reduction of m-nitrophenol on palladium nanoparticles modified glassy carbon electrodes

International Nuclear Information System (INIS)

Shi Qiaofang; Diao Guowang

2011-01-01

Highlights: ► The deposition of palladium on a GC electrode was performed by cyclic voltammetry. ► SEM images showed palladium nanoparticles deposited on a glassy carbon (GC) electrode. ► The Pd/GC electrode can effectively catalyze m-nitrophenol in aqueous media. ► The reduction of m-nitrophenol on the Pd/GC electrode depended on potential and pH. ► XPS spectra of the Pd/GC electrodes demonstrated the presence of palladium. - Abstract: Palladium nanoparticles modified glassy carbon electrodes (Pd/GC) were prepared via the electrodeposition of palladium on a glassy carbon (GC) electrode using cyclic voltammetry in different sweeping potential ranges. The scanning electron microscope images of palladium particles on the GC electrodes indicate that palladium particles with diameters of 20–50 nm were homogeneously dispersed on the GC electrode at the optimal deposition conditions, which can effectively catalyze the reduction of m-nitrophenol in aqueous solutions, but their catalytic activities are strongly related to the deposition conditions of Pd. The X-ray photoelectron spectroscopy spectra of the Pd/GC electrode confirmed that 37.1% Pd was contained in the surface composition of the Pd/GC electrode. The cyclic voltammograms of the Pd/GC electrode in the solution of m-nitrophenol show that the reduction peak of m-nitrophenol shifts towards the more positive potentials, accompanied with an increase in the peak current compared to the bare GC electrode. The electrocatalytic activity of the Pd/GC electrode is affected by pH values of the solution. In addition, the electrolysis of m-nitrophenol under a constant potential indicates that the reduction current of m-nitrophenol on the Pd/GC electrode is approximately 20 times larger than that on the bare GC electrode.

Field-induced optically isotropic state in bent core nematic liquid crystals: unambiguous proof of field-induced optical biaxiality

International Nuclear Information System (INIS)

Elamain, Omaima; Komitov, Lachezar; Hegde, Gurumurthy; Fodor-Csorba, Katalin

2013-01-01

The behaviour of bent core (BC) nematic liquid crystals was investigated under dc applied electric field. The optically isotropic state of a sample containing BC nematic was observed under application of low dc electric fields. The quality of the dark state when the sample was inserted between two crossed polarizers was found to be superb and it did not change when rotating the sample between the polarizers. The coupling between the net molecular dipole moment and the applied dc electric field was considered as the origin of the out-of-plane switching of the BC molecules resulting in switching from the field-off bright state to the field-on dark state. The field-induced optically isotropic state is an unambiguous proof of the field-induced biaxiality in the BC nematic liquid crystal. A simple model explaining the appearance of the isotropic optical state in BC nematics and the switching of the sample slow axis between three mutually orthogonal directions under dc applied electric field is proposed. (paper)

Effect of Sn additive on the structure and crystallization kinetics in Ge–Se alloy

Energy Technology Data Exchange (ETDEWEB)

Abd-Elrahman, M.I., E-mail: mostafaia11@yahoo.com; Hafiz, M.M.; Abdelraheem, A.M.; Abu-Sehly, A.A.

2016-08-05

The structure of Ge{sub 20}Se{sub 80−x}Snx glassy alloys and crystallization phases are identified using the X-ray diffraction (XRD) and Scanning Electron Microscope (SEM). The glass transition kinetics and the crystallization mechanism of the system are studied using Differential Scanning Calorimeter (DSC) under non-isothermal condition. The results reveal that glass transition temperature (Tg) increases with increasing Sn content which is attributed to the increase in the coordination number. The increase of the glass transition activation energy (Eg) with increasing Sn content is attributed to the decrease in the internal energy of the system as Sn increases. The compositional dependence of both glass forming ability and thermal stability are studied. From the experimental data, the thermal stability parameter (S) is found to be maximum for Ge{sub 20}Se{sub 78}Sn{sub 2} alloy, which indicates that this alloy is thermally more stable in the composition range under investigation. The effect of composition on the crystallization mechanism is discussed using different kinetic models. The crystallization activation energy (Ec) decreases with increasing Sn. This is attributed to the addition of Sn increases the tendency of crystallization. The calculated values of Avrami exponent (n) indicates the crystallization process occurs in one-and two dimensions for Sn is less than or equals 12 at%, respectively. - Highlights: • Glass and crystallization transitions in Ge{sub 20}Se{sub 80−x}Sn{sub x} candidate for devices. • The addition of Sn increases the tendency of Ge-Se alloy to crystallization. • The glass forming ability and thermal stability increase as Sn decreases. • The dimension of the crystals growth is one or two depending on the Sn content.

Crystal Growth Technology

Science.gov (United States)

Scheel, Hans J.; Fukuda, Tsuguo

2004-06-01

This volume deals with the technologies of crystal fabrication, of crystal machining, and of epilayer production and is the first book on industrial and scientific aspects of crystal and layer production. The major industrial crystals are treated: Si, GaAs, GaP, InP, CdTe, sapphire, oxide and halide scintillator crystals, crystals for optical, piezoelectric and microwave applications and more. Contains 29 contributions from leading crystal technologists covering the following topics: General aspects of crystal growth technology Silicon Compound semiconductors Oxides and halides Crystal machining Epitaxy and layer deposition Scientific and technological problems of production and machining of industrial crystals are discussed by top experts, most of them from the major growth industries and crystal growth centers. In addition, it will be useful for the users of crystals, for teachers and graduate students in materials sciences, in electronic and other functional materials, chemical and metallurgical engineering, micro-and optoelectronics including nanotechnology, mechanical engineering and precision-machining, microtechnology, and in solid-state sciences.

A nanoscale characterisation of extended defects in glassy-like As2Se3 semiconductors with PAL technique

International Nuclear Information System (INIS)

Shpotyuk, O.; Kovalskiy, A.; Filipecki, J.; Hyla, M.; Kozdras, A.

2003-01-01

A meaningful interpretation of positron lifetime characteristics for glassy-like g-As 2 Se 3 is developed taking into account calculations of Jensen et al. (J. Non-Cryst. Solids 170 (1994) 57) for positrons trapped by free-volume extended defects in orthorhombic As 2 Se 3 and void volume distribution for 146-atoms layer-biased model of amorphous As 2 Se 3 presented by Popescu (J. Non-Cryst. Solids 35-36 (1980) 549). The obtained results are compared for samples having different thermal pre-history. Two groups of experimental results with close lifetime characteristics are distinguished for each of the investigated samples. This feature is explained in terms of average positron lifetime by applying two-state positron trapping model for mathematical treatment of the obtained spectra

Formation and Applications of Bulk Glassy Alloys in Late Transition Metal Base System

International Nuclear Information System (INIS)

Inoue, Akihisa; Shen Baolong

2006-01-01

This paper reviews our recent results of the formation, fundamental properties, workability and applications of late transition metal (LTM) base bulk glassy alloys (BGAs) developed since 1995. The BGAs were obtained in Fe-(Al,Ga)-(P,C,B,Si), Fe-(Cr,Mo)-(C,B), Fe-(Zr,Hf,Nb,Ta)-B, Fe-Ln-B(Ln=lanthanide metal), Fe-B-Si-Nb and Fe-Nd-Al for Fe-based alloys, Co-(Ta,Mo)-B and Co-B-Si-Nb for Co-based alloys, Ni-Nb-(Ti,Zr)-(Co,Ni) for Ni-based alloys, and Cu-Ti-(Zr,Hf), Cu-Al-(Zr,Hf), Cu-Ti-(Zr,Hf)-(Ni,Co) and Cu-Al-(Zr,Hf)-(Ag,Pd) for Cu-based alloys. These BGAs exhibit useful properties of high mechanical strength, large elastic elongation and high corrosion resistance. In addition, Fe- and Co-based glassy alloys have good soft magnetic properties which cannot be obtained for amorphous and crystalline type magnetic alloys. The Fe- and Ni-based BGAs have already been used in some application fields. These LTM base BGAs are promising as new metallic engineering materials

Studies of the Action of Grain-Refining Particles in Aluminium Alloys

Science.gov (United States)

Schumacher, P.; Greer, A. L.

Crystallization from a melt and from a metallic glass both occur in an undercooled liquid. In this way identical nucleation mechanisms can operate in the two cases. However, in metallic glasses, unlike conventional solidification at low undercooling, the low atomic mobility permits the resolution and microscopical study of nucleation processes on added particles. Conventional aluminium grain-refiner based on Al-Ti-B has been used to obtain nucleant particles embedded in a glassy matrix of Al85Y8Ni5Co2 (at%). During crystallization from the glassy state, nucleation and growth of α-Al can be observed on TiB2 particles coated with a layer of Al3Ti Empirical relations found in casting practice of Al-alloys, such as excess Ti necessary for grain refinement, can be related to the observed nucleation mechanism, which is found to be very sensitive to both crystallographic and chemical factors.

Playback of natural vibrational signals in vineyard trellis for mating disruption of glassy-winged sharpshooter

Science.gov (United States)

The glassy-winged sharpshooter, Homalodisca vitripennis (Germar) (Hemiptera: Cicadellidae), is a vector of Xylella fastidiosa, an important bacterial pathogen of several crops in the Americas and Europe. Mating communication of this and many other cicadellid pests involves the exchange of substrate-...

Redox-active porous coordination polymer based on trinuclear pivalate: Temperature-dependent crystal rearrangement and redox-behavior

Energy Technology Data Exchange (ETDEWEB)

Lytvynenko, Anton S. [L.V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Prospekt Nauki 31, Kiev 03028 (Ukraine); Kiskin, Mikhail A., E-mail: mkiskin@igic.ras.ru [N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prospect 31, GSP-1, 119991 Moscow (Russian Federation); Dorofeeva, Victoria N.; Mishura, Andrey M.; Titov, Vladimir E.; Kolotilov, Sergey V. [L.V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Prospekt Nauki 31, Kiev 03028 (Ukraine); Eremenko, Igor L.; Novotortsev, Vladimir M. [N.S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky Prospect 31, GSP-1, 119991 Moscow (Russian Federation)

2015-03-15

Linking of trinuclear pivalate Fe{sub 2}NiO(Piv){sub 6} (Piv=O{sub 2}CC(CH{sub 3}){sub 3}) by 2,6-bis(4-pyridyl)-4-(1-naphthyl)pyridine (L) resulted in formation of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)·Solv, which was characterized in two forms: DMSO solvate Fe{sub 2}NiO(Piv){sub 6}(L)(DMSO)·2.5DMSO (1) or water solvate Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) (2). X-ray structure of 1 was determined. Crystal lattice of 1 at 160 K contained open channels, filled by captured solvent, while temperature growth to 296 K led to the crystal lattice rearrangement and formation of closed voids. Redox-behavior of 2 was studied by cyclic voltammetry for a solid compound, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. The presence of pores in desolvated sample Fe{sub 2}NiO(Piv){sub 6}(L) was confirmed by the measurements of N{sub 2} and H{sub 2} adsorption at 77 K. Potential barriers of the different molecules diffusion through pores were estimated by the means of molecular mechanics. - Graphical abstract: Redox-behavior of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) was studied by cyclic voltammetry in thin film, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. Potential barriers of different molecules diffusion through pores were estimated by the means of molecular mechanics. - Highlights: • Porous 1D coordination polymer was synthesized. • Temperature growth led to pores closing due to crystal lattice rearrangement. • Redox-activity of ligand preserved upon incorporation into coordination polymer. • Redox-properties of solid coordination polymer were studied in thin film. • Diffusion barriers were evaluated by molecular mechanics.

Crystal structure and spin state of mixed-crystals of Fe(NCS)x(NCBH3)2-x(bpp)2 (bpp = 1,3-BIS(4-pyridyl)propane)

International Nuclear Information System (INIS)

Dote, Haruka; Yasuhara, Hiroki; Nakashima, Satoru

2013-01-01

New mixed crystals, Fe(NCS) x (NCBH 3 ) (2-x) (bpp) 2 were synthesized. 57 Fe Mössbauer spectroscopy showed that the ratio of low-spin state in the Fe(NCBH 3 ) 2 unit changed with the change of x. The results revealed that the high spin site of Fe(NCS) 2 unit affects the spin state of Fe(NCBH 3 ) 2 unit. (author)

Structural and mechanical properties of glassy water in nanoscale confinement.

Science.gov (United States)

Lombardo, Thomas G; Giovambattista, Nicolás; Debenedetti, Pablo G

2009-01-01

We investigate the structure and mechanical properties of glassy water confined between silica-based surfaces with continuously tunable hydrophobicity and hydrophilicity by computing and analyzing minimum energy, mechanically stable configurations (inherent structures). The structured silica substrate imposes long-range order on the first layer of water molecules under hydrophobic confinement at high density (p > or = 1.0 g cm(-3)). This proximal layer is also structured in hydrophilic confinement at very low density (p approximately 0.4 g cm(-3)). The ordering of water next to the hydrophobic surface greatly enhances the mechanical strength of thin films (0.8 nm). This leads to a substantial stress anisotropy; the transverse strength of the film exceeds the normal strength by 500 MPa. The large transverse strength results in a minimum in the equation of state of the energy landscape that does not correspond to a mechanical instability, but represents disruption of the ordered layer of water next to the wall. In addition, we find that the mode of mechanical failure is dependent on the type of confinement. Under large lateral strain, water confined by hydrophilic surfaces preferentially forms voids in the middle of the film and fails cohesively. In contrast, water under hydrophobic confinement tends to form voids near the walls and fails by loss of adhesion.

EPR studies of excited state exchange and crystal-field effects in rare earth compounds

International Nuclear Information System (INIS)

Huang, C.Y.; Sugawara, K.; Cooper, B.R.

1976-01-01

EPR in excited crystal-field states of Tm 3+ , Pr 3+ , and Tb 3+ in singlet-ground-state systems and in the excited state of Ce 3+ in CeP are reviewed. Because one is looking at a crystal-field excited state resonance, the exchange, even if isotropic, does not act as a secular perturbation. This means that one obtains different effects and has access to more information about the dynamic effects of exchange than in conventional paramagnetic resonance experiments. The Tm and Pr monopnictides studied are paramagnetic at all temperatures. The most striking feature of the behavior of the GAMMA 5 /sup (2)/ EPR in the Tm compounds is the presence of an anomalous maximum in the temperature dependence of the g-factor. The relationship of this effect to anisotropic exchange is discussed. The results of the EPR of the excited GAMMA 5 /sup (2)/ level of Tb 3 + (g-factor becomes very large at T/sub N/ in antiferromagnetic TbX (X = P, As, Sb) and that of the excited GAMMA 8 level of Ce 3+ in antiferromagnetic CeP will also be reported. For sufficient dilution of the Tb 3+ in the terbium monopnictides, the systems become paramagnetic (Van Vleck paramagnets) down to 0 0 K. The Tb 3+ excited state resonance EPR in Tb/sub 0.1/ La/sub 0.9/P was studied as an example of behavior in such systems. 10 fig

Effects of thermo-order-mechanical coupling on band structures in liquid crystal nematic elastomer porous phononic crystals.

Science.gov (United States)

Yang, Shuai; Liu, Ying

2018-08-01

Liquid crystal nematic elastomers are one kind of smart anisotropic and viscoelastic solids simultaneously combing the properties of rubber and liquid crystals, which is thermal sensitivity. In this paper, the wave dispersion in a liquid crystal nematic elastomer porous phononic crystal subjected to an external thermal stimulus is theoretically investigated. Firstly, an energy function is proposed to determine thermo-induced deformation in NE periodic structures. Based on this function, thermo-induced band variation in liquid crystal nematic elastomer porous phononic crystals is investigated in detail. The results show that when liquid crystal elastomer changes from nematic state to isotropic state due to the variation of the temperature, the absolute band gaps at different bands are opened or closed. There exists a threshold temperature above which the absolute band gaps are opened or closed. Larger porosity benefits the opening of the absolute band gaps. The deviation of director from the structural symmetry axis is advantageous for the absolute band gap opening in nematic state whist constrains the absolute band gap opening in isotropic state. The combination effect of temperature and director orientation provides an added degree of freedom in the intelligent tuning of the absolute band gaps in phononic crystals. Copyright © 2018 Elsevier B.V. All rights reserved.

Investigations and Simulations of All optical Switches in linear state Based on Photonic Crystal Directional Coupler

Directory of Open Access Journals (Sweden)

S. Maktoobi

2014-10-01

Full Text Available Switching is a principle process in digital computers and signal processing systems. The growth of optical signal processing systems, draws particular attention to design of ultra-fast optical switches. In this paper, All Optical Switches in linear state Based On photonic crystal Directional coupler is analyzed and simulated. Among different methods, the finite difference time domain method (FDTD is a preferable method and is used. We have studied the application of photonic crystal lattices, the physics of optical switching and photonic crystal Directional coupler. In this paper, Electric field intensity and the power output that are two factors to improve the switching performance and the device efficiency are investigated and simulated. All simulations are performed by COMSOL software.

Detection and typing of Xylella fastidiosa from glassy-winged sharpshooter for Pierce’s disease epidemiology

Science.gov (United States)

Epidemiology of Pierce’s disease of grape, caused by the bacterial pathogen Xylella fastidiosa (Xf), is largely dependent on populations of insect vectors such as the invasive glassy-winged sharpshooter (GWSS) (Homalodisca vitripennis). In the grape-growing regions of the southern San Joaquin Valley...

Inelastic light scattering in crystals

Science.gov (United States)

Sushchinskii, M. M.

The papers presented in this volume are concerned with a variety of problems in optics and solid state physics, such as Raman scattering of light in crystals and disperse media, Rayleigh and inelastic scattering during phase transitions, characteristics of ferroelectrics in relation to the general soft mode concept, and inelastic spectral opalescence. A group-theory approach is used to classify the vibrational spectra of the crystal lattice and to analyze the properties of idealized crystal models. Particular attention is given to surface vibrational states and to the study of the surface layers of crystals and films by light scattering methods.

Quasi 2D electronic states with high spin-polarization in centrosymmetric MoS2 bulk crystals

Science.gov (United States)

Gehlmann, Mathias; Aguilera, Irene; Bihlmayer, Gustav; Młyńczak, Ewa; Eschbach, Markus; Döring, Sven; Gospodarič, Pika; Cramm, Stefan; Kardynał, Beata; Plucinski, Lukasz; Blügel, Stefan; Schneider, Claus M.

2016-06-01

Time reversal dictates that nonmagnetic, centrosymmetric crystals cannot be spin-polarized as a whole. However, it has been recently shown that the electronic structure in these crystals can in fact show regions of high spin-polarization, as long as it is probed locally in real and in reciprocal space. In this article we present the first observation of this type of compensated polarization in MoS2 bulk crystals. Using spin- and angle-resolved photoemission spectroscopy (ARPES), we directly observed a spin-polarization of more than 65% for distinct valleys in the electronic band structure. By additionally evaluating the probing depth of our method, we find that these valence band states at the point in the Brillouin zone are close to fully polarized for the individual atomic trilayers of MoS2, which is confirmed by our density functional theory calculations. Furthermore, we show that this spin-layer locking leads to the observation of highly spin-polarized bands in ARPES since these states are almost completely confined within two dimensions. Our findings prove that these highly desired properties of MoS2 can be accessed without thinning it down to the monolayer limit.

Advances in nonlinear polymers and inorganic crystals, liquid crystals, and laser media

International Nuclear Information System (INIS)

Musikant, S.

1987-01-01

These proceedings collect papers on laser materials. Topics include: solid state lasers, fracture mechanics in laser materials, optical second harmonic generation, nonlinear optics, molecular crystals, crystal-phase transformation, and materials for laser fusion reactors

Czochralski method of growing single crystals. State-of-art

International Nuclear Information System (INIS)

Bukowski, A.; Zabierowski, P.

1999-01-01

Modern Czochralski method of single crystal growing has been described. The example of Czochralski process is given. The advantages that caused the rapid progress of the method have been presented. The method limitations that motivated the further research and new solutions are also presented. As the example two different ways of the technique development has been described: silicon single crystals growth in the magnetic field; continuous liquid feed of silicon crystals growth. (author)

EIS study of the redox reaction of Fe(CN)63-/4- at glassy carbon electrode via diazonium reduction in aqueous and acetonitrile solutions

Energy Technology Data Exchange (ETDEWEB)

Khoshroo, M.; Rostami, A. [Mazandaran Univ., Babolsar (Iran, Islamic Republic of). Dept. of Physical Chemistry

2008-07-01

This paper reported on a study that characterized soluble electroactive species by cyclic voltammetry to investigate the presence of grafted films and their blocking properties. In particular, the authority of the glassy carbon electrode modification conditions on the cyclic voltammetric response of Fe(CN)63-/4- oxido-reduction was examined for 2 layers grafted by electrochemical reduction of diazonium salts in acetonitrile and aqueous solutions. PAA and Fast Black K modified glassy carbon electrodes exhibited a significant blocking behaviour for oxidation and reduction reactions of the Fe(CN)63-/4- redox system in aqueous and acetonitrile solutions. The study showed that the blocking effect increased which changes in time and concentration of diazonium salts in acetonitrile solution. Electrochemical impedance spectroscopy (EIS) measurements showed that the physical barrier of grafted layers prevent the access of Fe(CN)63-/4- to the underlying glassy carbon electrode. Therefore the RCT resistance increases during the modification treatment. The substituted phenyl layers are much more compact and less permeable in a nonaqueous solvent than with an aqueous solvent. Electrochemical impedance measurements indicate that the kinetics of electron transfer slow down when the time and the concentration used to modify the glassy carbon electrode increase. 4 refs., 1 fig.

Understanding the Composition Dependence of the Fragility of AgI-Ag2O-MxOy Glassy Systems

International Nuclear Information System (INIS)

Aniya, M

2011-01-01

It has been reported that the fragility in the AgI-Ag 2 O-M x O y (M = B, Ge, P, Mo) system is determined by Ag 2 O-M x O y and does not depend on the amount of AgI. This is an interesting result and provides a hint to understand the nature of the glassy state of these materials. However, the origin of such behavior has not been sufficiently discussed. In the present report a model for the above behavior is presented. According to the model, the behavior arises from the solid like nature of the network formed by Ag 2 O-M x O y and the liquid like AgI which flow between the networks. The model is consistent with the structural model of superionic glasses proposed previously.

