Striking role of non-bridging oxygen on glass transition temperature of calcium aluminosilicate glass-formers

International Nuclear Information System (INIS)

Bouhadja, M.; Jakse, N.; Pasturel, A.

2014-01-01

Molecular dynamics simulations are used to study the structural and dynamic properties of calcium aluminosilicate, (CaO-Al 2 O 3 ) 1−x (SiO 2 ) x , glass formers along three joins, namely, R = 1, 1.57, and 3, in which the silica content x can vary from 0 to 1. For all compositions, we determined the glass-transition temperature, the abundances of the non-bridging oxygen, triclusters, and AlO 5 structural units, as well as the fragility from the temperature evolution of the α-relaxation times. We clearly evidence the role played by the non-bridging oxygen linked either to Al atoms or Si atoms in the evolution of the glass-transition temperature as well as of the fragility as a function of silica content along the three joins

Characterization of frequency-dependent glass transition temperature by Vogel-Fulcher relationship

International Nuclear Information System (INIS)

Bai Yu; Jin Li

2008-01-01

The complex mechanical modulus of polymer and polymer based composite materials showed a frequency-dependent behaviour during glass transition relaxation, which was historically modelled by the Arrhenius equation. However, this might not be true in a broad frequency domain based on the experience from the frequency dependence of the complex dielectric permittivity, which resulted from the same glass transition relaxation as for the complex mechanical modulus. Considering a good correspondence between dielectric and mechanical relaxation during glass transition, the Vogel-Fulcher relationship, previously proposed for the frequency dependence of dielectric permittivity, is introduced for that of the mechanical modulus; and the corresponding static glass transition temperature (T f ) was first determined for polymer and polymer based composite materials. (fast track communication)

Relaxation dynamics of glass transition in PMMA + SWCNT composites by temperature-modulated DSC

Science.gov (United States)

Pradhan, N. R.; Iannacchione, G. S.

2010-03-01

The experimental technique offered by temperature-modulated differential scanning calorimeter (TMDSC) used to investigate the thermal relaxation dynamics through the glass transition as a function of frequency was studied for pure PMMA and PMMA-single wall carbon nanotubes (SWCNTs) composites. A strong dependence of the temperature dependence peak in the imaginary part of complex heat capacity (Tmax) is found during the transition from the glass-like to the liquid-like region. The frequency dependence of Tmax of the imaginary part of heat capacity (Cp) is described by Arrhenius law. The activation energy obtained from the fitting shows increases while the characteristic relaxation time decreases with increasing mass fraction (phim) of SWCNTs. The dynamics of the composites during glass transition, at slow and high scan rates, are also the main focus of this experimental study. The change in enthalpy during heating and cooling is also reported as a function of scan rate and frequency of temperature modulation. The glass transition temperature (Tg) shows increases with increasing frequency of temperature modulation and phim of SWCNTs inside the polymer host. Experimental results show that Tg is higher at higher scan rates but as the frequency of temperature modulation increases, the Tg values of different scan rates coincide with each other and alter the scan rate dependence. From the imaginary part of heat capacity, it is obvious that Tmax is not the actual glass transition temperature of pure polymer but Tmax and Tg values can be superimposed when phim increases in the polymer host or when the sample undergoes a transition with a certain frequency of temperature modulation.

Predictions of glass transition temperature for hydrogen bonding biomaterials.

Science.gov (United States)

van der Sman, R G M

2013-12-19

We show that the glass transition of a multitude of mixtures containing hydrogen bonding materials correlates strongly with the effective number of hydroxyl groups per molecule, which are available for intermolecular hydrogen bonding. This correlation is in compliance with the topological constraint theory, wherein the intermolecular hydrogen bonds constrain the mobility of the hydrogen bonded network. The finding that the glass transition relates to hydrogen bonding rather than free volume agrees with our recent finding that there is little difference in free volume among carbohydrates and polysaccharides. For binary and ternary mixtures of sugars, polyols, or biopolymers with water, our correlation states that the glass transition temperature is linear with the inverse of the number of effective hydroxyl groups per molecule. Only for dry biopolymer/sugar or sugar/polyol mixtures do we find deviations due to nonideal mixing, imposed by microheterogeneity.