Pressure sensor using liquid crystals

Science.gov (United States)

Parmar, Devendra S. (Inventor); Holmes, Harlan K. (Inventor)

1994-01-01

A pressure sensor includes a liquid crystal positioned between transparent, electrically conductive films (18 and 20), that are biased by a voltage (V) which induces an electric field (E) that causes the liquid crystal to assume a first state of orientation. Application of pressure (P) to a flexible, transparent film (24) causes the conductive film (20) to move closer to or farther from the conductive film (18), thereby causing a change in the electric field (E'(P)) which causes the liquid crystal to assume a second state of orientation. Polarized light (P.sub.1) is directed into the liquid crystal and transmitted or reflected to an analyzer (A or 30). Changes in the state of orientation of the liquid crystal induced by applied pressure (P) result in a different light intensity being detected at the analyzer (A or 30) as a function of the applied pressure (P). In particular embodiments, the liquid crystal is present as droplets (10) in a polymer matrix (12) or in cells (14) in a polymeric or dielectric grid (16) material in the form of a layer (13) between the electrically conductive films (18 and 20). The liquid crystal fills the open wells in the polymer matrix (12) or grid (16) only partially.

Statistics of energy levels and zero temperature dynamics for deterministic spin models with glassy behaviour

NARCIS (Netherlands)

Degli Esposti, M.; Giardinà, C.; Graffi, S.; Isola, S.

2001-01-01

We consider the zero-temperature dynamics for the infinite-range, non translation invariant one-dimensional spin model introduced by Marinari, Parisi and Ritort to generate glassy behaviour out of a deterministic interaction. It is argued that there can be a large number of metastable (i.e.,

Research and Development of Crystal Purification for Product of Uranium Crystallization Process

Energy Technology Data Exchange (ETDEWEB)

Yano, K. [Japan Atomic Energy Agency - JAEA (Japan)

2009-06-15

Uranium crystallization has been developed as a part of advanced aqueous reprocessing for FBR spent fuel. Although the purity of uranyl nitrate hexahydrate (UNH) crystal from the crystallization process is supposed to meet a specification of FBR blanket fuel, an improvement of its purity is able to reduce the cost of fuel fabrication and storage (in case interim storage of recovered uranium is required). In this work, UNH crystal purification was developed as additional process after crystallization. Contamination of the crystal is caused by mother solution and solid state impurities. They are inseparable by washing and filtration. Mother solution on the surface of UNH crystals is removable by washing, but it is difficult to remove that in an obstructed part of crystalline aggregate by washing. Major elements of solid state impurities are cesium and barium. Cesium precipitates with tetravalent plutonium as a double nitrate, Cs{sub 2}Pu(NO{sub 3}){sub 6}. Barium crystallizes as Ba(NO{sub 3}){sub 2} because of its low solubility in nitric acid solution. It is difficult to separate their particle from UNH crystal by solid-liquid separation such as simple filtration. As a kind of crystal purification, there are some methods using sweating. Sweating is a phenomenon that a crystal melts partly below its melting point and it is caused by depression of freezing point due to impurity. It is considerably applicable for removal of mother solution. Concerning the solid state impurities, which has higher melting point than that of UNH crystal, it is supposed that they are separable by melting UNH crystal and filtration. The behaviors of impurities and applicability of sweating and melting-filtration operations to the purification for UNH crystal were investigated experimentally on a beaker and an engineering scale. With regard to behaviors of impurities, the conditions of cesium and barium precipitation were surveyed and it was clarified that there were most impurities on the

Destruction-polymerization transformations as a source of radiation-induced extended defects in chalcogenide glassy semiconductors

International Nuclear Information System (INIS)

Shpotyuk, Oleh; Filipecki, Jacek; Shpotyuk, Mykhaylo

2013-01-01

Long-wave shift of the optical transmission spectrum in the region of fundamental optical absorption edge is registered for As 2 S 3 chalcogenide glassy semiconductors after γ-irradiation. This effect is explained in the frameworks of the destruction-polymerization transformations concept by accepting the switching of the heteropolar As-S covalent bonds into homopolar As-As ones. It is assumed that (As 4 + ; S 1 - ) defect pairs are created under such switching. Formula to calculate content of the induced defects in chalcogenide glassy semiconductors is proposed. It is assumed that defects concentration depends on energy of broken covalent bond, bond-switching energy balance, correlation energy, optical band-gap and energy of excitation light. It is shown that theoretically calculated maximally possible content of radiation-induced defects in As 2 S 3 is about 1.6% while concentration of native defects is negligible. (copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Influence of Y, Gd and Sm on the glass forming ability and thermal crystallization of aluminum based alloy

International Nuclear Information System (INIS)

Aliaga, L.C.R.; Bolfarini, C.; Kiminami, C.S.; Botta Filho, W.J.; Danez, G.P.

2010-01-01

Al-based amorphous alloys represent an important family of metals and a great scientific activity has been devoted to determine the main features of both glass forming ability (GFA) and crystallization behavior in order to have a comprehensive framework aimed at potential technological applications. Nowadays, it is well known that the best Al-based amorphous alloys are formed in ternary systems such as Al- RE-TM, where RE is a rare earth and TM a transition metal. This paper presents results of research in Al 85 Ni 10 RE 5 alloys (RE = Y, Gd and Sm). Amorphous ribbons were processed by melt-spinning under the same conditions and subsequently characterized by x-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results show appreciable micro structural differences as function of the rare earth, thus crystal is obtained for Y, nano-glassy for Gd and, fully amorphous structure for Sm. (author)

Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

International Nuclear Information System (INIS)

Minelli, Matteo; Doghieri, Ferruccio

2014-01-01

Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps

RNA Crystallization

Science.gov (United States)

Golden, Barbara L.; Kundrot, Craig E.

2003-01-01

RNA molecules may be crystallized using variations of the methods developed for protein crystallography. As the technology has become available to syntheisize and purify RNA molecules in the quantities and with the quality that is required for crystallography, the field of RNA structure has exploded. The first consideration when crystallizing an RNA is the sequence, which may be varied in a rational way to enhance crystallizability or prevent formation of alternate structures. Once a sequence has been designed, the RNA may be synthesized chemically by solid-state synthesis, or it may be produced enzymatically using RNA polymerase and an appropriate DNA template. Purification of milligram quantities of RNA can be accomplished by HPLC or gel electrophoresis. As with proteins, crystallization of RNA is usually accomplished by vapor diffusion techniques. There are several considerations that are either unique to RNA crystallization or more important for RNA crystallization. Techniques for design, synthesis, purification, and crystallization of RNAs will be reviewed here.

Structural transitions in crystals of native aspartate carbamoyltransferase

International Nuclear Information System (INIS)

Gouaux, J.E.; Lipscomb, W.N.

1989-01-01

Screened precession x-ray photographs of crystals of native aspartate carbamoyltransferase ligated with L-aspartate and phosphate reveal the presence of a crystal unit-cell dimension that is intermediate between the T (tense) and R (relaxed) states. Characterizing the intermediate (I) crystal is a c-axis unit-cell dimension of 149 angstrom, halfway between the c-axis length of the T (c = 142 angstrom) and R (c = 156 angstrom) states, in the space group P321. Preservation of the P321 space group indicates that the intermediate crystal form retains a threefold axis of symmetry, and therefore the enzyme has at minimum a threefold axis; however, it is not known whether the molecular twofold axis is conserved. The I crystals are formed by soaking T-state crystals with L-aspartate and phosphate. By raising the concentration of L-aspartate the authors can further transform the I crystals, without fragmentation, to a form that has the same unit-cell dimensions as R-state crystals grown in the presence of N-(phosphonoacetyl)-L-aspartate

Norepinephrine-modified glassy carbon electrode for the simultaneous determination of ascorbic acid and uric acid

International Nuclear Information System (INIS)

Zare, H.R.; Memarzadeh, F.; Ardakani, M. Mazloum; Namazian, M.; Golabi, S.M.

2005-01-01

The oxidation of norepinephrine (NE) on a preactivated glassy carbon electrode leads to the formation of a deposited layer of about 4.2 x 10 -10 mol cm -2 at the surface of the electrode. The electron transfer rate constant, k s , and charge transfer coefficient, α, for electron transfer between the electrode and immobilized NE film were calculated as 44 s -1 and 0.46, respectively. The NE-modified glassy carbon electrode exhibited good electrocatalytic properties towards ascorbic acid (AA) oxidation in phosphate buffer (pH 7.0) with an overpotential of about 475 mV lower than that of the bare electrode. The electrocatalytic response was evaluated by cyclic voltammetry, chronoamperometry, amperometry and rotating disk voltammetry. The overall number of electrons involved in the catalytic oxidation of AA and the number of electrons involved in the rate-determining step are 2 and 1, respectively. The rate constant for the catalytic oxidation of AA was evaluated by RDE voltammetry and an average value of k h was found to be 8.42 x 10 3 M -1 s -1 . Amperometric determination of AA in stirred solution exhibits a linear range of 2.0-1300.0 μM (correlation coefficient 0.9999) and a detection limit of 0.076 μM. The precision of amperometry was found to be 1.9% for replicate determination of a 49.0 μM solution of AA (n = 6). In differential pulse voltammetric measurements, the NE-modified glassy carbon electrode can separate the AA and uric acid (UA) signals. Ascorbic acid oxidizes at more negative potential than UA. Also, the simultaneous determination of UA and AA is achieved at the NE-modified electrode

Nonlinear magnetoelectric effect in paraelectric state of Co4Nb2O9 single crystal

Czech Academy of Sciences Publication Activity Database

Cao, Ym.; Deng, Gc.; Beran, Přemysl; Feng, Zj.; Kang, Bj.; Zhang, Jc.; Guiblin, N.; Dkhil, B.; Ren, W.; Cao, Sx.

2017-01-01

Roč. 7, č. 10 (2017), č. článku 14079. ISSN 2045-2322 Institutional support: RVO:61389005 Keywords : magnetoelectric * single crystal * neutron diffraction Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 4.259, year: 2016

Design of a candidate vibrational signal for mating disruption against the glassy-winged sharpshooter, Homalodisca Vitripennis

Science.gov (United States)

The glassy-winged sharpshooter (GWSS), Homalodisca vitripennis, is an important pest of grapevines due to its ability to transmit Xylella fastidiosa, the causal agent of Pierce’s disease. GWSS mating communication is based on vibrational signals; therefore, vibrational mating disruption could be an ...

Glass formation ability, structure and magnetocaloric effect of a heavy rare-earth bulk metallic glassy Gd{sub 55}Co{sub 20}Fe{sub 5}Al{sub 20} alloy

Energy Technology Data Exchange (ETDEWEB)

Jo, C.-L. [Shanghai University, School of Materials Science and Engineering, Yanchang Road 149, Zhabei District, 200072 Shanghai (China)], E-mail: jochollong@163.com; Xia Lei; Ding Ding; Dong Yuanda; Gracien, Ekoko [Shanghai University, School of Materials Science and Engineering, Yanchang Road 149, Zhabei District, 200072 Shanghai (China)

2008-06-30

The glass formation ability, the structure and the magnetocaloric effect of the bulk metallic glassy Gd{sub 55}Co{sub 20}Fe{sub 5}Al{sub 20} alloy were investigated. Bulk metallic glassy (BMGs) alloys were prepared by a copper-mold casting method. The glass forming ability and their structure were studied by using X-ray diffraction (XRD) and differential scanning calorimeter (DSC). The XRD analysis revealed that the as-cast cylinder of Gd{sub 55}Co{sub 20}Fe{sub 5}Al{sub 20} alloy showed fully amorphous structure in 2 mm diameter. The DSC revealed that the bulk cylinder of the Gd{sub 55}Co{sub 20}Fe{sub 5}Al{sub 20} alloy showed a distinct glass transition temperature and a relatively wide supercooled liquid region before crystallization. SQUID investigated the magnetic properties and the entropy changes. The Curie temperature of Gd{sub 55}Co{sub 20}Fe{sub 5}Al{sub 20} BMGs alloy was about 130 K, but the maximum magnetic entropy changes(-{delta}S{sub M}) showed at about 125 K, a little lower than the Curie temperature 130 K. The reason could probably be due to the presence of a little amount of nanocrystalline particles between amorphous phases. The BMG alloy has the characteristic of second-order transition (SOT) on Arrott plots. The results showed that the amorphous sample had a relatively improved magnetocaloric effect, indicating that the amorphous alloy could be considered as a candidate for magnetic refrigeration applications in the temperature interval range of 100-200 K.

Effect of chain rigidity on network architecture and deformation behavior of glassy polymer networks

Science.gov (United States)

Knowles, Kyler Reser

Processing carbon fiber composite laminates creates molecular-level strains in the thermoset matrix upon curing and cooling which can lead to failures such as geometry deformations, micro-cracking, and other issues. It is known strain creation is attributed to the significant volume and physical state changes undergone by the polymer matrix throughout the curing process, though storage and relaxation of cure-induced strains remain poorly understood. This dissertation establishes two approaches to address the issue. The first establishes testing methods to simultaneously measure key volumetric properties of a carbon fiber composite laminate and its polymer matrix. The second approach considers the rigidity of the polymer matrix in regards to strain storage and relaxation mechanisms which ultimately control composite performance throughout manufacturing and use. Through the use of a non-contact, full-field strain measurement technique known as digital image correlation (DIC), we describe and implement useful experiments which quantify matrix and composite parameters necessary for simulation efforts and failure models. The methods are compared to more traditional techniques and show excellent correlation. Further, we established relationships which represent matrix-fiber compatibility in regards to critical processing constraints. The second approach involves a systematic study of epoxy-amine networks which are chemically-similar but differ in chain segment rigidity. Prior research has investigated the isomer effect of glassy polymers, showing sizeable differences in thermal, volumetric, physical, and mechanical properties. This work builds on these themes and shows the apparent isomer effect is rather an effect of chain rigidity. Indeed, it was found that structurally-dissimilar polymer networks exhibit very similar properties as a consequence of their shared average network rigidity. Differences in chain packing, as a consequence of chain rigidity, were shown to

Mathematical model of the crystallizing blank`s thermal state at the horizontal continuous casting machine

Directory of Open Access Journals (Sweden)

Kryukov Igor Yu.

2017-01-01

Full Text Available Present article is devoted to the development of the mathematical model, which describes thermal state and crystallization process of the rectangular cross-section blank while continious process of extraction from a horysontal continious casting machine (HCCM.The developed model took cue for the heat-transfer properties of non-iron metal teeming; its temperature on entry to the casting mold; cooling conditions of blank in the carbon molds in the presence of a copper water cooler. Besides, has been considered the asymmetry of heat interchange from blank`s head and drag at mold, coming out from fluid contraction and features of the horizontal casting mold. The developed mathematical model allows to determine alterations in crystallizing blank of the following factors with respect to time: temperature pattern of crystallizing blank under different technical working regimes of HCCM; boundaries of solid two-phase field and liquid two-phase filed; blank`s thickness variation under shrinkage of the ingot`s material

Preparation of rod-like β-Si3N4 single crystal particles

International Nuclear Information System (INIS)

Hirao, K.; Tsuge, A.; Brito, M.E.; Kanzaki, S.

1994-01-01

The use of β-Si 3 N 4 particles as a seed material has been demonstrated to be effective for development of a self-reinforcing microstructure in sintered silicon nitride ceramics. We have confirmed the seeding effect and arrived at a concept that seed particles should consist of rod-like single crystals free from defects and with a large diameter. The present work describes our attempts to produce such particles with a controlled morphology and in high amount. β-Si 3 N 4 particles with a diameter of 1μm and length of 5μm were obtained by heating a mixture of α-Si 3 N 4 , SiO 2 and Y 2 O 3 , followed by acid rinse treatments to remove residual glassy phase. (orig.)

Crystal structure and electronic states of Co and Gd ions in a Gd0.4Sr0.6CoO2.85 single crystal

Science.gov (United States)

Platunov, M. S.; Dudnikov, V. A.; Orlov, Yu. S.; Kazak, N. V.; Solovyov, L. A.; Zubavichus, Ya. V.; Veligzhanin, A. A.; Dorovatovskii, P. V.; Vereshchagin, S. N.; Shaykhutdinov, K. A.; Ovchinnikov, S. G.

2016-02-01

X-ray diffraction and X-ray absorption near edge structure (XANES) spectra have been measured at the Co K-edge and Gd L 3-edge in GdCoO3 and Gd0.4Sr0.6CoO2.85 cobaltites. The effect of Sr substitution on the crystal structure and electronic and magnetic states of Co3+ ions in a Gd0.4Sr0.6CoO2.85 single crystal has been analyzed. The XANES measurements at the Co K-edge have not showed a noticeable shift of the absorption edge with an increase in the concentration of Sr. This indicates that the effective valence of cobalt does not change. An increase in the intensity of absorption at the Gd L 3-edge is due to an increase in the degree of hybridization of the Gd(5 d) and O(2 p) states. The effect of hole doping on the magnetic properties results in the appearance of the ferromagnetic component and in a significant increase in the magnetic moment.

Detection of dopamine in non-treated urine samples using glassy carbon electrodes modified with PAMAM dendrimer-Pt composites

International Nuclear Information System (INIS)

Garcia, M.G.; Armendariz, G.M.E.; Godinez, Luis A.; Torres, J.; Sepulveda-Guzman, S.; Bustos, E.

2011-01-01

Composites of hydroxyl-terminated PAMAM dendrimers, generation 4.0 (64 peripheral OH groups) containing Pt nanoparticles were synthesized at different reaction times using a microwave reactor. The synthetic procedure resulted in dendrimer encapsulated nanoparticles of Pt (DENs-Pt) of 1.53 ± 0.17 nm diameter that was calculated from transmission electron microscopy, and the Pt nanoparticles had single crystal plane in (1 1 1) orientation determinate by selective area diffraction. Each composite was electrochemically immobilized on a pre-functionalized glassy carbon (GC) electrode that was incorporated as a flow injection amperometric (FIA) detector, for the selective detection and quantification of dopamine (DA) in untreated urine samples. Comparison of the analytical performance of the novel electrochemical detector revealed that the DENs-Pt modified GC electrode with the composite synthesized for 30 min in the microwave reactor, showed the best response for the detection of DA in samples of non-treated urine, being the detection and quantification limits smaller (19 and 9 ppb, respectively) than those corresponding to the naked a GC electrode (846 and 423 ppb, respectively) using the FIA detector. In addition, it was found that this electroanalytical approach suffers minimal matrix effects that arise in the analysis of DA in untreated samples of urine.

Detection of dopamine in non-treated urine samples using glassy carbon electrodes modified with PAMAM dendrimer-Pt composites

Energy Technology Data Exchange (ETDEWEB)

Garcia, M.G. [Laboratory of Bioelectrochemistry, Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, S. C., Parque Tecnologico, Queretaro, Sanfandila, Pedro Escobedo 76703, Queretaro (Mexico); Department of Chemistry, Universidad de Guanajuato, Cerro de la Venada S/N Col. Pueblito de Rocha, 36040 Guanajuato, Gto (Mexico); Armendariz, G.M.E.; Godinez, Luis A.; Torres, J. [Laboratory of Bioelectrochemistry, Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, S. C., Parque Tecnologico, Queretaro, Sanfandila, Pedro Escobedo 76703, Queretaro (Mexico); Sepulveda-Guzman, S. [Centro de Innovacion, Investigacion y Desarrollo en Ingenieria y Tecnologia, Facultad de Ingenieria Mecanica y Electrica, Universidad Autonoma de Nuevo Leon, Av. Universidad, San Nicolas de los Garza, Nuevo Leon, 66451 Nuevo Leon (Mexico); Bustos, E., E-mail: ebustos@cideteq.mx [Laboratory of Bioelectrochemistry, Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, S. C., Parque Tecnologico, Queretaro, Sanfandila, Pedro Escobedo 76703, Queretaro (Mexico)

2011-09-01

Composites of hydroxyl-terminated PAMAM dendrimers, generation 4.0 (64 peripheral OH groups) containing Pt nanoparticles were synthesized at different reaction times using a microwave reactor. The synthetic procedure resulted in dendrimer encapsulated nanoparticles of Pt (DENs-Pt) of 1.53 {+-} 0.17 nm diameter that was calculated from transmission electron microscopy, and the Pt nanoparticles had single crystal plane in (1 1 1) orientation determinate by selective area diffraction. Each composite was electrochemically immobilized on a pre-functionalized glassy carbon (GC) electrode that was incorporated as a flow injection amperometric (FIA) detector, for the selective detection and quantification of dopamine (DA) in untreated urine samples. Comparison of the analytical performance of the novel electrochemical detector revealed that the DENs-Pt modified GC electrode with the composite synthesized for 30 min in the microwave reactor, showed the best response for the detection of DA in samples of non-treated urine, being the detection and quantification limits smaller (19 and 9 ppb, respectively) than those corresponding to the naked a GC electrode (846 and 423 ppb, respectively) using the FIA detector. In addition, it was found that this electroanalytical approach suffers minimal matrix effects that arise in the analysis of DA in untreated samples of urine.

Gold nanoparticle/multi-walled carbon nanotube modified glassy carbon electrode as a sensitive voltammetric sensor for the determination of diclofenac sodium

International Nuclear Information System (INIS)

Afkhami, Abbas; Bahiraei, Atousa; Madrakian, Tayyebeh

2016-01-01

A simple and highly sensitive sensor for the determination of diclofenac sodium based on gold nanoparticle/multi-walled carbon nanotube modified glassy carbon electrode is reported. Scanning electron microscopy along with energy dispersive X-ray spectroscopy, electrochemical impedance spectroscopy, cyclic voltammetry and square wave voltammetry was used to characterize the nanostructure and performance of the sensor and the results were compared with those obtained at the multi-walled carbon nanotube modified glassy carbon electrode and bare glassy carbon electrode. Under the optimized experimental conditions diclofenac sodium gave linear response over the range of 0.03–200 μmol L −1 . The lower detection limits were found to be 0.02 μmol L −1 . The effect of common interferences on the current response of DS was investigated. The practical application of the modified electrode was demonstrated by measuring the concentration of diclofenac sodium in urine and pharmaceutical samples. This revealed that the gold nanoparticle/multiwalled carbon nanotube modified glassy carbon electrode shows excellent analytical performance for the determination of diclofenac sodium in terms of a very low detection limit, high sensitivity, very good accuracy, repeatability and reproducibility. - Highlights: • GCE was modified with multiwalled carbon nanotube and gold nanoparticles. • AuNP/MWCNT/GCE was used for the determination of diclofenac sodium. • Modified electrode was characterized by SEM, EDS and EIS. • The proposed method showed excellent analytical figures of merit. • This sensor was used for the determination of diclofenac sodium in real samples.

Gold nanoparticle/multi-walled carbon nanotube modified glassy carbon electrode as a sensitive voltammetric sensor for the determination of diclofenac sodium

Energy Technology Data Exchange (ETDEWEB)

Afkhami, Abbas, E-mail: afkhami@basu.ac.ir; Bahiraei, Atousa; Madrakian, Tayyebeh

2016-02-01

A simple and highly sensitive sensor for the determination of diclofenac sodium based on gold nanoparticle/multi-walled carbon nanotube modified glassy carbon electrode is reported. Scanning electron microscopy along with energy dispersive X-ray spectroscopy, electrochemical impedance spectroscopy, cyclic voltammetry and square wave voltammetry was used to characterize the nanostructure and performance of the sensor and the results were compared with those obtained at the multi-walled carbon nanotube modified glassy carbon electrode and bare glassy carbon electrode. Under the optimized experimental conditions diclofenac sodium gave linear response over the range of 0.03–200 μmol L{sup −1}. The lower detection limits were found to be 0.02 μmol L{sup −1}. The effect of common interferences on the current response of DS was investigated. The practical application of the modified electrode was demonstrated by measuring the concentration of diclofenac sodium in urine and pharmaceutical samples. This revealed that the gold nanoparticle/multiwalled carbon nanotube modified glassy carbon electrode shows excellent analytical performance for the determination of diclofenac sodium in terms of a very low detection limit, high sensitivity, very good accuracy, repeatability and reproducibility. - Highlights: • GCE was modified with multiwalled carbon nanotube and gold nanoparticles. • AuNP/MWCNT/GCE was used for the determination of diclofenac sodium. • Modified electrode was characterized by SEM, EDS and EIS. • The proposed method showed excellent analytical figures of merit. • This sensor was used for the determination of diclofenac sodium in real samples.

Waterlike glass polyamorphism in a monoatomic isotropic Jagla model.

Science.gov (United States)

Xu, Limei; Giovambattista, Nicolas; Buldyrev, Sergey V; Debenedetti, Pablo G; Stanley, H Eugene

2011-02-14

We perform discrete-event molecular dynamics simulations of a system of particles interacting with a spherically-symmetric (isotropic) two-scale Jagla pair potential characterized by a hard inner core, a linear repulsion at intermediate separations, and a weak attractive interaction at larger separations. This model system has been extensively studied due to its ability to reproduce many thermodynamic, dynamic, and structural anomalies of liquid water. The model is also interesting because: (i) it is very simple, being composed of isotropically interacting particles, (ii) it exhibits polyamorphism in the liquid phase, and (iii) its slow crystallization kinetics facilitate the study of glassy states. There is interest in the degree to which the known polyamorphism in glassy water may have parallels in liquid water. Motivated by parallels between the properties of the Jagla potential and those of water in the liquid state, we study the metastable phase diagram in the glass state. Specifically, we perform the computational analog of the protocols followed in the experimental studies of glassy water. We find that the Jagla potential calculations reproduce three key experimental features of glassy water: (i) the crystal-to-high-density amorphous solid (HDA) transformation upon isothermal compression, (ii) the low-density amorphous solid (LDA)-to-HDA transformation upon isothermal compression, and (iii) the HDA-to-very-high-density amorphous solid (VHDA) transformation upon isobaric annealing at high pressure. In addition, the HDA-to-LDA transformation upon isobaric heating, observed in water experiments, can only be reproduced in the Jagla model if a free surface is introduced in the simulation box. The HDA configurations obtained in cases (i) and (ii) are structurally indistinguishable, suggesting that both processes result in the same glass. With the present parametrization, the evolution of density with pressure or temperature is remarkably similar to the

Aluminum-air battery crystallizer

Science.gov (United States)

Maimoni, A.

1987-01-01

A prototype crystallizer system for the aluminum-air battery operated reliably through simulated startup and shutdown cycles and met its design objectives. The crystallizer system allows for crystallization and removal of the aluminium hydroxide reaction product; it is required to allow steady-state and long-term operation of the aluminum-air battery. The system has to minimize volume and maintain low turbulence and shear to minimize secondary nucleation and energy consumption while enhancing agglomeration. A lamella crystallizer satisfies system constraints.

Single Crystal Growth of Pure Co3+ Oxidation State Material LaSrCoO4

Directory of Open Access Journals (Sweden)

Hanjie Guo

2016-08-01

Full Text Available We report on the single crystal growth of the single-layer perovskite cobaltate LaSrCoO4 that was grown by the optical floating zone method using high oxygen pressures. Phase purity and single crystallinity were confirmed by X-ray diffraction techniques. The pure Co3+ oxidation state was confirmed by X-ray absorbtion spectroscopy measurements. A transition to a spin glass state is observed at ∼7 K in magnetic susceptibility and specific heat measurements.

Trapped electron decay by the thermally-assisted tunnelling to electron acceptors in glassy matrices. A computer simulation study

International Nuclear Information System (INIS)

Feret, B.; Bartczak, W.M.; Kroh, J.

1991-01-01

The Redi-Hopefield quantum mechanical model of the thermally-assisted electron transfer has been applied to simulate the decay of trapped electrons by tunnelling to electron acceptor molecules added to the glassy matrix. It was assumed that the electron energy levels in donors and acceptors are statistically distributed and the electron excess energy after transfer is dissipated in the medium by the electron-phonon coupling. The electron decay curves were obtained by the method of computer simulation. It was found that for a given medium there exists a certain preferred value of the electronic excess energy which can be effectively converted into the matrix vibrations. If the mismatch of the electron states on the donor and acceptor coincides with the ''resonance'' energy the overall kinetics of electron transfer is accelerated. (author)

Glassy metals

CERN Document Server

Russew, Krassimir

2016-01-01

The topics discussed in this book focus on fundamental problems concerning the structural relaxation of amorphous metallic alloys, above all the possibility of studying it on the basis of viscous flow behavior and its relation to rheological anomalies, such as bend stress relaxation, thermal expansion, specific heat, density changes, and crystallization. Most relaxation studies deal with the relaxation changes of a single definite material property, and not with a wider spectrum of physical properties integrated into a common framework. This book shows that it is possible to describe these property changes on the basis of a more comprehensive theoretical understanding of their mechanism.

Cytochrome C Dynamics at Gold and Glassy Carbon Surfaces Monitored by in Situ Scanning Tunnel Microscopy

DEFF Research Database (Denmark)

Andersen, Jens Enevold Thaulov; Møller, Per; Pedersen, Marianne Vind

1995-01-01

We have investigated the absorption of cytochrome c on gold and glassy carbon substrates by in situ scanning tunnel microscopy under potentiostatic control of both substrate and tip. Low ionic strength and potential ranges where no Faradaic current flows were used. Cyt c aggregates into flat...

Structure and transformation behaviour of a rapidly solidified Al-Y-Ni-Co-Pd alloy

International Nuclear Information System (INIS)

Louzguine-Luzgin, D.V.; Inoue, A.

2005-01-01

An as-solidified structure and transformation behaviour on heating of the rapidly solidified Al-Y-Ni-Co-Pd alloy was studied by X-ray diffractometry (XRD), transmission electron microscopy (TEM), differential scanning and isothermal calorimetries. The Al-Y-Ni-Co-Pd ribbon samples have been produced by the melt spinning technique and heat treated using a differential scanning calorimeter (DSC). The addition of Pd to Al-Y-Ni-Co alloys caused disappearance of the supercooled liquid region as well as the formation of the highly dispersed primary α-Al nanoparticles about 3-7 nm in size homogeneously embedded in the glassy matrix upon solidification. An extremely high density of precipitates of the order of 10 24 m -3 is obtained. These particles start growing at the temperature below a glass-transition temperature. The results presented in this paper indicate that some of so-called 'marginal' glass-formers in as-solidified state are actually not glassy alloys with pre-existed nuclei but crystal-glassy nanocomposites

Nanocrystalline solids

International Nuclear Information System (INIS)

Gleiter, H.

1991-01-01

Nanocrystalline solids are polycrystals, the crystal size of which is a few (typically 1 to 10) nanometres so that 50% or more of the solid consists of incoherent interfaces between crystals of different orientations. Solids consisting primarily of internal interfaces represent a separate class of atomic structures because the atomic arrangement formed in the core of an interface is known to be an arrangement of minimum energy in the potential field of the two adjacent crystal lattices with different crystallographic orientations on either side of the boundary core. These boundary conditions result in atomic structures in the interfacial cores which cannot be formed elsewhere (e.g. in glasses or perfect crystals). Nanocrystalline solids are of interest for the following four reasons: (1) Nanocrystalline solids exhibit an atomic structure which differs from that of the two known solid states: the crystalline (with long-range order) and the glassy (with short-range order). (2) The properties of nanocrystalline solids differ (in some cases by several orders of magnitude) from those of glasses and/or crystals with the same chemical composition, which suggests that they may be utilized technologically in the future. (3) Nanocrystalline solids seem to permit the alloying of conventionally immiscible components. (4) If small (1 to 10 nm diameter) solid droplets with a glassy structure are consolidated (instead of small crystals), a new type of glass, called nanoglass, is obtained. Such glasses seem to differ structurally from conventional glasses. (orig.)

Functionalization of glassy carbon surface by means of aliphatic and aromatic amino acids. An experimental and theoretical integrated approach

International Nuclear Information System (INIS)

Vanossi, Davide; Benassi, Rois; Parenti, Francesca; Tassinari, Francesco; Giovanardi, Roberto; Florini, Nicola; De Renzi, Valentina; Arnaud, Gaelle; Fontanesi, Claudio

2012-01-01

Highlights: ► Glassy carbon is functionalized via electrochemical assisted grafting of amino acids. ► The grafting mechanism is suggested to involve the “zwitterionic” species. ► DFT calculations allowed to determine the electroactive species. ► An original grafting mechanism is proposed. - Abstract: Glassy carbon (GC) electrode surfaces are functionalized through electrochemical assisted grafting, in oxidation regime, of six amino acids (AA): β-alanine (β-Ala), L-aspartic acid (Asp), 11-aminoundecanoic acid (UA), 4-aminobenzoic acid (PABA), 4-(4-amino-phenyl)-butyric acid (PFB), 3-(4-amino-phenyl)-propionic acid (PFP). Thus, a GC/AA interface is produced featuring carboxylic groups facing the solution. Electrochemical (cyclic voltammetry and electrochemical impedance spectroscopy) and XPS techniques are used to experimentally characterize the grafting process and the surface state. The theoretical results are compared with the experimental evidence to determine, at a molecular level, the overall grafting mechanism. Ionization potentials, standard oxidation potentials, HOMO and electron spin distributions are calculated at the CCD/6-31G* level of the theory. The comparison of experimental and theoretical data suggests that the main electroactive species is the “zwitterionic” form for the three aliphatic amino acids, while the amino acids featuring the amino group bound to the phenyl aromatic moiety show a different behaviour. The comparison between experimental and theoretical results suggests that both the neutral and the zwitterionic forms are present in the acetonitrile solution in the case of 4-(4-amino-phenyl)-butyric acid (PFB) and 3-(4-amino-phenyl)-propionic acid.

Resistivity and Passivity Characterization of Ni-Base Glassy Alloys in NaOH Media

Directory of Open Access Journals (Sweden)

Khadijah M. Emran

2018-01-01

Full Text Available Resistivity and passivation behavior of two Ni-base bulk metallic glasses, with the nominal composition of Ni70Cr21Si0.5B0.5P8C ≤ 0.1Co ≤ 1Fe ≤ 1 (VZ1 and Ni72.65Cr7.3-Si6.7B2.15C ≤ 0.06Fe8.2Mo3 (VZ2, in various concentrations of NaOH solutions were studied. The investigations involved cyclic polarization (CP, electrochemical impedance spectroscopy (EIS, and electrochemical frequency modulation (EFM methods. Cyclic polarization measurements showed spontaneous passivation for both Ni-base glassy alloys at all alkaline concentrations, due to the presence of chromium as an alloying element that formed an oxide film on the alloy surface. The EIS analysis showed that the passive layers grown on the two Ni-base glassy alloy surfaces are formed by a double oxide layer structure. Scanning electron microscope (SEM examinations of the electrode surface showed Cr, Ni, Fe, and O rich corrosion products that reduced the extent of corrosion damage. Atomic force microscopy (AFM imaging technique was used to evaluate the topographic and morphologic features of surface layers formed on the surface of the alloys.

Electrochemical behavior of cysteine at a CuGeO3 nanowires modified glassy carbon electrode

International Nuclear Information System (INIS)

Dong Yongping; Pei Lizhai; Chu Xiangfeng; Zhang Wangbing; Zhang Qianfeng

2010-01-01

A CuGeO 3 nanowire modified glassy carbon electrode was fabricated and characterized by scanning electron microscopy. The results of electrochemical impedance spectroscopy reveal that electron transfer through nanowire film is facile compared with that of bare glassy carbon electrode. The modified electrode exhibited a novel electrocatalytic behavior to the electrochemical reactions of L-cysteine in neutral solution, which was not reported previously. Two pairs of semi-reversible electrochemical peaks were observed and assigned to the processes of oxidation/reduction and adsorption/desorption of cysteine at the modified electrode, respectively. The electrochemical response of cysteine is poor in alkaline condition and is enhanced greatly in acidic solution, suggesting that hydrogen ions participate in the electrochemical oxidation process of cysteine. The intensities of two anodic peaks varied linearly with the concentration of cysteine in the range of 1 x 10 -6 to 1 x 10 -3 mol L -1 , which make it possible to sensitive detection of cysteine with the CuGeO 3 nanowire modified electrode. Furthermore, the modified electrode exhibited good reproducibility and stability.

General crystal in prebiotic context

International Nuclear Information System (INIS)

Simon, I.

1993-09-01

General crystal is an extension of the crystal concept to any form of matter which exhibit neighbour structure determination. This extension makes many results of solid state physics applicable to heterogeneous matter. Among other it includes the description of phase transition from random to unique structure. The advantage of the general crystal approach is demonstrated on globular protein, on of the most important macromolecules of life, which are capable to adopt unique 3D structure spontaneously, regardless of the heterogeneous character of their chemical structure and conformation. It is suggested that the use of general crystal concept may help to find candidates among heterogeneous matters capable to spontaneous self-organization in the same way as crystallization results in unique structure of homogeneous matter, and to apply some of the results of solid state physics to describe the phase transition and other behaviour of this matter. (author). 10 refs

Effects of Xylem-Sap Composition on Glassy-Winged Sharpshooter (Hemiptera: Cicadellidae) Egg Maturation on High- and Low-Quality Host Plants.

Science.gov (United States)

Sisterson, Mark S; Wallis, Christopher M; Stenger, Drake C

2017-04-01

Glassy-winged sharpshooters must feed as adults to produce mature eggs. Cowpea and sunflower are both readily accepted by the glassy-winged sharpshooter for feeding, but egg production on sunflower was reported to be lower than egg production on cowpea. To better understand the role of adult diet in egg production, effects of xylem-sap chemistry on glassy-winged sharpshooter egg maturation was compared for females confined to cowpea and sunflower. Females confined to cowpea consumed more xylem-sap than females held on sunflower. In response, females held on cowpea produced more eggs, had heavier bodies, and greater lipid content than females held on sunflower. Analysis of cowpea and sunflower xylem-sap found that 17 of 19 amino acids were more concentrated in cowpea xylem-sap than in sunflower xylem-sap. Thus, decreased consumption of sunflower xylem-sap was likely owing to perceived lower quality, with decreased egg production owing to a combination of decreased feeding and lower return per unit volume of xylem-sap consumed. Examination of pairwise correlation coefficients among amino acids indicated that concentrations of several amino acids within a plant species were correlated. Principal component analyses identified latent variables describing amino acid composition of xylem-sap. For females held on cowpea, egg maturation was affected by test date, volume of excreta produced, and principal components describing amino acid composition of xylem-sap. Principal component analyses aided in identifying amino acids that were positively or negatively associated with egg production, although determining causality with respect to key nutritional requirements for glassy-winged sharpshooter egg production will require additional testing. Published by Oxford University Press on behalf of Entomological Society of America 2017. This work is written by US Government employees and is in the public domain in the US.

A multistep single-crystal-to-single-crystal bromodiacetylene dimerization

Science.gov (United States)

Hoheisel, Tobias N.; Schrettl, Stephen; Marty, Roman; Todorova, Tanya K.; Corminboeuf, Clémence; Sienkiewicz, Andrzej; Scopelliti, Rosario; Schweizer, W. Bernd; Frauenrath, Holger

2013-04-01

Packing constraints and precise placement of functional groups are the reason that organic molecules in the crystalline state often display unusual physical or chemical properties not observed in solution. Here we report a single-crystal-to-single-crystal dimerization of a bromodiacetylene that involves unusually large atom displacements as well as the cleavage and formation of several bonds. Density functional theory computations support a mechanism in which the dimerization is initiated by a [2 + 1] photocycloaddition favoured by the nature of carbon-carbon short contacts in the crystal structure. The reaction proceeded up to the theoretical degree of conversion without loss of crystallinity, and it was also performed on a preparative scale with good yield. Moreover, it represents the first synthetic pathway to (E)-1,2-dibromo-1,2-diethynylethenes, which could serve as synthetic intermediates for the preparation of molecular carbon scaffolds. Our findings both extend the scope of single-crystal-to-single-crystal reactions and highlight their potential as a synthetic tool for complex transformations.

Electrochemical evaluation and determination of antiretroviral drug fosamprenavir using boron-doped diamond and glassy carbon electrodes.

Science.gov (United States)

Gumustas, Mehmet; Ozkan, Sibel A

2010-05-01

Fosamprenavir is a pro-drug of the antiretroviral protease inhibitor amprenavir and is oxidizable at solid electrodes. The anodic oxidation behavior of fosamprenavir was investigated using cyclic and linear sweep voltammetry at boron-doped diamond and glassy carbon electrodes. In cyclic voltammetry, depending on pH values, fosamprenavir showed one sharp irreversible oxidation peak or wave depending on the working electrode. The mechanism of the oxidation process was discussed. The voltammetric study of some model compounds allowed elucidation of the possible oxidation mechanism of fosamprenavir. The aim of this study was to determine fosamprenavir levels in pharmaceutical formulations and biological samples by means of electrochemical methods. Using the sharp oxidation response, two voltammetric methods were described for the determination of fosamprenavir by differential pulse and square-wave voltammetry at the boron-doped diamond and glassy carbon electrodes. These two voltammetric techniques are 0.1 M H(2)SO(4) and phosphate buffer at pH 2.0 which allow quantitation over a 4 x 10(-6) to 8 x 10(-5) M range using boron-doped diamond and a 1 x 10(-5) to 1 x 10(-4) M range using glassy carbon electrodes, respectively, in supporting electrolyte. All necessary validation parameters were investigated and calculated. These methods were successfully applied for the analysis of fosamprenavir pharmaceutical dosage forms, human serum and urine samples. The standard addition method was used in biological media using boron-doped diamond electrode. No electroactive interferences from the tablet excipients or endogenous substances from biological material were found. The results were statistically compared with those obtained through an established HPLC-UV technique; no significant differences were found between the voltammetric and HPLC methods.

A roadmap to uranium ionic liquids: anti-crystal engineering.

Science.gov (United States)

Yaprak, Damla; Spielberg, Eike T; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja-Verena

2014-05-19

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C4mim) cation. As dithiocarbamate ligands binding to the UO2(2+) unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure-property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. These materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic structure of metallic glasses

International Nuclear Information System (INIS)

Oelhafen, P.; Lapka, R.; Gubler, U.; Krieg, J.; DasGupta, A.; Guentherodt, H.J.; Mizoguchi, T.; Hague, C.; Kuebler, J.; Nagel, S.R.

1981-01-01

This paper is organized in six sections and deals with (1) the glassy transition metal alloys, their d-band structure, the d-band shifts on alloying and their relation to the alloy heat of formation (ΔH) and the glass forming ability, (2) the glass to crystal phase transition viewed by valence band spectroscopy, (3) band structure calculations, (4) metallic glasses prepared by laser glazing, (5) glassy normal metal alloys, and (6) glassy hydrides

Photonic crystal light source

Science.gov (United States)

Fleming, James G [Albuquerque, NM; Lin, Shawn-Yu [Albuquerque, NM; Bur, James A [Corrales, NM

2004-07-27

A light source is provided by a photonic crystal having an enhanced photonic density-of-states over a band of frequencies and wherein at least one of the dielectric materials of the photonic crystal has a complex dielectric constant, thereby producing enhanced light emission at the band of frequencies when the photonic crystal is heated. The dielectric material can be a metal, such as tungsten. The spectral properties of the light source can be easily tuned by modification of the photonic crystal structure and materials. The photonic crystal light source can be heated electrically or other heating means. The light source can further include additional photonic crystals that exhibit enhanced light emission at a different band of frequencies to provide for color mixing. The photonic crystal light source may have applications in optical telecommunications, information displays, energy conversion, sensors, and other optical applications.

Non-Gaussian nature of glassy dynamics by cage to cage motion

International Nuclear Information System (INIS)

Vorselaars, Bart; Lyulin, Alexey V.; Michels, M. A. J.; Karatasos, K.