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

DEFF Research Database (Denmark)

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

2004-01-01

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

Phase transitions and glass transition in a hyperquenched silica–alumina glass

DEFF Research Database (Denmark)

Zhang, Y.F.; Zhao, D.H.; Yue, Yuanzheng

2017-01-01

We investigate phase transitions, glass transition, and dynamic behavior in the hyperquenched 69SiO2–31Al2O3 (mol%) glass (SA glass). Upon reheating, the SA glass exhibits a series of thermal responses. Subsequent to the sub-Tg enthalpy release, the glass undergoes a large jump in isobaric heat...... capacity (ΔCp) during glass transition, implying the fragile nature of the SA glass. The mullite starts to form before the end of glass transition, indicating that the SA glass is extremely unstable against crystallization. After the mullite formation, the remaining glass phase exhibits an increased Tg...... and a suppressed ΔCp. The formation of cristobalite at 1553 K indicates the dominance of silica in the remaining glass matrix. The cristobalite gradually re-melts as the isothermal heat-treatment temperature is raised from 1823 to 1853 K, which is well below the melting point of cristobalite, while the amount...

Relaxation Dynamics of the Glass Transition in PMMA+SWCNT Composites by Temperature-Modulated DSC

Science.gov (United States)

Pradhan, Nihar; Iannacchione, Germano

2010-03-01

Temperature Modulated Differential Scanning Calorimeter (TMDSC) used to investigate the thermal relaxation dynamics of PMMA-Single wall carbon nanotubes (SWCNTs) through the glass transition as a function of frequency. A strong dependence of the temperature dependence peak in imaginary part of complex heat capacity (Tmax) was found during the transition from glass like to liquid like region and can be described by Arhenius law. The activation energy shows increases while the charactersistic time decreases with increasing mass fraction (φm) of SWCNTs. Decreasing of enthalpy, while heating and slowly increasing while cooling at 2.0 K/min scan rate was observed and as frequency of temperature modulation increases. There is no relative change of enthalpy in heating and cooling observed at sufficiently slow scan rate. The glass transition temperature (Tg) shows increases as a function of frequency of temperature modulation, φm of SWCNTs and with increasing scan rate. From imaginary part of heat capacity, it obvious that Tmax is not the actual glass transition temperature of pure polymer but Tmax and Tg values can be superimpose when φm of SWCNT increases in polymer.

Glass transition in thin supported polystyrene films probed by temperature-modulated ellipsometry in vacuum.

Science.gov (United States)

Efremov, Mikhail Yu; Kiyanova, Anna V; Last, Julie; Soofi, Shauheen S; Thode, Christopher; Nealey, Paul F

2012-08-01

Glass transition in thin (1-200 nm thick) spin-cast polystyrene films on silicon surfaces is probed by ellipsometry in a controlled vacuum environment. A temperature-modulated modification of the method is used alongside a traditional linear temperature scan. A clear glass transition is detected in films with thicknesses as low as 1-2 nm. The glass transition temperature (T(g)) shows no substantial dependence on thickness for coatings greater than 20 nm. Thinner films demonstrate moderate T(g) depression achieving 18 K for thicknesses 4-7 nm. Less than 4 nm thick samples are excluded from the T(g) comparison due to significant thickness nonuniformity (surface roughness). The transition in 10-20 nm thick films demonstrates excessive broadening. For some samples, the broadened transition is clearly resolved into two separate transitions. The thickness dependence of the glass transition can be well described by a simple 2-layer model. It is also shown that T(g) depression in 5 nm thick films is not sensitive to a wide range of experimental factors including molecular weight characteristics of the polymer, specifications of solvent used for spin casting, substrate composition, and pretreatment of the substrate surface.