2007-01-01

A model based on a single Brownian particle moving in a periodic effective field is used to understand the non-Gaussian dynamics in glassy systems of cage escape and subsequent recaging, often thought to be caused by a heterogeneous glass structure. The results are compared to molecular-dynamics simulations of systems with varying complexity: quasi-two-dimensional colloidlike particles, atactic polystyrene, and a dendritic glass. The model nicely describes generic features of all three topologically different systems, in particular around the maximum of the non-Gaussian parameter. This maximum is a measure for the average distance between cages

In-Vivo Characterization of Glassy Carbon Micro-Electrode Arrays for Neural Applications and Histological Analysis of the Brain Tissue

Science.gov (United States)

Vomero, Maria

The aim of this work is to fabricate and characterize glassy carbon Microelectrode Arrays (MEAs) for sensing and stimulating neural activity, and conduct histological analysis of the brain tissue after the implant to determine long-term performance. Neural applications often require robust electrical and electrochemical response over a long period of time, and for those applications we propose to replace the commonly used noble metals like platinum, gold and iridium with glassy carbon. We submit that such material has the potential to improve the performances of traditional neural prostheses, thanks to better charge transfer capabilities and higher electrochemical stability. Great interest and attention is given in this work, in particular, to the investigation of tissue response after several weeks of implants in rodents' brain motor cortex and the associated materials degradation. As part of this work, a new set of devices for Electrocorticography (ECoG) has been designed and fabricated to improve durability and quality of the previous generation of devices, designed and manufactured by the same research group in 2014. In-vivo long-term impedance measurements and brain activity recordings were performed to test the functionality of the neural devices. In-vitro electrical characterization of the carbon electrodes, as well as the study of the adhesion mechanisms between glassy carbon and different substrates is also part of the research described in this book.

Atomic structure of glassy Mg60Cu30Y10 investigated with EXAFS, x-ray and neutron diffraction, and reverse Monte Carlo simulations

DEFF Research Database (Denmark)

Jovari, P.; Saksl, K.; Pryds, Nini

2007-01-01

Short range order of amorphous Mg60Cu30Y10 was investigated by x-ray and neutron diffraction, Cu and Y K-edge x-ray absorption fine structure measurements, and the reverse Monte Carlo simulation technique. We found that Mg-Mg and Mg-Cu nearest neighbor distances are very similar to values found...... in crystalline Mg2Cu. The Cu-Y coordination number is 1.1 +/- 0.2, and the Cu-Y distance is similar to 4% shorter than the sum of atomic radii, suggesting that attraction between Cu and Y plays an important role in stabilizing the glassy state. Thermal stability and structure evolution upon annealing were also...

Magnetocaloric effect of polycrystalline Sm0.5Ca0.5MnO3 compound: Investigation of low temperature magnetic state

Science.gov (United States)

Das, Kalipada; Banu, Nasrin; Das, I.; Dev, B. N.

2018-06-01

An attempt has been made to probe low temperature magnetic state of the polycrystalline Sm0.5Ca0.5MnO3 compound via magnetization and magnetocaloric studies. In the context of the earlier debatable reports on the above mentioned compound between the existence of glassy magnetic state and small ferromagnetic domains from the 'ac' susceptibility measurements, our experimental observation from magnetocaloric effect study clearly indicates the existence of ferromagnetic droplets along with certain amount of superparamagnetic component at low temperature (magnetization (even at H = 0.01 T) data do not exhibit the spin freezing nature at the low temperature which is almost a generic tendency of glassy magnetic state. Our study also highlights the competence of magnetocaloric effect as a tool to distinguish between different magnetic states of a compound.

Thermal Barrier Coatings Resistant to Glassy Deposits

Science.gov (United States)

Drexler, Julie Marie

Engineering of alloys has for years allowed aircraft turbine engines to become more efficient and operate at higher temperatures. As advancements in these alloy systems have become more difficult, ceramic thermal barrier coatings (TBCs), often yttria (7 wt %) stabilized zirconia (7YSZ), have been utilized for thermal protection. TBCs have allowed for higher engine operating temperatures and better fuel efficiency but have also created new engineering problems. Specifically, silica based particles such as sand and volcanic ash that enter the engine during operation form glassy deposits on the TBCs. These deposits can cause the current industrial 7YSZ thermal barrier coatings to fail since the glass formed penetrates and chemically interacts with the TBC. When this occurs, coating failure may occur due to a loss of strain tolerance, which can lead to fracture, and phase changes of the TBC material. There have been several approaches used to stop calcium-magnesium aluminio-silcate (CMAS) glasses (molten sand) from destroying the entire TBC, but overall there is still limited knowledge. In this thesis, 7YSZ and new TBC materials will be examined for thermochemical and thermomechanical performance in the presence of molten CMAS and volcanic ash. Two air plasma sprayed TBCs will be shown to be resistant to volcanic ash and CMAS. The first type of coating is a modified 7YSZ coating with 20 mol% Al2O3 and 5 mol% TiO2 in solid solution (YSZ+20Al+5Ti). The second TBC is made of gadolinium zirconate. These novel TBCs impede CMAS and ash penetration by interacting with the molten CMAS or ash and drastically changing the chemistry. The chemically modified CMAS or ash will crystallize into an apatite or anorthite phase, blocking the CMAS or ash from further destroying the coating. A presented mechanism study will show these coatings are effective due to the large amount of solute (Gd, Al) in the zirconia structure, which is the key to creating the crystalline apatite or

A nanoscale characterisation of extended defects in glassy-like As{sub 2}Se{sub 3} semiconductors with PAL technique

Energy Technology Data Exchange (ETDEWEB)

Shpotyuk, O.; Kovalskiy, A.; Filipecki, J.; Hyla, M.; Kozdras, A

2003-12-31

A meaningful interpretation of positron lifetime characteristics for glassy-like g-As{sub 2}Se{sub 3} is developed taking into account calculations of Jensen et al. (J. Non-Cryst. Solids 170 (1994) 57) for positrons trapped by free-volume extended defects in orthorhombic As{sub 2}Se{sub 3} and void volume distribution for 146-atoms layer-biased model of amorphous As{sub 2}Se{sub 3} presented by Popescu (J. Non-Cryst. Solids 35-36 (1980) 549). The obtained results are compared for samples having different thermal pre-history. Two groups of experimental results with close lifetime characteristics are distinguished for each of the investigated samples. This feature is explained in terms of average positron lifetime by applying two-state positron trapping model for mathematical treatment of the obtained spectra.

Concentration and electrode material dependence of the voltammetric response of iodide on platinum, glassy carbon and boron-doped diamond in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide

International Nuclear Information System (INIS)

Bentley, Cameron L.; Bond, Alan M.; Hollenkamp, Anthony F.; Mahon, Peter J.; Zhang, Jie

2013-01-01

The electro-oxidation of iodide has been investigated as a function of concentration using steady-state microelectrode voltammetry, transient cyclic voltammetry and linear-sweep semi-integral voltammetry on platinum, glassy carbon and boron-doped diamond electrodes in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. Two oxidation processes are observed on all of the investigated electrode materials, with the first being assigned to the oxidation of iodide to triiodide (confirmed by UV/visible spectroscopy) and the second being attributed to the oxidation of triiodide to iodine. Iodide oxidation is kinetically more facile on platinum compared to glassy carbon or boron-doped diamond. At elevated bulk iodide concentrations, the nucleation and growth of sparingly soluble electrogenerated iodine at the electrode surface was observed and imaged in situ using optical microscopy. The diffusion coefficient of iodide was determined to be 2.59 (±0.04) × 10 −7 cm 2 s −1 and independent of the bulk concentration of iodide. The steady-state iodide oxidation current measured at a platinum microelectrode was found to be a linear function of iodide concentration, as expected if there are no contributions from non-Stokesian mass-transport processes (electron hopping and/or Grotthuss-type exchange) under the investigated conditions

Voltammetric behavior of sedative drug midazolam at glassy carbon electrode in solubilized systems

OpenAIRE

Jain, Rajeev; Yadav, Rajeev Kumar

2012-01-01

Redox behavior of midazolam was studied at a glassy carbon electrode in various buffer systems, supporting electrolytes and pH using differential pulse, square-wave and cyclic voltammetry. Based on its reduction behavior, a direct differential pulse voltammetric method has been developed and validated for the determination of midazolam in parenteral dosage. Three well-defined peaks were observed in 0.1% SLS, BrittonâRobinson (BR) buffer of pH 2.5. The effect of surfactants like sodium lauryl ...

Voltammetric behavior of sedative drug midazolam at glassy carbon electrode in solubilized systems

OpenAIRE

Jain, Rajeev; Yadav, Rajeev Kumar

2011-01-01

Redox behavior of midazolam was studied at a glassy carbon electrode in various buffer systems, supporting electrolytes and pH using differential pulse, square-wave and cyclic voltammetry. Based on its reduction behavior, a direct differential pulse voltammetric method has been developed and validated for the determination of midazolam in parenteral dosage. Three well-defined peaks were observed in 0.1% SLS, Britton–Robinson (BR) buffer of pH 2.5. The effect of surfactants like sodium lauryl ...

Crystals in the LHC

CERN Multimedia

Antonella Del Rosso

2012-01-01

Bent crystals can be used to deflect charged particle beams. Their use in high-energy accelerators has been investigated for almost 40 years. Recently, a bent crystal was irradiated for the first time in the HiRadMat facility with an extreme particle flux, which crystals would have to withstand in the LHC. The results were very encouraging and confirmed that this technology could play a major role in increasing the beam collimation performance in future upgrades of the machine.   UA9 bent crystal tested with a laser. Charged particles interacting with a bent crystal can be trapped in channelling states and deflected by the atomic planes of the crystal lattice (see box). The use of bent crystals for beam manipulation in particle accelerators is a concept that has been well-assessed. Over the last three decades, a large number of experimental findings have contributed to furthering our knowledge and improving our ability to control crystal-particle interactions. In modern hadron colliders, su...

Zak phase induced multiband waveguide by two-dimensional photonic crystals.

Science.gov (United States)

Yang, Yuting; Xu, Tao; Xu, Yun Fei; Hang, Zhi Hong

2017-08-15

Interface states in photonic crystals provide efficient approaches to control the flow of light. Photonic Zak phase determines the bulk band properties of photonic crystals, and, by assembling two photonic crystals with different bulk band properties together, deterministic interface states can be realized. By translating each unit cell of a photonic crystal by half the lattice constant, another photonic crystal with identical common gaps but a different Zak phase at each photonic band can be created. By assembling these two photonic crystals together, multiband waveguide can thus be easily created and then experimentally characterized. Our experimental results have good agreement with numerical simulations, and the propagation properties of these measured interface states indicate that this new type of interface state will be a good candidate for future applications of optical communications.

Ground and excited state absorption of Ni{sup 2+} ions in MgAl{sub 2}O{sub 4}: Crystal field analysis

Energy Technology Data Exchange (ETDEWEB)

Brik, M.G. [Fukui Institute for Fundamental Chemistry, Kyoto University, 34-4 Takano Nishihiraki-cho, Sakyo-ku, Kyoto 606-8103 (Japan) and Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337 (Japan)]. E-mail: brik@fukui.kyoto-u.ac.jp; Avram, N.M. [Department of Physics, West University of Timisoara, Bd. V. Parvan No. 4, 300223 Timisoara (Romania); Avram, C.N. [Department of Physics, West University of Timisoara, Bd. V. Parvan No. 4, 300223 Timisoara (Romania); Rudowicz, C. [Institute of Physics, Szczecin University of Technology, Al. Piastow 17, 70-310 Szczecin (Poland); Yeung, Y.Y. [Department of Mathematics, Science, Social Sciences and Technology, The Hong Kong Institute of Education, 10 Lo Ping Road, Tai Po, New Territories (Hong Kong); Gnutek, P. [Institute of Physics, Szczecin University of Technology, Al. Piastow 17, 70-310 Szczecin (Poland)

2007-04-25

The exchange charge model (ECM) of crystal field is utilized to provide the theoretical explanation of the ground state absorption and the excited state absorption observed for the octahedrally coordinated Ni{sup 2+} ions in the spinel MgAl{sub 2}O{sub 4}. The ECM enables modeling of the crystal field parameters (CFPs) for the impurity ions based on the crystal structure data of the host lattice. To ensure the reliability of the CFPs, the convergence of the CFP values with the increasing number of the coordination spheres taken into account in the ECM calculations is considered. The trigonal CFPs B{sub 2}{sup 0},B{sub 4}{sup 0}andB{sub 4}{sup -3} determined by the ECM, together with the appropriate Racah parameters B and C, serve as input to two crystal field analysis computer packages, which compute the energy level schemes within the whole 3d{sup 8} configuration. The cubic approximation utilizing only one CFP Dq is also discussed. Basic features of the ground and excited state absorption spectra observed for MgAl{sub 2}O{sub 4}:Ni{sup 2+} are satisfactorily explained by our crystal field analysis. In order to model the pressure dependence of the CFPs (and thus of the absorption spectra when relevant experimental data become available), the variation of the CFPs induced by possible distortions of the lattice due to, e.g. overall relaxation of the ions or accommodation of the impurity ions in the lattice, is studied. Analysis of the experimental absorption spectra enables us to evaluate also the Huang-Rhys parameter, the effective phonon energy, and the zero-phonon line position.

Local structure, composition, and crystallization mechanism of a model two-phase “composite nanoglass”

Energy Technology Data Exchange (ETDEWEB)

Chattopadhyay, Soma; Shibata, Tomohiro [CSRRI-IIT, MRCAT, Sector 10, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Kelly, S. D. [EXAFS Analysis, Bolingbrook, Illinois 60440 (United States); Balasubramanian, M. [Sector 20 XOR, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Srinivasan, S. G.; Du, Jincheng; Banerjee, Rajarshi [Department of Materials Science and Engineering, University of North Texas, Denton, Texas 76203-5017 (United States); Ayyub, Pushan, E-mail: pushan@tifr.res.in [Department of Condensed Matter Physics and Materials Science, Tata Institute of Fundamental Research, Mumbai 400005 (India)

2016-02-14

We report a detailed study of the local composition and structure of a model, bi-phasic nanoglass with nominal stoichiometry Cu{sub 55}Nb{sub 45}. Three dimensional atom probe data suggest a nanoscale-phase-separated glassy structure having well defined Cu-rich and Nb-rich regions with a characteristic length scale of ≈3 nm. However, extended x-ray absorption fine structure analysis indicates subtle differences in the local environments of Cu and Nb. While the Cu atoms displayed a strong tendency to cluster and negligible structural order beyond the first coordination shell, the Nb atoms had a larger fraction of unlike neighbors (higher chemical order) and a distinctly better-ordered structural environment (higher topological order). This provides the first experimental indication that metallic glass formation may occur due to frustration arising from the competition between chemical ordering and clustering. These observations are complemented by classical as well as ab initio molecular dynamics simulations. Our study indicates that these nanoscale phase-separated glasses are quite distinct from the single phase nanoglasses (studied by Gleiter and others) in the following three respects: (i) they contain at least two structurally and compositionally distinct, nanodispersed, glassy phases, (ii) these phases are separated by comparatively sharp inter-phase boundaries, and (iii) thermally induced crystallization occurs via a complex, multi-step mechanism. Such materials, therefore, appear to constitute a new class of disordered systems that may be called a composite nanoglass.

Dynamics of polymers in the bulk state by neutron scattering

International Nuclear Information System (INIS)

Kanaya, Toshiji; Kaji, Keisuke; Kawaguchi, Tatsuya; Inoue, Kazuhiko.

1992-01-01

Dynamics of polymers in the bulk state was studied by quasi- and inelastic neutron scattering techniques in the time range of 10 -13 to 10 -10 s. The present work can be classified into three parts: (i) dynamics in the glassy, state, (ii) dynamics near the glass transition and (iii) dynamics in the molten state. In the first section, we discuss the low energy excitation in glassy polymers, which is an origin of anomalous thermal properties of amorphous materials at low temperatures. In the next section, we study dynamics of amorphous polymers near the glass transition which is one of the current topics of solid state physics as well as polymer physics. It was found that two modes of motion appear near the glass transition in the energy ranges near 1 meV and of 10-30μeV. These fast and slow modes arising ca. 50K below T g and just above T g , respectively, are discussed from viewpoints of molecular basis. In the last section, dynamics in the molten state is investigated by focusing on the mechanism of local conformational transition of polymer chains. The results are analyzed in terms of jump diffusion model with damped vibrational motions and compared with the Kramers' rate theory. (author)

An all-solid-state electrochemical double-layer capacitor based on a plastic crystal electrolyte

Directory of Open Access Journals (Sweden)

Ali eaabouimrane

2015-08-01

Full Text Available A plastic crystal, solid electrolyte was prepared by mixing tetrabutylammonium hexafluorophosphate salt, (C4H94NPF6, (10 molar % with succinonitrile, SCN, (N C−CH2−CH2−C N, [SCN-10%TBA-PF6]. The resultant waxy material shows a plastic crystalline phase that extend from -36 °C up to its melting at 23 °C. It shows a high ionic conductivity reaching 4 × 10−5 S/cm in the plastic crystal phase (15 °C and ~ 3 × 10−3 S/cm in the molten state (25 °C. These properties along with the high electrochemical stability rendered the use of this material as an electrolyte in an electrochemical double-layer capacitor (EDLC. The EDLC was assembled and its performance was tested by cyclic voltammetry, AC impedance spectroscopy and galvanostatic charge-discharge methods. Specific capacitance values in the range of 4-7 F/g. (of electrode active material were obtained in the plastic crystal phase at 15 °C, that although compare well with those reported for some polymer electrolytes, can be still enhanced with further development of the device and its components, and only demonstrate their great potential use for capacitors as a new application.

An All-Solid-State Electrochemical Double-Layer Capacitor Based on a Plastic Crystal Electrolyte

Energy Technology Data Exchange (ETDEWEB)

Abouimrane, Ali; Belharouak, Ilias [Qatar Environment and Energy Research Institute, Qatar Foundation, Doha (Qatar); Abu-Lebdeh, Yaser A., E-mail: yaser.abu-lebdeh@nrc.gc.ca [Energy, Mining and Environment Portfolio and Automotive and Surface Transportation Portfolio, National Research Council of Canada, Ottawa, ON (Canada)

2015-08-18

A plastic crystal, solid electrolyte was prepared by mixing tetrabutylammonium hexafluorophosphate salt, (C{sub 4}H{sub 9}){sub 4}-NPF{sub 6}, (10 molar %) with succinonitrile, SCN, (N≡C−CH{sub 2}−CH{sub 2}−C≡N), [SCN-10%TBA-PF{sub 6}]. The resultant waxy material shows a plastic crystalline phase that extends from −36°C up to its melting at 23°C. It shows a high ionic conductivity reaching 4 × 10{sup -5} S/cm in the plastic crystal phase (15°C) and ~ 3 × 10{sup -3} S/cm in the molten state (25°C). These properties along with the high electrochemical stability rendered the use of this material as an electrolyte in an electrochemical double-layer capacitor (EDLC). The EDLC was assembled, and its performance was tested by cyclic voltammetry, AC impedance spectroscopy, and galvanostatic charge–discharge methods. Specific capacitance values in the range of 4–7 F/g (of electrode active material) were obtained in the plastic crystal phase at 15°C, that although compare well with those reported for some polymer electrolytes, can be still enhanced with further development of the device and its components, and only demonstrate their great potential use for capacitors as a new application.

An All-Solid-State Electrochemical Double-Layer Capacitor Based on a Plastic Crystal Electrolyte

International Nuclear Information System (INIS)

Abouimrane, Ali; Belharouak, Ilias; Abu-Lebdeh, Yaser A.

2015-01-01

A plastic crystal, solid electrolyte was prepared by mixing tetrabutylammonium hexafluorophosphate salt, (C 4 H 9 ) 4 -NPF 6 , (10 molar %) with succinonitrile, SCN, (N≡C−CH 2 −CH 2 −C≡N), [SCN-10%TBA-PF 6 ]. The resultant waxy material shows a plastic crystalline phase that extends from −36°C up to its melting at 23°C. It shows a high ionic conductivity reaching 4 × 10 -5 S/cm in the plastic crystal phase (15°C) and ~ 3 × 10 -3 S/cm in the molten state (25°C). These properties along with the high electrochemical stability rendered the use of this material as an electrolyte in an electrochemical double-layer capacitor (EDLC). The EDLC was assembled, and its performance was tested by cyclic voltammetry, AC impedance spectroscopy, and galvanostatic charge–discharge methods. Specific capacitance values in the range of 4–7 F/g (of electrode active material) were obtained in the plastic crystal phase at 15°C, that although compare well with those reported for some polymer electrolytes, can be still enhanced with further development of the device and its components, and only demonstrate their great potential use for capacitors as a new application.

Structural and surface changes in glassy carbon due to strontium implantation and heat treatment

Science.gov (United States)

Odutemowo, O. S.; Malherbe, J. B.; Prinsloo, L. C.; Njoroge, E. G.; Erasmus, R.; Wendler, E.; Undisz, A.; Rettenmayr, M.

2018-01-01

There are still questions around the microstructure of glassy carbon (GC), like the observation of the micropores. These were proposed to explain the low density of GC. This paper explains the effect of ion bombardment (200 keV Sr+, 1 × 1016 Sr+/cm2 at RT) on the microstructure of GC. TEM and AFM show that micropores in pristine GC are destroyed leading to densification of GC from 1.42 g/cm3 to 2.03 g/cm3. The amorphisation of glassy carbon was also not complete with graphitic strands embedded within the GC. These were relatively few, as Raman analysis showed that the Sr implantation resulted in a typical amorphous Raman spectrum. Annealing of the sample at 900 °C only resulted in a slight recovery of the GC structure. AFM and SEM analysis showed that the surface of the sample became rougher after Sr implantation. The roughness increased after the sample was annealed at 600 °C due to segregation of Sr towards the surface of the GC. SEM measurements of a sample with both implanted and un-implanted edges after annealing at 900 °C, showed that the high temperature heat treatment did not affect the surface topography of un-irradiated GC.

Temperature and frequency response of conductivity in Ag2S doped chalcogenide glassy semiconductor

Science.gov (United States)

Ojha, Swarupa; Das, Anindya Sundar; Roy, Madhab; Bhattacharya, Sanjib

2018-06-01

The electric conductivity of chalcogenide glassy semiconductor xAg2S-(1-x)(0.5S-0.5Te) has been presented here as a function of temperature and frequency. Formation of different nanocrystallites has been confirmed from X-ray diffraction study. It is also noteworthy that average size of nanocrystallites decreases with the increase of dislocation density. Dc conductivity data have been interpreted using Mott's model and Greaves's model in low and high temperature regions respectively. Ac conductivity above the room temperature has been analyzed using Meyer-Neldel (MN) conduction rule. It is interestingly noted that Correlated Barrier Hopping (CBH) model is the most appropriate conduction mechanism for x = 0.35, where pairs of charge carrier are considered to hop over the potential barrier between the sites via thermal activation. To interpret experimental data for x = 0.45, modified non-overlapping small polaron tunnelling (NSPT) model is supposed to be appropriate model due to tunnelling through grain boundary. The conductivity spectra at various temperatures have been analyzed using Almond-West Formalism (power law model). Scaling of conductivity spectra reveals that electrical relaxation process of charge carriers (polaron) is temperature independent but depends upon the composition of the present chalcogenide glassy system.

Glass Forming Ability in Systems with Competing Orderings

Science.gov (United States)

Russo, John; Romano, Flavio; Tanaka, Hajime

2018-04-01

Some liquids, if cooled rapidly enough to avoid crystallization, can be frozen into a nonergodic glassy state. The tendency for a material to form a glass when quenched is called "glass-forming ability," and it is of key significance both fundamentally and for materials science applications. Here, we consider liquids with competing orderings, where an increase in the glass-forming ability is signaled by a depression of the melting temperature towards its minimum at triple or eutectic points. With simulations of two model systems where glass-forming ability can be tuned by an external parameter, we are able to interpolate between crystal-forming and glass-forming behavior. We find that the enhancement of the glass-forming ability is caused by an increase in the structural difference between liquid and crystal: stronger competition in orderings towards the melting point minimum makes a liquid structure more disordered (more complex). This increase in the liquid-crystal structure difference can be described by a single adimensional parameter, i.e., the interface energy cost scaled by the thermal energy, which we call the "thermodynamic interface penalty." Our finding may provide a general physical principle for not only controlling the glass-forming ability but also the emergence of glassy behavior of various systems with competing orderings, including orderings of structural, magnetic, electronic, charge, and dipolar origin.

Local density of optical states in the band gap of a finite one-dimensional photonic crystal

NARCIS (Netherlands)

Yeganegi Dastgerdi, Elahe; Lagendijk, Aart; Mosk, Allard; Vos, Willem L.

2014-01-01

We study the local density of states (LDOS) in a finite photonic crystal, in particular in the frequency range of the band gap. We propose an original point of view on the band gap, which we consider to be the result of vacuum fluctuations in free space that tunnel in the forbidden range in the

Thermodynamics of Crystals

Science.gov (United States)

Navrotsky, Alexandra

Thermodynamics of Crystals is a gold mine of a references bargain with more derivations of useful equations per dollar, or per page, than almost any other book I know. Useful to whom? To the solid state physicist, the solid state chemist working the geophysicist, the rock mechanic, the mineral physicist. Useful for what? For lattice dynamics, crystal potentials, band structure. For elegant, rigorous, and concise derivations of fundamental equations. For comparison of levels of approximation. For some data and physical insights, especially for metals and simple halides. This book is a reissue, with some changes and additions, of a 1970 treatise. It ages well, since the fundamentals do not change.

Impacts of Co-doping on the superconductivity and the orbital ordering state in Fe1-xCoxSe single crystal studied by the electrical transport.

Science.gov (United States)

Urata, Takahiro; Tanabe, Yoichi; Heguri, Satoshi; Tanigaki, Katsumi

2015-03-01

In the FeSe with the simplest crystal structure in the Fe-based superconductor families, although both the superconductivity and the orbital ordering states are investigated, the relation between them is still unclear. Here, we report Co doping effects on the superconductivity and the orbital ordering state in Fe1-xCoxSe single crystals. The electrical transport measurements demonstrated that the superconductivity vanishes at 4 % Co doping while the orbital ordering state may be robust against Co doping. Present results suggest that the orbital ordering state is not related to the emergence of the superconductivity in FeSe.

Proton nuclear magnetic resonance studies of hydrogen diffusion and electron tunneling in Ni-Nb-Zr-H glassy alloys

Energy Technology Data Exchange (ETDEWEB)

Niki, Haruo; Okuda, Hiroyuki; Oshiro, Morihito; Yogi, Mamoru [Department of Physics, Faculty of Science, University of the Ryukyus, Nishihara, Okinawa 903-0213 (Japan); Seki, Ichiro; Fukuhara, Mikio [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan)

2012-06-15

Using the Fourier transform of the echo envelope, the proton line shapes, spin-lattice relaxation time, and spin-spin relaxation time have been measured in a (Ni{sub 0.36}Nb{sub 0.24}Zr{sub 0.40}){sub 90}H{sub 10} glassy alloy at 1.83 T ({approx}78 MHz) and at temperatures between 1.8 and 300 K. First, the spectral line width decreases abruptly between 1.8 and 2.1 K. Next, it remains almost constant at 13 kHz up to {approx}150 K. Finally, the line width decreases as the temperature increases from {approx}150 to 300 K. The initial decrease in the spectral line width is ascribed to the distribution of the external field, which is caused by the penetration of vortices in the superconducting state. The subsequent leveling off in the spectral line width is ascribed to the dipole-dipole interaction between protons when hydrogen atoms are trapped into vacancies among the Zr-centered icosahedral Zr{sub 5}Ni{sub 5}Nb{sub 3} clusters. The final decrease in the spectral line width is ascribed to the motional narrowing of the width that is caused by the movement of hydrogen atoms. The temperature dependences of the spin-lattice and spin-spin relaxation time showed that at temperature above 150 K and the activation energy of 8.7 kJ/mol allowed the hydrogen atoms to migrate among the clusters. The distance between the hydrogen atoms is estimated to be 2.75 A. Hydrogen occupancies among clusters in the (Ni{sub 0.36}Nb{sub 0.24}Zr{sub 0.40}){sub 90}H{sub 10} glassy alloy play an important role in the diffusion behavior and in the electronic properties of this alloy.

Effect of grain-boundary crystallization on the high-temperature strength of silicon nitride

Science.gov (United States)

Pierce, L. A.; Mieskowski, D. M.; Sanders, W. A.

1986-01-01

Si3N4 specimens having the composition 88.7 wt pct Si3N4-4.9 wt pct SiO2-6.4 wt pct Y2O3 were sintered at 2140 C under 25 atm N2 for 1 h and then subjected to a 5 h anneal at 1500 C. Crystallization of an amorphous grain-boundary phase resulted in the formation of Y2Si2O7. The short-time 1370 C strength of this material was compared with that of material of the same composition having no annealing treatment. No change in strength was noted. This is attributed to the refractory nature of the yttrium-rich grain-boundary phase (apparently identical in both glassy and crystalline phases) and the subsequent domination of the failure process by common processing flaws.

Eutectic crystallization behavior of new Zr48Cu36Al8Ag8 alloy with high glass-forming ability

International Nuclear Information System (INIS)

Zhang, Q S; Zhang, W; Xie, G Q; Inoue, A

2009-01-01

A water quenching method is used to produce as-cast Zr 48 Cu 36 Al 8 Ag 8 rods with diameters from 20 mm to 25 mm. The microstructures of the as-cast samples were investigated by X-ray diffraction, optical microscopy and scanning electron microscopy. Furthermore, the crystallization behavior of the Zr 48 Cu 36 Al 8 Ag 8 glassy alloy was examined by XRD and transmission electron microscopy. Based on the results obtained one can assume that the simultaneous precipitation of the Zr 2 Cu+AlCu 2 Zr eutectic phases is the possible reason for the high stabilization of the quaternary Zr 48 Cu 36 Al 8 Ag 8 supercooled liquid.

Pressure-induced emission band separation of the hybridized local and charge transfer excited state in a TPE-based crystal.

Science.gov (United States)

Liu, Xuedan; Li, Aisen; Xu, Weiqing; Ma, Zhiyong; Jia, Xinru

2018-05-08

We herein report a newly synthesized simple molecule, named TPE[double bond, length as m-dash]C4, with twisted D-A structure. TPE[double bond, length as m-dash]C4 showed two intrinsic emission bands ascribed to the locally excited (LE) state and the intramolecular charge transfer (ICT) state, respectively. In the crystal state, the LE emission band is usually observed. However, by applying hydrostatic pressure to the powder sample and the single crystal sample of TPE[double bond, length as m-dash]C4, dual-fluorescence (445 nm and 532 nm) was emerged under high pressure, owing to the pressure-induced emission band separation of the hybridized local and charge transfer excited state (HLCT). It is found that the emission of TPE[double bond, length as m-dash]C4 is generally determined by the ratio of the LE state to the ICT state. The ICT emission band is much more sensitive to the external pressure than the LE emission band. The HLCT state leads to a sample with different responsiveness to grinding and hydrostatic pressure. This study is of significance in the molecular design of such D-A type molecules and in the control of photoluminescence features by molecular structure. Such results are expected to pave a new way to further understand the relationship between the D-A molecular structure and stimuli-responsive properties.

Automation in biological crystallization.

Science.gov (United States)

Stewart, Patrick Shaw; Mueller-Dieckmann, Jochen

2014-06-01

Crystallization remains the bottleneck in the crystallographic process leading from a gene to a three-dimensional model of the encoded protein or RNA. Automation of the individual steps of a crystallization experiment, from the preparation of crystallization cocktails for initial or optimization screens to the imaging of the experiments, has been the response to address this issue. Today, large high-throughput crystallization facilities, many of them open to the general user community, are capable of setting up thousands of crystallization trials per day. It is thus possible to test multiple constructs of each target for their ability to form crystals on a production-line basis. This has improved success rates and made crystallization much more convenient. High-throughput crystallization, however, cannot relieve users of the task of producing samples of high quality. Moreover, the time gained from eliminating manual preparations must now be invested in the careful evaluation of the increased number of experiments. The latter requires a sophisticated data and laboratory information-management system. A review of the current state of automation at the individual steps of crystallization with specific attention to the automation of optimization is given.

A consequence of local equilibration and heterogeneity in glassy materials

International Nuclear Information System (INIS)

Berthier, Ludovic

2003-01-01

The existence of a generalized fluctuation-dissipation theorem observed in simulations and experiments performed in various glassy materials is related to the concepts of local equilibration and heterogeneity in space. Assuming the existence of a dynamic coherence length scale up to which the system is locally equilibrated, we extend previous generalizations of the FDT relating static to dynamic quantities to the physically relevant domain where asymptotic limits of large times and sizes are not reached. The formulation relies on a simple scaling argument and thus does not have the character of a theorem. Extensive numerical simulations support this proposition. Our results quite generally apply to systems with slow dynamics, independently of the space dimensionality, the chosen dynamics or the presence of disorder

Optically Anomalous Crystals

CERN Document Server

Shtukenberg, Alexander; Kahr, Bart

2007-01-01

Optical anomalies in crystals are puzzles that collectively constituted the greatest unsolved problems in crystallography in the 19th Century. The most common anomaly is a discrepancy between a crystal’s symmetry as determined by its shape or by X-ray analysis, and that determined by monitoring the polarization state of traversing light. These discrepancies were perceived as a great impediment to the development of the sciences of crystals on the basis of Curie’s Symmetry Principle, the grand organizing idea in the physical sciences to emerge in the latter half of the 19th Century. Optically Anomalous Crystals begins with an historical introduction covering the contributions of Brewster, Biot, Mallard, Brauns, Tamman, and many other distinguished crystallographers. From this follows a tutorial in crystal optics. Further chapters discuss the two main mechanisms of optical dissymmetry: 1. the piezo-optic effect, and 2. the kinetic ordering of atoms. The text then tackles complex, inhomogeneous crystals, and...

Organic semiconductor crystals.

Science.gov (United States)

Wang, Chengliang; Dong, Huanli; Jiang, Lang; Hu, Wenping

2018-01-22

Organic semiconductors have attracted a lot of attention since the discovery of highly doped conductive polymers, due to the potential application in field-effect transistors (OFETs), light-emitting diodes (OLEDs) and photovoltaic cells (OPVs). Single crystals of organic semiconductors are particularly intriguing because they are free of grain boundaries and have long-range periodic order as well as minimal traps and defects. Hence, organic semiconductor crystals provide a powerful tool for revealing the intrinsic properties, examining the structure-property relationships, demonstrating the important factors for high performance devices and uncovering fundamental physics in organic semiconductors. This review provides a comprehensive overview of the molecular packing, morphology and charge transport features of organic semiconductor crystals, the control of crystallization for achieving high quality crystals and the device physics in the three main applications. We hope that this comprehensive summary can give a clear picture of the state-of-art status and guide future work in this area.

Molecular imprinted polypyrrole modified glassy carbon electrode for the determination of tobramycin

International Nuclear Information System (INIS)

Gupta, Vinod Kumar; Yola, Mehmet Lütfi; Özaltın, Nuran; Atar, Necip; Üstündağ, Zafer; Uzun, Lokman

2013-01-01

Graphical abstract: Atomic force microscopic images of (A) bare GCE and (B) TOB imprinted PPy/GCE surface. - Highlights: • Glassy carbon electrode based on molecularly imprinted polypyrrole was prepared. • The developed surfaces were characterized by AFM, FTIR, EIS and CV. • The developed nanosensor was applied to egg and milk samples. - Abstract: Over the past two decades, molecular imprinted polymers have attracted a broad interest from scientists in sensor development. In the preparation of molecular imprinted polymers the desired molecule (template) induces the creation of specific recognition sites in the polymer. In this study, the glassy carbon electrode (GCE) based on molecularly imprinted polypyrrole (PPy) was fabricated for the determination of tobramycin (TOB). The developed electrode was prepared by incorporation of a template molecule (TOB) during the electropolymerization of pyrrole on GCE in aqueous solution using cyclic voltammetry (CV) method. The performance of the imprinted and non-imprinted electrodes was evaluated by square wave voltammetry (SWV). The effect of pH, monomer and template concentrations, electropolymerization cycles on the performance of the imprinted and non-imprinted electrodes was investigated and optimized. The non-modified and TOB-imprinted surfaces were characterized by using atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), electrochemical impedance spectroscopy (EIS) and CV. The linearity range of TOB was 5.0 × 10 −10 –1.0 × 10 −8 M with the detection limit of 1.4 × 10 −10 M. The developed nanosensor was applied successfully for the determination of TOB in egg and milk

Voltammetric Determination of Acetaminophen in the Presence of Codeine and Ascorbic Acid at Layer-by-Layer MWCNT/Hydroquinone Sulfonic Acid-Overoxidized Polypyrrole Modified Glassy Carbon Electrode

OpenAIRE

Shahrokhian, Saeed; Saberi, Reyhaneh-Sadat

2011-01-01

A very sensitive electrochemical sensor constructed of a glassy carbon electrode modified with a layer-by-layer MWCNT/doped-overoxidized polypyrrole (oppy/MWCNT /GCE) was used for the determination of acetaminophen (AC) in the presence of codeine and ascorbic acid (AA). In comparison to the bare glassy carbon electrode, a considerable shift in the peak potential together with an increase in the peak current was observed for AC on the surface of oppy/MWCNT/GCE, which can be related to the enla...

Glassy-state stabilization of a dominant negative inhibitor anthrax vaccine containing aluminum hydroxide and glycopyranoside lipid A adjuvants.

Science.gov (United States)

Hassett, Kimberly J; Vance, David J; Jain, Nishant K; Sahni, Neha; Rabia, Lilia A; Cousins, Megan C; Joshi, Sangeeta; Volkin, David B; Middaugh, C Russell; Mantis, Nicholas J; Carpenter, John F; Randolph, Theodore W

2015-02-01

During transport and storage, vaccines may be exposed to temperatures outside of the range recommended for storage, potentially causing efficacy losses. To better understand and prevent such losses, dominant negative inhibitor (DNI), a recombinant protein antigen for a candidate vaccine against anthrax, was formulated as a liquid and as a glassy lyophilized powder with the adjuvants aluminum hydroxide and glycopyranoside lipid A (GLA). Freeze-thawing of the liquid vaccine caused the adjuvants to aggregate and decreased its immunogenicity in mice. Immunogenicity of liquid vaccines also decreased when stored at 40°C for 8 weeks, as measured by decreases in neutralizing antibody titers in vaccinated mice. Concomitant with efficacy losses at elevated temperatures, changes in DNI structure were detected by fluorescence spectroscopy and increased deamidation was observed by capillary isoelectric focusing (cIEF) after only 1 week of storage of the liquid formulation at 40°C. In contrast, upon lyophilization, no additional deamidation after 4 weeks at 40°C and no detectable changes in DNI structure or reduction in immunogenicity after 16 weeks at 40°C were observed. Vaccines containing aluminum hydroxide and GLA elicited higher immune responses than vaccines adjuvanted with only aluminum hydroxide, with more mice responding to a single dose. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Forced-ferromagnetic state in a Tm.sub.2./sub.Fe.sub.17./sub.H.sub.5./sub. single crystal

Czech Academy of Sciences Publication Activity Database

Tereshina, Evgeniya; Kuz'min, M.D.; Skourski, Y.; Doerr, M.; Iwasieczko, W.; Wosnitza, J.; Tereshina, I. S.

2017-01-01

Roč. 29, č. 24 (2017), s. 1-6, č. článku 24LT01. ISSN 0953-8984 Institutional support: RVO:68378271 Keywords : single crystal * hydride * forced-ferromagnetic state * rare- earth -iron intermetallic compound Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 2.649, year: 2016

Crystals in light.

Science.gov (United States)

Kahr, Bart; Freudenthal, John; Gunn, Erica

2010-05-18

We have made images of crystals illuminated with polarized light for almost two decades. Early on, we abandoned photosensitive chemicals in favor of digital electrophotometry with all of the attendant advantages of quantitative intensity data. Accurate intensities are a boon because they can be used to analytically discriminate small effects in the presence of larger ones. The change in the form of our data followed camera technology that transformed picture taking the world over. Ironically, exposures in early photographs were presumed to correlate simply with light intensity, raising the hope that photography would replace sensorial interpretation with mechanical objectivity and supplant the art of visual photometry. This was only true in part. Quantitative imaging accurate enough to render the separation of crystalloptical quantities had to await the invention of the solid-state camera. Many pioneers in crystal optics were also major figures in the early history of photography. We draw out the union of optical crystallography and photography because the tree that connects the inventors of photography is a structure unmatched for organizing our work during the past 20 years, not to mention that silver halide crystallites used in chemical photography are among the most consequential "crystals in light", underscoring our title. We emphasize crystals that have acquired optical properties such as linear birefringence, linear dichroism, circular birefringence, and circular dichroism, during growth from solution. Other crystalloptical effects were discovered that are unique to curiously dissymmetric crystals containing embedded oscillators. In the aggregate, dyed crystals constitute a generalization of single crystal matrix isolation. Simple crystals provided kinetic stability to include guests such as proteins or molecules in excited states. Molecular lifetimes were extended for the preparation of laser gain media and for the study of the photodynamics of single

Unique Reversible Crystal-to-Crystal Phase Transition – Structural and Functional Properties of Fused Ladder Thienoarenes

KAUST Repository

Abe, Yuichiro

2017-08-15

Donor-acceptor type molecules based on fused ladder thienoarenes, indacenodithiophene (IDT) and dithienocyclopenta-thienothiophene (DTCTT), coupled with benzothiadiazole, are prepared and their solid-state structures are investigated. They display a rich variety of solid phases ranging from amorphous glass states to crystalline states, upon changes in the central aromatic core and side group structures. Most notably, the DTCTT-based derivatives showed reversible crystal-to-crystal phase transitions in heating and cooling cycles. Unlike what has been seen in π−conjugated molecules variable temperature XRD revealed that structural change occurs continuously during the transition. A columnar self-assembled structure with slip-stacked π−π interaction is proposed to be involved in the solid-state. This research provides the evidence of unique structural behavior of the DTCTT-based molecules through the detailed structural analysis. This unique structural transition paves the way for these materials to have self-healing of crystal defects, leading to improved optoelectronic properties.

Unique Reversible Crystal-to-Crystal Phase Transition – Structural and Functional Properties of Fused Ladder Thienoarenes

KAUST Repository

Abe, Yuichiro; Savikhin, Victoria; Yin, Jun; Grimsdale, Andrew C.; Soci, Cesare; Toney, Michael F.; Lam, Yeng Ming

2017-01-01

Donor-acceptor type molecules based on fused ladder thienoarenes, indacenodithiophene (IDT) and dithienocyclopenta-thienothiophene (DTCTT), coupled with benzothiadiazole, are prepared and their solid-state structures are investigated. They display a rich variety of solid phases ranging from amorphous glass states to crystalline states, upon changes in the central aromatic core and side group structures. Most notably, the DTCTT-based derivatives showed reversible crystal-to-crystal phase transitions in heating and cooling cycles. Unlike what has been seen in π−conjugated molecules variable temperature XRD revealed that structural change occurs continuously during the transition. A columnar self-assembled structure with slip-stacked π−π interaction is proposed to be involved in the solid-state. This research provides the evidence of unique structural behavior of the DTCTT-based molecules through the detailed structural analysis. This unique structural transition paves the way for these materials to have self-healing of crystal defects, leading to improved optoelectronic properties.

Evaluation of liquid fragility and thermal stability of Al-based metallic glasses by equivalent structure parameter

International Nuclear Information System (INIS)

Li Xuelian; Bian Xiufang; Hu Lina

2010-01-01

Based on extended Ideal-Atomic-Packing model, we propose an equivalent structure parameter '6x+11y' to evaluate fragility and thermal stability of Al-TM-RE metallic glasses, where x and y are composition concentrations of transition metal (TM) and rare earth (RE), respectively. Experimental results show that glass forming compositions with '6x+11y' near 100 have the smallest fragility parameter and best structure stability. In addition, '6x+11y' parameter has a positive relationship with onset-crystallization temperature, T x . Al-TM-RE glassy alloys with (6x+11y)≤100 undergo primary crystallization of fcc-Al nanocrystals, while alloys with (6x+11y)>100 exhibit nanoglassy or glassy crystallization behavior.