Note on the glass transition temperature of poly(vinylphenol)

Czech Academy of Sciences Publication Activity Database

Kratochvíl, Jaroslav; Šturcová, Adriana; Sikora, Antonín; Dybal, Jiří

2009-01-01

Roč. 45, č. 6 (2009), s. 1851-1856 ISSN 0014-3057 Institutional research plan: CEZ:AV0Z40500505 Keywords : Poly(4-vinylphenol) * glass transition temperature * differential scanning calorimetry Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.310, year: 2009

Glass transition temperature of PMMA/modified alumina nanocomposite: Molecular dynamic study

OpenAIRE

Mohammadi, Maryam; Davoodi, Jamal; Javanbakht, Mahdi; Rezaei, Hamidreza

2017-01-01

In this study, the effect of alumina and modified alumina nanoparticles in a PMMA/alumina nanocomposite was investigated. To attain this goal, the glass transition behavior of poly methyl methacrylate (PMMA), PMMA/alumina and PMMA/hydroxylated alumina nanocomposites were investigated by molecular dynamic simulations (MD). All the MD simulations were performed using the Materials Studio 6.0 software package of Accelrys. To obtain the glass transition temperature, the variation of density vs. t...

Determination of the glass transition temperature of cyclodextrin polymers.

Science.gov (United States)

Tabary, Nicolas; Garcia-Fernandez, Maria Jose; Danède, Florence; Descamps, Marc; Martel, Bernard; Willart, Jean-François

2016-09-05

The aim of this work was to determine the main physical characteristics of β-cyclodextrin polymers, well known for improving complexation capacities and providing enhanced and sustained release of a large panel of drugs. Two polymers were investigated: a polymer of β-cyclodextrin (polyβ-CD) and a polymer of partially methylated (DS=0.57) β-cyclodextrin (polyMe-β-CD). The physical characterizations were performed by powder X-ray diffraction and differential scanning calorimetry. The results indicate that these polymers are amorphous and that their glass transition is located above the thermal degradation point of the materials preventing their direct observation and thus their full characterization. We could however estimate the virtual glass transition temperatures by mixing the polymers with different plasticizers (trehalose and mannitol) which decreases Tg sufficiently to make the glass transition observable. Extrapolation to zero plasticizer concentration then yield the following Tg values: Tg (polyMe-β-CD)=317°C±5°C and Tg (polyβ-CD)=418°C±6°C. Copyright © 2016 Elsevier Ltd. All rights reserved.

Deformation, Stress Relaxation, and Crystallization of Lithium Silicate Glass Fibers Below the Glass Transition Temperature

Science.gov (United States)

Ray, Chandra S.; Brow, Richard K.; Kim, Cheol W.; Reis, Signo T.

2004-01-01

The deformation and crystallization of Li(sub 2)O (center dot) 2SiO2 and Li(sub 2)O (center dot) 1.6SiO2 glass fibers subjected to a bending stress were measured as a function of time over the temperature range -50 to -150 C below the glass transition temperature (Tg). The glass fibers can be permanently deformed at temperatures about 100 C below T (sub)g, and they crystallize significantly at temperatures close to, but below T,, about 150 C lower than the onset temperature for crystallization for these glasses in the no-stress condition. The crystallization was found to occur only on the surface of the glass fibers with no detectable difference in the extent of crystallization in tensile and compressive stress regions. The relaxation mechanism for fiber deformation can be best described by a stretched exponential (Kohlrausch-Williams-Watt (KWW) approximation), rather than a single exponential model.The activation energy for stress relaxation, Es, for the glass fibers ranges between 175 and 195 kJ/mol, which is considerably smaller than the activation energy for viscous flow, E, (about 400 kJ/mol) near T, for these glasses at normal, stress-free condition. It is suspected that a viscosity relaxation mechanism could be responsible for permanent deformation and crystallization of the glass fibers below T,

Predicting bioactive glass properties from the molecular chemical composition: glass transition temperature.

Science.gov (United States)

O'Donnell, Matthew D

2011-05-01

The glass transition temperature (T(g)) of inorganic glasses is an important parameter than can be used to correlate with other glass properties, such as dissolution rate, which governs in vitro and in vivo bioactivity. Seven bioactive glass compositional series reported in the literature (77 in total) were analysed here with T(g) values obtained by a number of different methods: differential thermal analysis, differential scanning calorimetry and dilatometry. An iterative least-squares fitting method was used to correlate T(g) from thermal analysis of these compositions with the levels of individual oxide and fluoride components in the glasses. When all seven series were fitted a reasonable correlation was found between calculated and experimental values (R(2)=0.89). When the two compositional series that were designed in weight percentages (the remaining five were designed in molar percentage) were removed from the model an improved fit was achieved (R(2)=0.97). This study shows that T(g) for a wide range in compositions (e.g. SiO(2) content of 37.3-68.4 mol.%) can be predicted to reasonable accuracy enabling processing parameters to be predicted such as annealing, fibre-drawing and sintering temperatures. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Exploration of a new method in determining the glass transition temperature of BMGs by electrical resistivity