Impedance aspect of charge storage at graphite and glassy carbon electrodes in potassium hexacyanoferrate (II redox active electrolyte

Directory of Open Access Journals (Sweden)

Katja Magdić

2016-04-01

Full Text Available Different types of charge storage mechanisms at unmodified graphite vs. glassy carbon electrodes in acid sulphate supporting solution containing potassium hexacyanoferrate (II redox active electrolyte, have been revealed by electrochemical impedance spectroscopy and supported by cyclic voltammetry experiments. Reversible charge transfer of Fe(CN63-/4- redox reaction detected by assessment of CVs of glassy carbon electrode, is in impedance spectra indicated by presence of bulk diffusion impedance and constant double-layer/pseudocapacitive electrode impedance compared to that measured in the pure supporting electrolyte. Some surface retention of redox species detected by assessment of CVs of graphite electrode is in impedance spectra indicated by diffusion impedance coupled in this case by diminishing of double-layer/pseudo­capacitive impedance compared to that measured in the pure supporting electrolyte. This phenomenon is ascribed to contribution of additional pseudocapacitive impedance generated by redox reaction of species confined at the electrode surface.

Electrochemical deposition of gold nanoparticles on carbon nanotube coated glassy carbon electrode for the improved sensing of tinidazole

International Nuclear Information System (INIS)

Shahrokhian, Saeed; Rastgar, Shokoufeh

2012-01-01

The electrochemical reduction of tinidazole (TNZ) is studied on gold-nanoparticle/carbon-nanotubes (AuNP/CNT) modified glassy carbon electrodes using the linear sweep voltammetry. An electrochemical procedure was used for the deposition of gold nanoparticles onto the carbon nanotube film pre-cast on a glassy carbon electrode surface. The resulting nanoparticles were characterized by scanning electron microscopy and cyclic voltammetry. The effect of the electrodeposition conditions, e.g., salt concentration and deposition time on the response of the electrode was studied. Also, the effect of experimental parameters, e.g., potential and time of accumulation, pH of the buffered solutions and the potential sweep rate on the response is examined. Under the optimal conditions, the modified electrode showed a wide linear response toward the concentration of TNZ in the range of 0.1–50 μM with a detection limit of 10 nM. The prepared electrode was successfully applied for the determination of TNZ in pharmaceutical and clinical samples.

A 3D Microfluidic Chip for Electrochemical Detection of Hydrolysed Nucleic Bases by a Modified Glassy Carbon Electrode

Directory of Open Access Journals (Sweden)

Jana Vlachova

2015-01-01

Full Text Available Modification of carbon materials, especially graphene-based materials, has wide applications in electrochemical detection such as electrochemical lab-on-chip devices. A glassy carbon electrode (GCE modified with chemically alternated graphene oxide was used as a working electrode (glassy carbon modified by graphene oxide with sulphur containing compounds and Nafion for detection of nucleobases in hydrolysed samples (HCl pH = 2.9, 100 °C, 1 h, neutralization by NaOH. It was found out that modification, especially with trithiocyanuric acid, increased the sensitivity of detection in comparison with pure GCE. All processes were finally implemented in a microfluidic chip formed with a 3D printer by fused deposition modelling technology. As a material for chip fabrication, acrylonitrile butadiene styrene was chosen because of its mechanical and chemical stability. The chip contained the one chamber for the hydrolysis of the nucleic acid and another for the electrochemical detection by the modified GCE. This chamber was fabricated to allow for replacement of the GCE.

A 3D microfluidic chip for electrochemical detection of hydrolysed nucleic bases by a modified glassy carbon electrode.

Science.gov (United States)

Vlachova, Jana; Tmejova, Katerina; Kopel, Pavel; Korabik, Maria; Zitka, Jan; Hynek, David; Kynicky, Jindrich; Adam, Vojtech; Kizek, Rene

2015-01-22

Modification of carbon materials, especially graphene-based materials, has wide applications in electrochemical detection such as electrochemical lab-on-chip devices. A glassy carbon electrode (GCE) modified with chemically alternated graphene oxide was used as a working electrode (glassy carbon modified by graphene oxide with sulphur containing compounds and Nafion) for detection of nucleobases in hydrolysed samples (HCl pH = 2.9, 100 °C, 1 h, neutralization by NaOH). It was found out that modification, especially with trithiocyanuric acid, increased the sensitivity of detection in comparison with pure GCE. All processes were finally implemented in a microfluidic chip formed with a 3D printer by fused deposition modelling technology. As a material for chip fabrication, acrylonitrile butadiene styrene was chosen because of its mechanical and chemical stability. The chip contained the one chamber for the hydrolysis of the nucleic acid and another for the electrochemical detection by the modified GCE. This chamber was fabricated to allow for replacement of the GCE.

Study of the In2O3 molecule in the free state and in the crystal

Science.gov (United States)

Kaplan, Ilya G.; Miranda, Ulises; Trakhtenberg, Leonid I.

2018-03-01

The nanomaterials based on the In2O3 molecule are widely used as catalysts and sensors among other applications. In the present study, we discuss the possibility of using nanoclusters of In2O3 as molecular photomotors. A comparative analysis of the electronic structure of the In2O3 molecule in the free state and in the crystal is performed. For the free In2O3 molecule the geometry of its lowest structures, V-shape and linear, was optimised at the CCSD(T) level, which is the most precise computational method applied up to date to study In2O3. Using experimental crystallographic data, we determined the geometry of In2O3 in the crystal. It has a zigzag, not symmetric structure and possesses a dipole moment with magnitude slightly smaller than that of the V-structure of the free molecule (the linear structure due to its symmetry has no dipole moment). According to the Natural Atomic population analysis, the chemical structure of the linear In2O3 can be represented as O = In-O-In = O; the V-shaped molecule has the similar double- and single-bond structure. The construction of nanoclusters from ´bricksʼ of In2O3 with geometry extracted from crystal (or nanoclusters extracted directly from crystal) and their use as photo-driven molecular motors are discussed.

A roadmap to uranium ionic liquids: Anti-crystal engineering

Energy Technology Data Exchange (ETDEWEB)

Yaprak, Damla; Spielberg, Eike T.; Baecker, Tobias; Richter, Mark; Mallick, Bert [Inorganic Chemistry III, Ruhr-University Bochum (Germany); Klein, Axel [Institut fuer Anorganische Chemie, Koeln Univ. (Germany); Mudring, Anja-Verena [Inorganic Chemistry III, Ruhr-University Bochum (Germany); Materials Science and Engineering, Iowa State University and Critical Materials Institute, Ames Laboratory, Ames, IA (United States)

2014-05-19

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C{sub 4}mim) cation. As dithiocarbamate ligands binding to the UO{sub 2}{sup 2+} unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure-property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. These materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

A roadmap to uranium ionic liquids: Anti-crystal engineering

International Nuclear Information System (INIS)

Yaprak, Damla; Spielberg, Eike T.; Baecker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja-Verena

2014-01-01

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C_4mim) cation. As dithiocarbamate ligands binding to the UO_2"2"+ unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure-property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. These materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Growth and characterization of nonlinear optical single crystals: bis ...

Indian Academy of Sciences (India)

Administrator

molecules have received great attention for NLO applica- tions. However ... Figure 3. Single crystals of bis(cyclohexylammonium) terephthalate (crystal a) and cyclohexylammo- .... from ground state to higher energy states.17 Optical window ...

Beating Homogeneous Nucleation and Tuning Atomic Ordering in Glass-Forming Metals by Nanocalorimetry.

Science.gov (United States)

Zhao, Bingge; Yang, Bin; Abyzov, Alexander S; Schmelzer, Jürn W P; Rodríguez-Viejo, Javier; Zhai, Qijie; Schick, Christoph; Gao, Yulai

2017-12-13

In this paper, the amorphous Ce 68 Al 10 Cu 20 Co 2 (atom %) alloy was in situ prepared by nanocalorimetry. The high cooling and heating rates accessible with this technique facilitate the suppression of crystallization on cooling and the identification of homogeneous nucleation. Different from the generally accepted notion that metallic glasses form just by avoiding crystallization, the role of nucleation and growth in the crystallization behavior of amorphous alloys is specified, allowing an access to the ideal metallic glass free of nuclei. Local atomic configurations are fundamentally significant to unravel the glass forming ability (GFA) and phase transitions in metallic glasses. For this reason, isothermal annealing near T g from 0.001 s to 25,000 s following quenching becomes the strategy to tune local atomic configurations and facilitate an amorphous alloy, a mixed glassy-nanocrystalline state, and a crystalline sample successively. On the basis of the evolution of crystallization enthalpy and overall latent heat on reheating, we quantify the underlying mechanism for the isothermal nucleation and crystallization of amorphous alloys. With Johnson-Mehl-Avrami method, it is demonstrated that the coexistence of homogeneous and heterogeneous nucleation contributes to the isothermal crystallization of glass. Heterogeneous rather than homogeneous nucleation dominates the isothermal crystallization of the undercooled liquid. For the mixed glassy-nanocrystalline structure, an extraordinary kinetic stability of the residual glass is validated, which is ascribed to the denser packed interface between amorphous phase and ordered nanocrystals. Tailoring the amorphous structure by nanocalorimetry permits new insights into unraveling GFA and the mechanism that correlates local atomic configurations and phase transitions in metallic glasses.

Degradation of L-Ascorbic Acid in the Amorphous Solid State.

Science.gov (United States)

Sanchez, Juan O; Ismail, Yahya; Christina, Belinda; Mauer, Lisa J

2018-03-01

Ascorbic acid degradation in amorphous solid dispersions was compared to its degradation in the crystalline state. Physical blends and lyophiles of ascorbic acid and polymers (pectins and polyvinylpyrrolidone [PVP]) were prepared initially at 50:50 (w/w), with further studies using the polymer that best inhibited ascorbic acid crystallization in the lyophiles in 14 vitamin : PVP ratios. Samples were stored in controlled environments (25 to 60 °C, 0% to 23% RH) for 1 mo and analyzed periodically to track the physical appearance, change in moisture content, physical state (powder x-ray diffraction and polarized light microscopy), and vitamin loss (high performance liquid chromatography) over time. The glass transition temperatures of select samples were determined using differential scanning calorimetry, and moisture sorption profiles were generated. Ascorbic acid in the amorphous form, even in the glassy amorphous state, was more labile than in the crystalline form in some formulations at the highest storage temperature. Lyophiles stored at 25 and 40 °C and those in which ascorbic acid had crystallized at 60 °C (≥70% ascorbic acid : PVP) had no significant difference in vitamin loss (P > 0.05) relative to physical blend controls, and the length of storage had little effect. At 60 °C, amorphous ascorbic acid lyophiles (≤60% ascorbic acid : PVP) lost significantly more vitamin (P vitamin loss significantly increased over time. In these lyophiles, vitamin degradation also significantly increased (P vitamins are naturally present or added at low concentrations and production practices may promote amorphization of the vitamin. Vitamin C is one of the most unstable vitamins in foods. This study documents that amorphous ascorbic acid is less stable than crystalline ascorbic acid in some environments (for example, higher temperatures within 1 wk), especially when the vitamin is present at low concentrations in a product. These findings increase the understanding of

Triphenylene columnar liquid crystals: spectroscopic study of triplets states and charge carriers

International Nuclear Information System (INIS)

Bondkowski, Jens

2000-01-01

This research thesis reports the study of three oxygenated derivatives of triphenylene (two monomers, a symmetric one and an asymmetric one, and a tetramer) by using different experimental techniques: absorption spectroscopy and fluorescence spectroscopy in stationary regime, and time-resolved fluorescence spectroscopy (also said single photon counting). Moreover, the author adapted an existing experiment of transient absorption spectroscopy time-resolved at the microsecond level to obtain spectra of thin layers under electric field. A cyclic voltammetry experiment and a spectro-electrochemistry experiment have also been performed. The report first presents the studied materials, the characterisation of singlet states, and the study of the effect molecular symmetry decreasing have on molecular transitions. Then, the author reports the study of cationic species of the triphenylene derivatives. The next chapters address the characterisation of derivative triplet states, and the study of energy transfer within the meso phase of one of these derivatives. The last chapters address charge carriers of columnar liquid crystals, and the molecular nature of these charge carriers

Influence of crystal habit on trimethoprim suspension formulation.

Science.gov (United States)

Tiwary, A K; Panpalia, G M

1999-02-01

The role of crystal habit in influencing the physical stability and pharmacokinetics of trimethoprim suspensions was examined. Different habits for trimethoprim (TMP) were obtained by recrystallizing the commercial sample (PD) utilizing solvent-change precipitation method. Four distinct habits (microscopic observation) belonging to the same polymorphic state (DSC studies) were selected for studies. Preformulation and formulation studies were carried out on suspension dosage forms containing these crystals. The freshly prepared suspensions were also evaluated for their pharmacokinetic behaviour on healthy human volunteers using a cross over study. Variation of crystallization conditions produces different habits of TMP. Among the different crystal habits exhibiting same polymorphic state, the most anisometric crystal showed best physical stability in terms of sedimentation volume and redispersibility. However, habit did not significantly affect the extent of TMP excreted in urine. Modification of surface morphology without significantly altering the polymorphic state can be utilized for improving physical stability of TMP suspensions. However, the pharmacokinetic profile remains unaltered.

Moessbauer effect study of oxidation and coordination states of iron in some sodium borate glasse:;

International Nuclear Information System (INIS)

Eissa, N.A.; Sanad, A.M.; Youssef, S.M.; El-Henawii, S.A.; Gomaa, S.Sh.; Mostafa, A.G.

1980-01-01

A structural study of some sodium borate glasses containing iron was carried out applying ME spectroscopy. Both oxidation and coordination states of iron were investigated under the effect of gradual replacing of sodium carbonate by sodium nitrate in the glass batches. The glasses were melted in porcelain crucibles using an electrically heated furnace at 1000+-10 deg C, then were quenched on a steel plate at room temperature (R.T.). The ME source was 20 mCi radioactive Co-57 in chromium. The obtained ME spectra indicated that at lower sodium nitrate content both Fe 2+ and Fe 3+ are present in these glasses. At moderate concentrations some Fe 3+ ions were separated in a crystalline phase and the rest of the iron ions appeared as ferric ions in glassy state. At high sodium nitrate content only Fe 3+ ions in glassy state were detected. The values of the ME parameters for all iron ions indicated that all of them are in the octahedral coordination state. The density measurements confirm the separation of a crystalline phase at moderate sodium nitrate content. (author)

Photogeneration of singlet oxygen by the phenothiazine derivatives covalently bound to the surface-modified glassy carbon

Energy Technology Data Exchange (ETDEWEB)

Blacha-Grzechnik, Agata, E-mail: agata.blacha@polsl.pl [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland); Piwowar, Katarzyna; Krukiewicz, Katarzyna [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland); Koscielniak, Piotr; Szuber, Jacek [Institute of Electronics, Silesian University of Technology, Akademicka 16, 44-100 Gliwice (Poland); Zak, Jerzy K. [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland)

2016-05-15

Highlights: • The selected group of four NH{sub 2}-derivatives of phenothiazine was grafted to Glassy Carbon (GC) surface. • The grafted phenothiazines are able to generate {sup 1}O{sub 2} when activated by the radiation. • Such modified solid surfaces may find their application in the wastewater treatment. - Abstract: The selected group of four amine-derivatives of phenothiazine was covalently grafted to the glassy carbon surface in the four-step procedure consisting of the electrochemical reduction of the diazonium salt followed by the electrochemical and chemical post-modification steps. The proposed strategy involves the bonding of linker molecule to which the photosensitizer is attached. The synthesized organic layers were characterized by means of cyclic voltammetry, XPS and Raman Spectroscopy. It was shown that the phenothiazines immobilized via proposed strategy retain their photochemical properties and are able to generate {sup 1}O{sub 2} when activated by the laser radiation. The effectiveness of in situ singlet oxygen generation by those new solid photoactive materials was determined by means of UVVis spectroscopy. The reported, covalently modified solid surfaces may find their application as the singlet oxygen photogenerators in the fine chemicals’ synthesis or in the wastewater treatment.

Electrocatalytic Determination of Isoniazid by a Glassy Carbon Electrode Modified with Poly (Eriochrome Black T

Directory of Open Access Journals (Sweden)

Karim Asadpour-Zeynali

2017-06-01

Full Text Available In this work poly eriochrome black T (EBT was electrochemically synthesized on the glassy carbon electrode as electrode modifier. On the modified electrode, voltammetric behavior of isoniazid (INH was investigated. The poly (EBT-modified glassy carbon electrode has excellent electrocatalytic ability for the electrooxidation of isoniazid. This fact was appeared as a reduced overpotential of INH oxidation in a wide operational pH range from 2 to 13. It has been found that the catalytic peak current depends on the concentration of INH and solution pH. The number of electrons involved in the rate determining step was found 1. The diffusion coefficient of isoniazid was also estimated using chronoamperometry technique. The experimental results showed that the mediated oxidation peak current of isoniazid is linearly dependent on the concentration of isoniazid in the ranges of 8.0 × 10-6 – 1.18 × 10-3 M and 2.90 × 10-5 M – 1.67× 10-3 M with differential pulse voltammetry (DPV and amperometry methods, respectively. The detection limits (S/N = 3 were found to be 6.0 μM and 16.4 μM by DPV and amperometry methods, respectively. This developed method was applied to the determination of isoniazid in tablet samples with satisfactory results.

Crystal phases of a glass-forming Lennard-Jones mixture

International Nuclear Information System (INIS)

Fernandez, Julian R.; Harrowell, Peter

2003-01-01

We compare the potential energy at zero temperature of a range of crystal structures for a glass-forming binary mixture of Lennard-Jones particles. The lowest-energy ordered state consists of coexisting phases of a single component face centered cubic structure and an equimolar cesium chloride structure. An infinite number of layered crystal structures are identified with energies close to this ground state. We demonstrate that the finite size increase of the energy of the coexisting crystal with incoherent interfaces is sufficient to destabilize this ordered phase in simulations of typical size. Two specific local coordination structures are identified as of possible structural significance in the amorphous state. We observe rapid crystal growth in the equimolar mixture

Age and petrogenetic constraints on the Lower Glassy Ignimbrite of the Mount Somers Volcanic Group, New Zealand

DEFF Research Database (Denmark)

van der Meer, Quinten; Waight, Tod Earle; Whitehouse, Martin

2017-01-01

The Mount Somers Volcanic Group (MSVG) forms a large (~18000 km2) calc-alkaline volcanic complex on New Zealand’s Eastern Province. U-Pb SIMS spot ages on zircon from the lower glassy ignimbrite in Rakaia Gorge reveal a bimodal distribution of 99.0 ± 0.5 and 96.3 ± 0.5 Ma (2σ). These ages...

Glassy carbon electrode modified with multi-walled carbon nanotubes sensor for the quantification of antihistamine drug pheniramine in solubilized systems

Directory of Open Access Journals (Sweden)

Rajeev Jain

2012-02-01

Full Text Available A sensitive electroanalytical method for quantification of pheniramine in pharmaceutical formulation has been investigated on the basis of the enhanced electrochemical response at glassy carbon electrode modified with multi-walled carbon nanotubes in the presence of sodium lauryl sulfate. The experimental results suggest that the pheniramine in anionic surfactant solution exhibits electrocatalytic effect resulting in a marked enhancement of the peak current response. Peak current response is linearly dependent on the concentration of pheniramine in the range 200–1500 μg/mL with correlation coefficient 0.9987. The limit of detection is 58.31 μg/mL. The modified electrode shows good sensitivity and repeatability. Keywords: Pheniramine, Sodium lauryl sulfate (SLS, Glassy carbon electrode modified with multi-walled carbon nanotubes (GCE-MWCNTs, Solubilized systems, Voltammetric quantification

Spin-State Transition in La1-xSrxCoO3 Single Crystals

Science.gov (United States)

Bhardwaj, S.; Prabhakaran, D.; Awasthi, A. M.

2011-07-01

We present a study of the thermal conductivity (κ), specific heat (Cp) and Raman spectra of La1-xSrxCoO3 (x = 0,0.1) single crystals. Both the specimens have low thermal conductivity and board Raman peaks, arising from strong scattering of phonons by lattice disorder, produced by (and doping-enhanced) spin-states admixture of the Co3+ ions. The thermal conductivity anomalously deviates from ˜1/T behaviour at high (room) temperatures, expected of an insulator. High-temperature specific heat reveals large decrease in the metal-insulator (M-I) transition temperature with Sr-doping.

High Temperature NMR Studies of the Glass-Crystal Transition in the Cs2S2O7-V2O5 System

DEFF Research Database (Denmark)

Lapina, Olga B.; Terskikh, Viktor V.; Shubin, Aleksander A.

1997-01-01

133Cs and 51V NMR spectra have been recorded of Cs2S2O7 and the catalytically important Cs2S2O7-V2O5 mixtures in the temperature range 20 - 550 C. A high mobility of Cs+ in the solid Cs2S2O7 was observed. The transformation from glassy state to crystalline state was investigated for the compositi...