Science.gov (United States)

Guo, Jing; Zu, Fangqiu; Chen, Zhihao; Zheng, Shubin; Yuan, Yuan

2005-07-01

Based on a brief retrospect of the method in establishing Tg of the bulk metallic glasses (BMGs), some perplexities concerning this are pointed out. With the experimental results of Zr-Al-Ni-Cu-X (Nb,Ti) BMGs, a electrical resistivity method is proposed to determine the glass transition temperature of BMGs. With the method, we define two kinds of characteristic temperature related to the glass transition, Tg-dep and Tg-int, respectively. By comparing Tg-dep and Tg-int with Tg determined by the DSC method, we have found that, for the same alloy at the same heating rate, Tg-dep is very close to Tg-onset while Tg-int is approximate to Tg-mid. As a method to determine the glass transition temperature, the electrical resistivity method has proved to be more convenient and practical in comparison with the DSC method, especially when the DSC curve cannot show the glass transition character of BMGs. In addition, we would emphasize that when we refer to Tg, it is necessary to expatiate on the way of denoting the glass transition temperature, such as Tg-dep or Tg-int ( Tg-onset or Tg-mid), and on the heating rate, in order to avoid ambiguity.

Glass transition temperature of dried lens tissue pretreated with trehalose, maltose, or cyclic tetrasaccharide.

Science.gov (United States)

Kawata, Tetsuhiro; Matsuo, Toshihiko; Uchida, Tetsuya

2014-01-01

Glass transition temperature is a main indicator for amorphous polymers and biological macromolecules as materials, and would be a key for understanding the role of trehalose in protecting proteins and cells against desiccation. In this study, we measured the glass transition temperature by differential scanning calorimetry of dried lens tissues as a model of a whole biological tissue to know the effect of pretreatment by trehalose and other sugars. Isolated porcine lenses were incubated with saline, 100 or 1000 mM concentration of trehalose, maltose, or cyclic tetrasaccharide dissolved in saline at room temperature for 150 minutes. The solutions were removed and all samples were dried at room temperature in a desiccator until no weight change. The dried tissues were ground into powder and placed in a measuring pan for differential scanning calorimetry. The glass transition temperature of the dried lens tissues, as a mean and standard deviation, was 63.0 ± 6.4°C (n = 3) with saline pretreatment; 53.0 ± 0.8°C and 56.3 ± 2.7°C (n = 3), respectively, with 100 and 1000 mM trehalose pretreatment; 56.0 ± 1.6°C and 55.8 ± 1.1°C (n = 3), respectively, with 100 and 1000 mM maltose pretreatment; 60.0 ± 8.8°C and 59.2 ± 6.3°C (n = 3), respectively, with 100 and 1000 mM cyclic tetrasaccharide pretreatment. The glass transition temperature appeared lower, although not significantly, with trehalose and maltose pretreatments than with saline and cyclic tetrasaccharide pretreatments (P > 0.05, Kruskal-Wallis test). The glass transition temperature of the dried lens tissues with trehalose pretreatment appeared more noticeable on the thermogram, compared with other pretreatments. The glass transition temperature was measured for the first time in the dried lens tissues as an example of a whole biological tissue and might provide a basis for tissue preservation in the dried condition.

Photoacoustic investigation of glass transition in AsxTe1-x glasses

International Nuclear Information System (INIS)

Madhusoodanan, K.N.; Nandakumar, K.; Philip, J.; Titus, S.S.K.; Asokan, S.; Gopal, E.S.R.