Electrocatalytic reduction of nitrite on tetraruthenated metalloporphyrins/Nafion glassy carbon modified electrode

Energy Technology Data Exchange (ETDEWEB)

Calfuman, Karla [Facultad de Ciencias, Departamento de Quimica, Universidad de Chile, Las Palmeras 3425, Casilla 653, Nunoa, Santiago (Chile); Aguirre, Maria Jesus [Facultad de Quimica y Biologia, Departamento de Quimica de los Materiales, Universidad de Santiago de Chile, Santiago (Chile); Canete-Rosales, Paulina; Bollo, Soledad [Facultad de Ciencias Quimicas y Farmaceuticas, Departamento de Quimica Farmacologica y Toxicologica, Universidad de Chile, Santiago (Chile); Llusar, Rosa [Departamento de Quimica Fisica y Analitica, Universidad de Jaume I, Castellon (Spain); Isaacs, Mauricio, E-mail: misaacs@uchile.cl [Facultad de Ciencias, Departamento de Quimica, Universidad de Chile, Las Palmeras 3425, Casilla 653, Nunoa, Santiago (Chile)

2011-10-01

Highlights: > Preparation and characterization of modified electrodes with M(II) Tetraruthenated porphyrins onto a Nafion film. > The electrodes were characterized by SEM, TEM, AFM and SECM techniques. > The modified electrodes are active in the electrochemical reduction of nitrite at -660 mV vs Ag/AgCl. > GC/Nf/CoTRP modified electrode is more electrochemically active than their Ni and Zn analogues. - Abstract: This paper describes the electrochemical reduction of nitrite ion in neutral aqueous solution mediated by tetraruthenated metalloporphyrins (Co(II), Ni(II) and Zn(II)) electrostatically assembled onto a Nafion film previously adsorbed on glassy carbon or ITO electrodes. Scanning electron microscope (SEM-EDX) and transmission electron microscopy (TEM) results have shown that on ITO electrodes the macrocycles forms multiple layers with a disordered stacking orientation over the Nafion film occupying hydrophobic and hydrophilic sites in the polyelectrolyte. Atomic force microscopy (AFM) results demonstrated that the Nafion film is 35 nm thick and tetraruthenated metalloporphyrins layers 190 nm thick presenting a thin but compacted morphology. Scanning electrochemical microscopy (SECM) images shows that the Co(II) tetraruthenated porphyrins/Nf/GC modified electrode is more electrochemically active than their Ni and Zn analogues. These modified electrodes are able to reduce nitrite at -660 mV showing enhanced reduction current and a decrease in the required overpotential compared to bare glassy carbon electrode. Controlled potential electrolysis experiments verify the production of ammonia, hydrazine and hydroxylamine at potentials where reduction of solvent is plausible demonstrating some selectivity toward the nitrite ion. Rotating disc electrode voltammetry shows that the factor that governs the kinetics of nitrite reduction is the charge propagation in the film.

Creation and evolution of excited states in α particle tracks in anthracene crystals

International Nuclear Information System (INIS)

Klein, G.

1977-01-01

The kinematics of excited states in anthracene crystals bombarded by 5MeV α particles is studied. The elementary processes which account for the transitions from the primary excited states to the lowest singlet S 1 and triplet T 1 excited states is described. The equation governing the evolution of the S 1 and T 1 excitons in the α particle track are then solved, and the scintillation decay curve is calculated. This calculated result is in good agreement with all available experimental results. The experimental part of this work are scintillation decay curves measurements. The scintillation decay was measured between 0.5nsec and 40μsec. The influence of the initial very fast singlet excitons quenching by triplet excitons can be seen in the beginning of scintillation. The delayed component is described by the triplet excitons kinematics. The magnetic field effect on the scintillation was investigated. This effect is attributed to an effect on the T 1 -T 1 annihilation and an effect on the triplet excitons quenching by radicals which are formed in the α particle track

Strong and anisotropic magnetoelectricity in composites of magnetostrictive Ni and solid-state grown lead-free piezoelectric BZT–BCT single crystals

Directory of Open Access Journals (Sweden)

Haribabu Palneedi

2017-03-01

Full Text Available Aimed at developing lead-free magnetoelectric (ME composites with performances as good as lead (Pb-based ones, this study employed (001 and (011 oriented 82BaTiO3-10BaZrO3-8CaTiO3 (BZT–BCT piezoelectric single crystals, fabricated by the cost-effective solid-state single crystal growth (SSCG method, in combination with inexpensive, magnetostrictive base metal Nickel (Ni. The off-resonance, direct ME coupling in the prepared Ni/BZT–BCT/Ni laminate composites was found to be strongly dependent on the crystallographic orientation of the BZT–BCT single crystals, as well as the applied magnetic field direction. Larger and anisotropic ME voltage coefficients were observed for the composite made using the (011 oriented BZT–BCT single crystal. The optimized ME coupling of 1 V/cm Oe was obtained from the Ni/(011 BZT–BCT single crystal/Ni composite, in the d32 mode of the single crystal, when a magnetic field was applied along its [100] direction. This performance is similar to that reported for the Ni/Pb(Mg1/3Nb2/3O3-Pb(Zr,TiO3 (PMN–PZT single crystal/Ni, but larger than that obtained from the Ni/Pb(Zr,TiO3 ceramic/Ni composites. The results of this work demonstrate that the use of lead-free piezoelectric single crystals with special orientations permits the selection of desired anisotropic properties, enabling the realization of customized ME effects in composites.

X-ray Free Electron Laser Determination of Crystal Structures of Dark and Light States of a Reversibly Photoswitching Fluorescent Protein at Room Temperature

Directory of Open Access Journals (Sweden)

Christopher D. M. Hutchison

2017-09-01

Full Text Available The photochromic fluorescent protein Skylan-NS (Nonlinear Structured illumination variant mEos3.1H62L is a reversibly photoswitchable fluorescent protein which has an unilluminated/ground state with an anionic and cis chromophore conformation and high fluorescence quantum yield. Photo-conversion with illumination at 515 nm generates a meta-stable intermediate with neutral trans-chromophore structure that has a 4 h lifetime. We present X-ray crystal structures of the cis (on state at 1.9 Angstrom resolution and the trans (off state at a limiting resolution of 1.55 Angstrom from serial femtosecond crystallography experiments conducted at SPring-8 Angstrom Compact Free Electron Laser (SACLA at 7.0 keV and 10.5 keV, and at Linac Coherent Light Source (LCLS at 9.5 keV. We present a comparison of the data reduction and structure determination statistics for the two facilities which differ in flux, beam characteristics and detector technologies. Furthermore, a comparison of droplet on demand, grease injection and Gas Dynamic Virtual Nozzle (GDVN injection shows no significant differences in limiting resolution. The photoconversion of the on- to the off-state includes both internal and surface exposed protein structural changes, occurring in regions that lack crystal contacts in the orthorhombic crystal form.

Raman spectra of zinc phthalocyanine monolayers absorbed on glassy carbon and gold electrodes by application of a confocal Raman microspectrometer

NARCIS (Netherlands)

Palys-Staron, B.J.; Palys, B.J.; Puppels, G.J.; Puppels, G.J.; van den Ham, D.M.W.; van den Ham, D.M.W.; Feil, D.; Feil, D.

1992-01-01

Raman spectra of zinc phthalocyanine monolayers, adsorbed on gold and on glassy carbon surfaces (electrodes), are presented. These spectra have been recorded with the electrodes inside and outside an electrochemical cell filled with an aqueous electrolyte. A confocal Raman microspectrometer was

Modified method for registration of particle deflection by bent crystal

International Nuclear Information System (INIS)

Afanas'ev, S.V.; Kovalenko, A.D.; Kuznetsov, V.N.; Romanov, S.V.; Sajfulin, Sh.Z.; Taratin, A.M.; Volkov, V.I.; Voevodin, M.A.; Bojko, V.V.

2003-01-01

The modified method for registration of particle deflection by a bent crystal was proposed and studied at the external proton beam of the Nuclotron. The telescope of scintillation counters was placed at the angle that was smaller than a crystal bending angle. The count dependence of the telescope on the crystal orientation was formed by the particles, which passed in channeling states only some part of the crystal length. Two maximums were observed in the dependencies due to particles captured into the channeling states on the crystal surface and in the crystal volume. This allows one to obtain, using the telescope and high-intensity beams, useful data about the particle channeling and the crystal, which usually demands more complicated registration by means of the coordinate detectors

Activation of glassy carbon electrodes by photocatalytic pretreatment

Energy Technology Data Exchange (ETDEWEB)

Dumanli, Onur [Department of Chemistry, Faculty of Science and Art, Ondokuz Mayis University, Kurupelit, 55139 Samsun (Turkey); Onar, A. Nur [Department of Chemistry, Faculty of Science and Art, Ondokuz Mayis University, Kurupelit, 55139 Samsun (Turkey)], E-mail: nonar@omu.edu.tr

2009-11-01

This paper describes a simple and rapid photocatalytic pretreatment procedure that removes contaminants from glassy carbon (GC) surfaces. The effectiveness of TiO{sub 2} mediated photocatalytic pretreatment procedure was compared to commonly used alumina polishing procedure. Cyclic voltammetric and chronocoulometric measurements were carried out to assess the changes in electrode reactivity by using four redox systems. Electrochemical measurements obtained on photocatalytically treated GC electrodes showed a more active surface relative to polished GC. In cyclic voltammograms of epinephrine, Fe(CN){sub 6}{sup 3-/4-} and ferrocene redox systems, higher oxidation and reduction currents were observed. The heterogeneous electron transfer rate constants (k{sup o}) were calculated for Fe(CN){sub 6}{sup 3-/4-} and ferrocene which were greater for photocatalytic pretreatment. Chronocoulometry was performed in order to find the amount of adsorbed methylene blue onto the electrode and was calculated as 0.34 pmol cm{sup -2} for photocatalytically pretreated GC. The proposed photocatalytic GC electrode cleansing and activating pretreatment procedure was more effective than classical alumina polishing.

Simulations of tensile failure in glassy polymers: effect of cross-link density

International Nuclear Information System (INIS)

Panico, M; Narayanan, S; Brinson, L C

2010-01-01

Molecular dynamics simulations are adopted to investigate the failure mechanisms of glassy polymers, particularly with respect to increasing density of cross-links. In our simulations thermosetting polymers, which are cross-linked, exhibit an embrittlement compared with uncross-linked thermoplastics in a similar fashion to several experimental investigations (Levita et al 1991 J. Mater. Sci. 26 2348; Sambasivam et al 1997 J. Appl. Polym. Sci. 65 1001; Iijima et al 1992 Eur. Polym. J. 28 573). We perform a detailed analysis of this phenomenon and propose an interpretation based on the predominance of chain scission process over disentanglement in thermosetting polymers. We also elucidate the brittle fracture response of the thermosetting polymers

A neutron diffraction study of macroscopically entangled proton states in the high temperature phase of the KHCO3 crystal at 340 K

International Nuclear Information System (INIS)

Fillaux, Francois; Cousson, Alain; Gutmann, Matthias J

2008-01-01

We utilize single-crystal neutron diffraction to study the C 2/m structure of potassium hydrogen carbonate (KHCO 3 ) and macroscopic quantum entanglement above the phase transition at T c = 318 K. Whereas split atom sites could be due to disorder, the diffraction pattern at 340 K evidences macroscopic proton states identical to those previously observed below T c by Fillaux et al (2006 J. Phys.: Condens. Matter 18 3229). We propose a theoretical framework for decoherence-free proton states and the calculated differential cross-section accords with observations. The structural transition occurs from one ordered P 2 1 /a structure (T c ) to another ordered C 2/m structure. There is no breakdown of the quantum regime. It is suggested that the crystal is a macroscopic quantum object which can be represented by a state vector. Raman spectroscopy and quasi-elastic neutron scattering suggest that the |C2/m> state vector is a superposition of the state vectors for two P 2 1 /a-like structures symmetric with respect to (a,c) planes

Economic analysis of crystal growth in space

Science.gov (United States)

Ulrich, D. R.; Chung, A. M.; Yan, C. S.; Mccreight, L. R.

1972-01-01

Many advanced electronic technologies and devices for the 1980's are based on sophisticated compound single crystals, i.e. ceramic oxides and compound semiconductors. Space processing of these electronic crystals with maximum perfection, purity, and size is suggested. No ecomonic or technical justification was found for the growth of silicon single crystals for solid state electronic devices in space.

Defining Time Crystals via Representation Theory

OpenAIRE

Khemani, Vedika; von Keyserlingk, C. W.; Sondhi, S. L.

2016-01-01

Time crystals are proposed states of matter which spontaneously break time translation symmetry. There is no settled definition of such states. We offer a new definition which follows the traditional recipe for Wigner symmetries and order parameters. Supplementing our definition with a few plausible assumptions we find that a) systems with time independent Hamiltonians should not exhibit TTSB while b) the recently studied $\\pi$ spin glass/Floquet time crystal can be viewed as breaking a globa...

Crystal structure of a Na+-bound Na+,K+-ATPase preceding the E1P state.

Science.gov (United States)

Kanai, Ryuta; Ogawa, Haruo; Vilsen, Bente; Cornelius, Flemming; Toyoshima, Chikashi

2013-10-10

Na(+),K(+)-ATPase pumps three Na(+) ions out of cells in exchange for two K(+) taken up from the extracellular medium per ATP molecule hydrolysed, thereby establishing Na(+) and K(+) gradients across the membrane in all animal cells. These ion gradients are used in many fundamental processes, notably excitation of nerve cells. Here we describe 2.8 Å-resolution crystal structures of this ATPase from pig kidney with bound Na(+), ADP and aluminium fluoride, a stable phosphate analogue, with and without oligomycin that promotes Na(+) occlusion. These crystal structures represent a transition state preceding the phosphorylated intermediate (E1P) in which three Na(+) ions are occluded. Details of the Na(+)-binding sites show how this ATPase functions as a Na(+)-specific pump, rejecting K(+) and Ca(2+), even though its affinity for Na(+) is low (millimolar dissociation constant). A mechanism for sequential, cooperative Na(+) binding can now be formulated in atomic detail.

UV and electron radiation-induced luminescence of Cu- and Eu-doped lithium tetraborates

Energy Technology Data Exchange (ETDEWEB)

Ignatovych, M.; Holovey, V.; Watterich, A.; Vidoczy, T.; Baranyai, P.; Kelemen, A.; Ogenko, V.; Chuiko, O

2003-06-01

Cu- and Eu-doped Li{sub 2}B{sub 4}O{sub 7} has been characterized using steady-state and time-resolved photoluminescence, radioluminescence and optical absorption techniques. The effect of dopant content (7.0x10{sup -4}-5.0x10{sup -2} wt% for Cu and 1.6x10{sup -3}-8.0x10{sup -3} wt% for Eu) and of host modification (single crystal, polycrystalline and glassy) has been investigated.

Solid-state reaction kinetics and optical studies of cadmium doped magnesium hydrogen phosphate crystals

Science.gov (United States)

Verma, Madhu; Gupta, Rashmi; Singh, Harjinder; Bamzai, K. K.

2018-04-01

The growth of cadmium doped magnesium hydrogen phosphate was successfully carried out by using room temperature solution technique i.e., gel encapsulation technique. Grown crystals were confirmed by single crystal X-ray diffraction (XRD). The structure of the grown crystal belongs to orthorhombic crystal system and crystallizes in centrosymmetric space group. Kinetics of the decomposition of the grown crystals were studied by non-isothermal analysis. Thermo gravimetric / differential thermo analytical (TG/DTA) studies revealed that the grown crystal is stable upto 119 °C. The various steps involved in the thermal decomposition of the material have been analysed using Horowitz-Metzger, Coats-Redfern and Piloyan-Novikova equations for evaluating various kinetic parameters. The optical studies shows that the grown crystals possess wide transmittance in the visible region and significant optical band gap of 5.5ev with cut off wavelength of 260 nm.

A novel highly selective and sensitive detection of serotonin based on Ag/polypyrrole/Cu2O nanocomposite modified glassy carbon electrode.

Science.gov (United States)

Selvarajan, S; Suganthi, A; Rajarajan, M

2018-06-01

A silver/polypyrrole/copper oxide (Ag/PPy/Cu 2 O) ternary nanocomposite was prepared by sonochemical and oxidative polymerization simple way, in which Cu 2 O was decorated with Ag nanoparticles, and covered by polyprrole (PPy) layer. The as prepared materials was characterized by UV-vis-spectroscopy (UV-vis), FT-IR, X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM) with EDX, high resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). Sensing of serotonin (5HT) was evaluated electrocatalyst using polypyrrole/glassy carbon electrode (PPy/GCE), polypyrrole/copper oxide/glassy carbon electrode (PPy/Cu 2 O/GCE) and silver/polypyrrole/copper oxide/glassy carbon electrode (Ag/PPy/Cu 2 O/GCE). The Ag/PPy/Cu 2 O/GCE was electrochemically treated in 0.1MPBS solution through cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The peak current response increases linearly with 5-HT concentration from 0.01 to 250 µmol L -1 and the detection limit was found to be 0.0124 μmol L -1 . It exhibits high electrocatalytic activity, satisfactory repeatability, stability, fast response and good selectivity against potentially interfering species, which suggests its potential in the development of sensitive, selective, easy-operation and low-cost serotonin sensor for practical routine analyses. The proposed method is potential to expand the possible applied range of the nanocomposite material for detection of various concerned electro active substances. Copyright © 2018 Elsevier B.V. All rights reserved.

Liquid Crystal Colloids

Science.gov (United States)

Smalyukh, Ivan I.

2018-03-01

Colloids are abundant in nature, science, and technology, with examples ranging from milk to quantum dots and the colloidal atom paradigm. Similarly, liquid crystal ordering is important in contexts ranging from biological membranes to laboratory models of cosmic strings and liquid crystal displays in consumer devices. Some of the most exciting recent developments in both of these soft matter fields emerge at their interface, in the fast-growing research arena of liquid crystal colloids. Mesoscale self-assembly in such systems may lead to artificial materials and to structures with emergent physical behavior arising from patterning of molecular order and nano- or microparticles into precisely controlled configurations. Liquid crystal colloids show exceptional promise for new discovery that may impinge on composite material fabrication, low-dimensional topology, photonics, and so on. Starting from physical underpinnings, I review the state of the art in this fast-growing field, with a focus on its scientific and technological potential.

Bistable switching in dual-frequency liquid crystals

Energy Technology Data Exchange (ETDEWEB)

Palto, S. P., E-mail: palto@online.ru; Barnik, M I [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

2006-06-15

Various bistable switching modes in nematic liquid crystals with frequency inversion of the sign of dielectric anisotropy are revealed and investigated. Switching between states with different helicoidal distributions of the director field of a liquid crystal, as well as between uniform and helicoidal states, is realized by dual-frequency waveforms of a driving voltage. A distinctive feature of the dual-frequency switching is that the uniform planar distribution of the director field may correspond to a thermodynamically equilibrium state, and the chirality of an LC is not a necessary condition for switching to a helicoidal state.

Effect of compositional variations on charge compensation of AlO4 and BO4 entities and on crystallization tendency of a rare-earth-rich aluminoborosilicate glass

International Nuclear Information System (INIS)

Quintas, A.; Caurant, D.; Majerus, O.; Charpentier, T.; Dussossoy, J.-L.

2009-01-01

This paper presents the structural and crystallization study of a rare-earth-rich aluminoborosilicate glass that is a simplified version of a new nuclear glass proven to be a potential candidate for the immobilization of highly concentrated radioactive wastes that will be produced in the future. In this work, we studied the impact of changing the nature of alkali (Li + , Na + , K + , Rb + , Cs + ) or alkaline-earth (Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ ) cations present in glass composition on glass structure (by 27 Al and 11 B nuclear magnetic resonance spectroscopy) and on its crystallization tendency during melt cooling at 1 K/min (average cooling rate during industrial process). From these composition changes, it was established that alkali cations were preferentially involved in charge compensation of (AlO 4 ) - and (BO 4 ) - entities in the glassy network comparatively to alkaline-earth cations. Whatever the nature of alkali cations, glass compositions containing calcium gave way to the crystallization of an apatite silicate phase bearing calcium and rare-earth (RE) cations (Ca 2 RE 8 (SiO 4 ) 6 O 2 , RE = Nd or La) but melt crystallization tendency during cooling strongly varied with the nature of alkaline-earth cations.

Do cracks melt their way through solids?

International Nuclear Information System (INIS)

Okamoto, P. R.

1998-01-01

Real-time, in situ fracture studies in the high-voltage electron microscope (HVEM) show that microscopically thin regions of amorphous NiTi form ahead of moving crack tips in the B2-NiTi intermetallic compound during tensile straining at temperatures equal to or below 600K. The upper cutoff temperature of 600K for this stress-induced melting (or amorphization) is identical to the upper cutoff temperatures reported in the literature for both heavy-ion-induced amorphization of the intermetallic NiTi and ion-beam-mixing-induced amorphization of Ni and Ti multilayer. These results, together with the fact that the higher crystallization temperatures (∼800K)of unrelaxed amorphous NiTi alloys obtained by rapid quenching can also be reduced to, but not lower than 600K, by heavy-ion irradiation, strongly suggest that structural relaxation processes enhanced or induced by dynamic atomic disordering allow the formation of a unique, fully-relaxed glassy state which is characterized by a unique isothermal crystallization temperature. We believe that this unique temperature is the Kauzmann glass-transition temperature, corresponding to the ideal glass having the same entropy as the crystalline state. As the glassy state with the lowest global free energy, the preferential formation of this ideal glass by disorder-induced amorphization processes can be understood as the most energetically-favored, kinetically-constrained melting response of crystalline materials driven far from equilibrium at low temperatures

Local atomic and electronic structure in glassy metallic alloys. Final report, March 1, 1979-May 31, 1982

International Nuclear Information System (INIS)

Messmer, R.P.; Wong, J.

1982-01-01

The research results reported, represent the first coordinated experimental-theoretical effort to arrive at important local atomic and electronic structure information in glassy alloys. During the three years covered by the contract, significant experimental and theoretical developments have taken place both in the general technical community and at General Electric which have had an important impact on the approach to this problem. This is particularly true in the theoretical area where two important advances, the development of a general Xα-LCAO approach, and the development of a general and accurate effective potential approach for density functional methods, have allowed us to construct a new computational capability which combines these two advances. Two subsections briefly review the experimental and theoretical technical developments, respectively. These developments have changed initial perspectives regarding research on local atomic and electronic structure in glassy metallic alloys. Section II presents a synopsis of our accomplishments during the contract period and Section III contains a more detailed discussion of some of these accomplishments, namely those portions of the work which have been published or submitted for publication at the time of writing this final report

Electrochemical Determination of Caffeine Content in Ethiopian Coffee Samples Using Lignin Modified Glassy Carbon Electrode

Directory of Open Access Journals (Sweden)

Meareg Amare

2017-01-01

Full Text Available Lignin film was deposited at the surface of glassy carbon electrode potentiostatically. In contrast to the unmodified glassy carbon electrode, an oxidative peak with an improved current and overpotential for caffeine at modified electrode showed catalytic activity of the modifier towards oxidation of caffeine. Linear dependence of peak current on caffeine concentration in the range 6×10-6 to 100×10-6 mol L−1 with determination coefficient and method detection limit (LoD = 3 s/slope of 0.99925 and 8.37×10-7 mol L−1, respectively, supplemented by recovery results of 93.79–102.17% validated the developed method. An attempt was made to determine the caffeine content of aqueous coffee extracts of Ethiopian coffees grown in four coffee cultivating localities (Wonbera, Wolega, Finoteselam, and Zegie and hence to evaluate the correlation between users preference and caffeine content. In agreement with reported works, caffeine contents (w/w% of 0.164 in Wonbera coffee; 0.134 in Wolega coffee; 0.097 in Finoteselam coffee; and 0.089 in Zegie coffee were detected confirming the applicability of the developed method for determination of caffeine in a complex matrix environment. The result indicated that users’ highest preference for Wonbera and least preference for Zegie cultivated coffees are in agreement with the caffeine content.

Electrochemical Determination of Caffeine Content in Ethiopian Coffee Samples Using Lignin Modified Glassy Carbon Electrode.

Science.gov (United States)

Amare, Meareg; Aklog, Senait

2017-01-01

Lignin film was deposited at the surface of glassy carbon electrode potentiostatically. In contrast to the unmodified glassy carbon electrode, an oxidative peak with an improved current and overpotential for caffeine at modified electrode showed catalytic activity of the modifier towards oxidation of caffeine. Linear dependence of peak current on caffeine concentration in the range 6 × 10 -6 to 100 × 10 -6  mol L -1 with determination coefficient and method detection limit (LoD = 3 s/slope) of 0.99925 and 8.37 × 10 -7  mol L -1 , respectively, supplemented by recovery results of 93.79-102.17% validated the developed method. An attempt was made to determine the caffeine content of aqueous coffee extracts of Ethiopian coffees grown in four coffee cultivating localities (Wonbera, Wolega, Finoteselam, and Zegie) and hence to evaluate the correlation between users preference and caffeine content. In agreement with reported works, caffeine contents (w/w%) of 0.164 in Wonbera coffee; 0.134 in Wolega coffee; 0.097 in Finoteselam coffee; and 0.089 in Zegie coffee were detected confirming the applicability of the developed method for determination of caffeine in a complex matrix environment. The result indicated that users' highest preference for Wonbera and least preference for Zegie cultivated coffees are in agreement with the caffeine content.

A study of the electro-catalytic oxidation of methanol on a cobalt hydroxide modified glassy carbon electrode

International Nuclear Information System (INIS)

Jafarian, M.; Mahjani, M.G.; Heli, H.; Gobal, F.; Khajehsharifi, H.; Hamedi, M.H.

2003-01-01

Cobalt hydroxide modified glassy carbon electrodes (CHM/GC) prepared by the anodic deposition in presence of tartrate ions have been used for the electro-catalytic oxidation of methanol in alkaline solutions where the methods of cyclic voltammetery (CV), chronoamperometry (CA) and impedance spectroscopy (IS) have been employed. In CV studies, in the presence of methanol the peak current of the oxidation of cobalt hydroxide increase is followed by a decrease in the corresponding cathodic current. This suggests that the oxidation of methanol is being catalysed through the mediated electron transfer across the cobalt hydroxide layer comprising of cobalt ions of various valence states. A mechanism based on the electro-chemical generation of Co(IV) active sites and their subsequent consumptions by methanol have been discussed and the corresponding rate law under the control of charge transfer has been developed and kinetic parameters have been derived. In this context the charge transfer resistance accessible both theoretically and through the IS studies have been used as a criteria. Under the CA regimes the reaction followed a Cottrellian behaviour

Absence of Quantum Time Crystals.

Science.gov (United States)

Watanabe, Haruki; Oshikawa, Masaki

2015-06-26

In analogy with crystalline solids around us, Wilczek recently proposed the idea of "time crystals" as phases that spontaneously break the continuous time translation into a discrete subgroup. The proposal stimulated further studies and vigorous debates whether it can be realized in a physical system. However, a precise definition of the time crystal is needed to resolve the issue. Here we first present a definition of time crystals based on the time-dependent correlation functions of the order parameter. We then prove a no-go theorem that rules out the possibility of time crystals defined as such, in the ground state or in the canonical ensemble of a general Hamiltonian, which consists of not-too-long-range interactions.

Plasticity induced phase transformation in molecular crystals

OpenAIRE

Koslowski, Marisol

2014-01-01

Solid state amorphization (SSA) can be achieved in crystalline materials including metal alloys, intermetallics, semiconductors, minerals and molecular crystals. Even though the mechanisms may differ in different materials, the crystalline to amorphous transformation occurs when the crystal reaches a metastable state in which its free energy is higher than that of the amorphous phase. SSA is observed in metal alloys because of interdiffusion of the crystalline elements during mechanical milli...

Self-assembled tunable photonic hyper-crystals.

Science.gov (United States)

Smolyaninova, Vera N; Yost, Bradley; Lahneman, David; Narimanov, Evgenii E; Smolyaninov, Igor I

2014-07-16

We demonstrate a novel artificial optical material, the "photonic hyper-crystal", which combines the most interesting features of hyperbolic metamaterials and photonic crystals. Similar to hyperbolic metamaterials, photonic hyper-crystals exhibit broadband divergence in their photonic density of states due to the lack of usual diffraction limit on the photon wave vector. On the other hand, similar to photonic crystals, hyperbolic dispersion law of extraordinary photons is modulated by forbidden gaps near the boundaries of photonic Brillouin zones. Three dimensional self-assembly of photonic hyper-crystals has been achieved by application of external magnetic field to a cobalt nanoparticle-based ferrofluid. Unique spectral properties of photonic hyper-crystals lead to extreme sensitivity of the material to monolayer coatings of cobalt nanoparticles, which should find numerous applications in biological and chemical sensing.

Deformed lattice states in a Zn{sub 0.9}V{sub 0.1}Se cubic crystal

Energy Technology Data Exchange (ETDEWEB)

Maksimov, V. I., E-mail: kokailo@rambler.ru; Dubinin, S. F.; Surkova, T. P.; Parkhomenko, V. D. [Russian Academy of Sciences, Institute of Metal Physics, Ural Branch (Russian Federation)

2016-01-15

Neutron scattering patterns have been recorded for a bulk Zn{sub 0.9}V{sub 0.1}Se cubic crystal at room temperature; they are indicative of macroscopic deformation in the material and its significant inhomogeneity. Specific features of the previously found state, preceding the fcc ↔ hcp structural transformation of the sphalerite lattice upon strong destabilization induced by vanadium ions in the doped ZnSe matrix, are discussed taking into account the data obtained.

Crystallization of copper metaphosphate glass

Science.gov (United States)

Bae, Byeong-Soo; Weinberg, Michael C.

1993-01-01

The effect of the valence state of copper in copper metaphosphate glass on the crystallization behavior and glass transition temperature has been investigated. The crystallization of copper metaphosphate is initiated from the surface and its main crystalline phase is copper metaphosphate (Cu(PO)3),independent of the (Cu sup 2+)/(Cu(total)). However, the crystal morphology, the relative crystallization rates, and their temperature dependences are affected by the (Cu sup 2+)/(Cu (total)) ratio in the glass. On the other hand, the totally oxidized glass crystallizes from all over the surface. The relative crystallization rate of the reduced glass to the totally oxidized glass is large at low temperature, but small at high temperature. The glass transition temperature of the glass increases as the (Cu sup 2+)/(Cu(total)) ratio is raised. It is also found that the atmosphere used during heat treatment does not influence the crystallization of the reduced glass, except for the formation of a very thin CuO surface layer when heated in air.

Investigation of lactose crystallization process during condensed milk cooling using native vacuum-crystallizer

Directory of Open Access Journals (Sweden)

E. I. Dobriyan

2016-01-01

Full Text Available One of the most general defects of condensed milk with sugar is its consistency heterogeneity – “candying”. The mentioned defect is conditioned by the presence of lactose big crystals in the product. Lactose crystals size up to 10 µm is not organoleptically felt. The bigger crystals impart heterogeneity to the consistency which can be evaluated as “floury”, “sandy”, “crunch on tooth”. Big crystals form crystalline deposit on the can or industrial package bottom in the form of thick layer. Industrial processing of the product with the defective process of crystallization results in the expensive equipment damage of the equipment at the confectionary plant accompanied with heavy losses. One of the factors influencing significantly lactose crystallization is the product cooling rate. Vacuum cooling is the necessary condition for provision of the product consistency homogeneity. For this purpose the vacuum crystallizers of “Vigand” company, Germany, are used. But their production in the last years has been stopped. All-Russian dairy research institute has developed “The references for development of the native vacuum crystallizer” according to which the industrial model has been manufactured. The produced vacuum – crystallizer test on the line for condensed milk with sugar production showed that the product cooling on the native vacuum-crystallizer guarantees production of the finished product with microstructure meeting the requirements of State standard 53436–2009 “Canned Milk. Milk and condensed cream with sugar”. The carried out investigations evidences that the average lactose crystals size in the condensed milk with sugar cooled at the native crystallizer makes up 6,78 µm. The granulometric composition of the product crystalline phase cooled at the newly developed vacuum-crystallizer is completely identical to granulometric composition of the product cooled at “Vigand” vacuum-crystallizer.

Colloidal glasses

Indian Academy of Sciences (India)

First page Back Continue Last page Overview Graphics. Colloidal glasses. Glassy state is attained when system fails to reach equilibrium due to crowding of constituent particles. In molecular glasses, glassy state is reached by rapidly lowering the temperature. In colloidal glasses, glassy state is reached by increasing the ...

Features of the structural states of KNbO{sub 3} single crystals before and after fast-neutron irradiation

Energy Technology Data Exchange (ETDEWEB)

Stash, A. I., E-mail: astas@yandex.ru; Ivanov, S. A.; Stefanovich, S. Yu.; Mosunov, A. V.; Boyko, V. M.; Ermakov, V. S.; Korulin, A. V.; Kalyukanov, A. I. [State Scientific Center of the Russian Federation Karpov Institute of Physical Chemistry (Russian Federation)

2017-01-15

Neutron irradiation is a unique tool for forming new structural states of ferroelectrics, which cannot be obtained by conventional methods. The inf luence of the irradiation by two doses of fast neutrons (F = 1 × 10{sup 17} and 3 × 10{sup 17} cm{sup –2}) on the structure and properties of KNbO{sub 3} single crystals has been considered for the first time. The developed method for taking into account the experimental correction to the diffuse scattering has been used to analyze the structural changes occurring in KNbO{sub 3} samples at T = 295 K and their correlations with the behavior of dielectric and nonlinear optical characteristics. The irradiation to the aforementioned doses retains the KNbO{sub 3} polar structure, shifting Т{sub Ð}¡ to lower temperatures and significantly affecting only the thermal parameters and microstructure of single crystals. Neutron irradiation with small atomic displacements provides a structure similar to the high-temperature modification of an unirradiated KNbO{sub 3} crystal.

Local structure and influence of bonding on the phase-change behavior of the chalcogenide compounds K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8}

Energy Technology Data Exchange (ETDEWEB)

Wachter, J B [Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States); Chrissafis, K [Department of Physics, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Petkov, V [Department of Physics, Central Michigan University, Mount Pleasant, MI 48859 (United States); Malliakas, C D [Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States); Bilc, D [Department of Physics, Central Michigan University, Mount Pleasant, MI 48859 (United States); Kyratsi, Th [Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States); Paraskevopoulos, K M [Department of Physics, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Mahanti, S D [Department of Physics, Michigan State University, East Lansing, MI 48824 (United States); Torbruegge, T [Institut fuer Physikalische Chemie, Westf. Wilhelms-Universitaet Muenster (Germany); Eckert, H [Institut fuer Physikalische Chemie, Westf. Wilhelms-Universitaet Muenster (Germany); Kanatzidis, M.G. [Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States)], E-mail: m-kanatzidis@northwestern.edu

2007-02-15

KSb{sub 5}S{sub 8} and its solid solution analogs with Rb and Tl were found to exhibit a reversible and tunable glass{sup {yields}}crystal{sup {yields}}glass phase transition. Selected members of this series were analyzed by differential scanning calorimetry to measure the effect of the substitution on the thermal properties. The solid solutions K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8} exhibited clear deviations in melting and crystallization behavior and temperatures from the parent structure. The crystallization process of the glassy KSb{sub 5}S{sub 8} as a function of temperature could clearly be followed with Raman spectroscopy. The thermal conductivity of both glassy and crystalline KSb{sub 5}S{sub 8} at room temperature is {approx}0.40 W/m K, among the lowest known values for any dense solid-state material. Electronic band structure calculations carried out on KSb{sub 5}S{sub 8} and TlSb{sub 5}S{sub 8} show the presence of large indirect band-gaps and confirm the coexistence of covalent Sb-S bonding and predominantly ionic K(Tl)...S bonding. Pair distribution function analyses based on total X-ray scattering data on both crystalline and glassy K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8} showed that the basic structure-defining unit is the same and it involves a distorted polyhedron of 'SbS{sub 7}' fragment of {approx}7 A diameter. The similarity of local structure between the glassy and crystalline phases accounts for the facile crystallization rate in this system. - Graphical abstract: The KSb{sub 5}S{sub 8} is a good example of a phase-change material with a mixed ionic/covalent bonding. The members of the K{sub 1-} {sub x} Rb {sub x} Sb{sub 5}S{sub 8} series exhibit phase-change properties with greater glass forming ability (GFA) than KSb{sub 5}S{sub 8}. The GFA increases with increasing Rb content. In this case, the random alloy disorder in the alkali metal sublattice seems to predominate over the increased degree of ionicity in going from K

Use of Plastic Capillaries for Macromolecular Crystallization

Science.gov (United States)

Potter, Rachel R.; Hong, Young-Soo; Ciszak, Ewa M.

2003-01-01

Methods of crystallization of biomolecules in plastic capillaries (Nalgene 870 PFA tubing) are presented. These crystallization methods used batch, free-interface liquid- liquid diffusion alone, or a combination with vapor diffusion. Results demonstrated growth of crystals of test proteins such as thaumatin and glucose isomerase, as well as protein studied in our laboratory such dihydrolipoamide dehydrogenase. Once the solutions were loaded in capillaries, they were stored in the tubes in frozen state at cryogenic temperatures until the desired time of activation of crystallization experiments.

Ab initio calculations of the electron spectrum and density of states of TlFeS{sub 2} and TlFeSe{sub 2} crystals

Energy Technology Data Exchange (ETDEWEB)

Ismayilova, N. A., E-mail: ismayilova-narmin-84@mail.ru; Orudjev, H. S.; Jabarov, S. H. [Azerbaijan National Academy of Sciences, Institute of Physics (Azerbaijan)

2017-04-15

The results of ab initio calculations of the electron spectrum of TlFeS{sub 2} and TlFeSe{sub 2} crystals in the antiferromagnetic phase are reported. Calculations are carried out in the context of the density functional theory. The origin of the bands of s, p, and d electron states of Tl, Fe, S, and Se atoms is studied. It is established that, in the antiferromagnetic phase, the crystals possess semiconductor properties. The band gaps are found to be 0.05 and 0.34 eV for TlFeS{sub 2} and TlFeSe{sub 2} crystals, respectively.

Instability of the critical state in NdBa2Cu3O7-δ single crystals

DEFF Research Database (Denmark)

Koblischka, M.R.; Murakami, M.; Koishikawa, S.

1999-01-01

Instabilities of the critical state are observed in various NdBa2Cu3O7-delta single crystals by means of direct magneto-optic (MO) imaging while warming up flux states containing vortices of opposite polarity. Using the same samples as in the MO investigations, we observe for the first time......, and also in the orientations H-a parallel to c and H-a perpendicular to c. As a result, we find turbulence not only in a narrow window of temperatures (65 less than or equal to T less than or equal to 80 K), but also in a window of applied negative fields ranging between 30 and 80 mT....

SANS study of deformation and relaxation of a comb-like liquid crystal polymer in the nematic phase

Science.gov (United States)

Brûlet, A.; Boué, F.; Keller, P.; Davidson, P.; Strazielle, C.; Cotton, J. P.

1994-06-01

A comb-like liquid crystal polymer is stretched and quenched after a certain time in the nematic phase. The conformation of the deformed chain is determined using small angle neutron scattering (SANS) as a function of the temperature of stretching, the stretching ratio and the duration of the relaxation. The scattering data are well fitted to junction affine and phantom network models. Some data are even well fitted by a totally affine model that we call “ pseudo affine ” because the only parameter, the stretching ratio, is found to be well below the macroscopic stretching ratio. The latter result, never encountered with amorphous polymers, is attributed to the cooperative effects of the nematic phase. We also note that the form factors of the chain in the underformed sample remain similar in the isotropic, nematic and glassy state ; they correspond to a Gaussian chain. The same samples were studied by wide angle X-ray scattering. On one hand, the orientation of the mesogenic groups is found to be parallel or perpendicular to the stretching direction depending on the stretching temperature. This result is discussed as a function of the presence of smectic fluctuations. On the other hand, longer relaxations at constant elongation ratio do not lead to a disorganization of the mesogenic group orientation whereas the polymer chains are partly relaxed.

Electrochemical parameters of ethamsylate at multi-walled carbon nanotube modified glassy carbon electrodes.

Science.gov (United States)

Wang, Sheng-Fu; Xu, Qiao

2007-05-01

In this paper, some electrochemical parameters of ethamsylate at a multi-walled carbon nanotube modified glassy carbon electrode, such as the charge number, exchange current density, standard heterogeneous rate constant and diffusion coefficient, were measured by cyclic voltammetry, chronoamperometry and chronocoulometry. The modified electrode exhibits good promotion of the electrochemical reaction of ethamsylate and increases the standard heterogeneous rate constant of ethamsylate greatly. The differential pulse voltammetry responses of ethamsylate were linearly dependent on its concentrations in a range from 2.0 x 10(-6) to 6.0 x 10(-5) mol L(-1), with a detection limit of 4.0 x 10(-7) mol L(-1).

Electronic Transport Behaviors due to Charge Density Waves in Ni-Nb-Zr-H Glassy Alloys

Science.gov (United States)

Fukuhara, Mikio; Umemori, Yoshimasa

2013-11-01

The amorphous Ni-Nb-Zr-H glassy alloy containing subnanometer-sized icosahedral Zr5 Nb5Ni3 clusters exhibited four types of electronic phenomena: a metal/insulator transition, an electric current-induced voltage oscillation (Coulomb oscillation), giant capacitor behavior and an electron avalanche with superior resistivity. These findings could be excluded by charge density waves that the low-dimensional component of clusters, in which the atoms are lined up in chains along the [130] direction, plays important roles in various electron transport phenomena.

Electrocatalytic performance of Pu(IV)/Pu(III) redox reaction at graphene modified glassy carbon electrode

International Nuclear Information System (INIS)

Gupta, Ruma; Gamare, J.S.; Kamat, J.V.; Aggarwal, S.K.

2014-01-01

In this paper we explore the analytical perspectives of graphene modified electrode utilising commercially available graphene, which is well characterised, completely free from surfactants and has not been purposely oxidised or treated. We compare and critically contrast the electro-analytical performance of graphene modified glassy carbon electrodes (Gr/GC) with that of unmodified GC electrode towards Pu(IV)/Pu(III) redox reaction, monitoring of which has considerable importance in a plethora of areas where electrochemistry is conveniently and beneficially utilised for determination of nuclear fuels

The Effect of Cellulose Crystal Structure and Solid-State Morphology on the Activity of Cellulases

Energy Technology Data Exchange (ETDEWEB)

Stipanovic, Arthur J [SUNY College of Environmental Science and Forestry

2014-11-17

Consistent with the US-DOE and USDA “Roadmap” objective of producing ethanol and chemicals from cellulosic feedstocks more efficiently, a three year research project entitled “The Effect of Cellulose Crystal Structure and Solid-State Morphology on the Activity of Cellulases” was initiated in early 2003 under DOE sponsorship (Project Number DE-FG02-02ER15356). A three year continuation was awarded in June 2005 for the period September 15, 2005 through September 14, 2008. The original goal of this project was to determine the effect of cellulose crystal structure, including allomorphic crystalline form (Cellulose I, II, III, IV and sub-allomorphs), relative degree of crystallinity and crystallite size, on the activity of different types of genetically engineered cellulase enzymes to provide insight into the mechanism and kinetics of cellulose digestion by “pure” enzymes rather than complex mixtures. We expected that such information would ultimately help enhance the accessibility of cellulose to enzymatic conversion processes thereby creating a more cost-effective commercial process yielding sugars for fermentation into ethanol and other chemical products. Perhaps the most significant finding of the initial project phase was that conversion of native bacterial cellulose (Cellulose I; BC-I) to the Cellulose II (BC-II) crystal form by aqueous NaOH “pretreatment” provided an increase in cellulase conversion rate approaching 2-4 fold depending on enzyme concentration and temperature, even when initial % crystallinity values were similar for both allomorphs.

Defining time crystals via representation theory

Science.gov (United States)

Khemani, Vedika; von Keyserlingk, C. W.; Sondhi, S. L.

2017-09-01

Time crystals are proposed states of matter which spontaneously break time translation symmetry. There is no settled definition of such states. We offer a new definition which follows the traditional recipe for Wigner symmetries and order parameters. Supplementing our definition with a few plausible assumptions we find that a) systems with time-independent Hamiltonians should not exhibit time translation symmetry breaking while b) the recently studied π spin glass/Floquet time crystal can be viewed as breaking a global internal symmetry and as breaking time translation symmetry, as befits its two names.

Crystal Deflectors for High Energy Ion Beams

CERN Document Server