1989-01-01

Photoacoustic (Pa) technique is used to study glass transition and temperature dependence of thermal diffusivity in As x Te 1-x glasses with 0.25 ≤ x ≤ 0.60. PA amplitude goes through a minimum and the phase shows a maximum at glass transition temperature T g . The variation of thermal diffusivity with temperature shows sharp decrease near T g . The variation of thermal diffusivity with composition shows maximum at x = 0.40 for all temperatures T ≤ T g . (author)

Strong-Superstrong Transition in Glass Transition of Metallic Glass

International Nuclear Information System (INIS)

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

2010-01-01

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

Depression of Glass Transition Temperatures of Polymer Networks by Diluents

NARCIS (Netherlands)

Brinke, Gerrit ten; Karasz, Frank E.; Ellis, Thomas S.

1983-01-01

A classical thermodynamic theory is used to derive expressions for the depression of the glass transition temperature Tg of a polymer network by a diluent. The enhanced sensitivity of Tg in cross-linked systems to small amounts of diluent is explained. Predictions of the theory are in satisfactory

Glass Transition Temperature Measurement for Undercured Cyanate Ester Networks: Challenges, Tips, and Tricks (Briefing Charts)

Science.gov (United States)

2014-01-29

DISTRIBUTION A: Approved for public release; distribution is unlimited. Thermosetting Polymers Have a TG Envelope – Not Just a TG 4 • The glass transition...glass transition temperature of a thermosetting polymer can vary over a wide range of temperatures depending on how the polymer is processed • A... thermosetting polymer with only one kind of network formation and negligible side reactions, the conversion may be determined at every point in the scan. • By

Glass transition temperature of hard chairside reline materials after post-polymerisation treatments.

Science.gov (United States)

Urban, Vanessa M; Machado, Ana L; Alves, Marinês O; Maciel, Adeilton P; Vergani, Carlos E; Leite, Edson R

2010-09-01

This study evaluated the effect of post-polymerisation treatments on the glass transition temperature (T(g)) of five hard chairside reline materials (Duraliner II-D, Kooliner-K, New Truliner-N, Ufi Gel hard-U and Tokuso Rebase Fast-T). Specimens (10 x 10 x 1 mm) were made following the manufacturers' instructions and divided into three groups (n = 5). Control group specimens were left untreated. Specimens from the microwave group were irradiated with pre-determined power/time combinations, and specimens from the water-bath group were immersed in hot water at 55 degrees C for 10 min. Glass transition ( degrees C) was performed by differential scanning calorimetry. Data were analysed using anova, followed by post hoc Tukey's test (alpha = 0.05). Both post-polymerisation treatments promoted a significant (p glass transition of material Kooliner, with the effect being more pronounced for microwave irradiation.

Practical Considerations for Determination of Glass Transition Temperature of a Maximally Freeze Concentrated Solution.

Science.gov (United States)

Pansare, Swapnil K; Patel, Sajal Manubhai

2016-08-01

Glass transition temperature is a unique thermal characteristic of amorphous systems and is associated with changes in physical properties such as heat capacity, viscosity, electrical resistance, and molecular mobility. Glass transition temperature for amorphous solids is referred as (T g), whereas for maximally freeze concentrated solution, the notation is (T g'). This article is focused on the factors affecting determination of T g' for application to lyophilization process design and frozen storage stability. Also, this review provides a perspective on use of various types of solutes in protein formulation and their effect on T g'. Although various analytical techniques are used for determination of T g' based on the changes in physical properties associated with glass transition, the differential scanning calorimetry (DSC) is the most commonly used technique. In this article, an overview of DSC technique is provided along with brief discussion on the alternate analytical techniques for T g' determination. Additionally, challenges associated with T g' determination, using DSC for protein formulations, are discussed. The purpose of this review is to provide a practical industry perspective on determination of T g' for protein formulations as it relates to design and development of lyophilization process and/or for frozen storage; however, a comprehensive review of glass transition temperature (T g, T g'), in general, is outside the scope of this work.

Transport properties of glass-forming liquids suggest that dynamic crossover temperature is as important as the glass transition temperature.

Science.gov (United States)

Mallamace, Francesco; Branca, Caterina; Corsaro, Carmelo; Leone, Nancy; Spooren, Jeroen; Chen, Sow-Hsin; Stanley, H Eugene

2010-12-28

It is becoming common practice to partition glass-forming liquids into two classes based on the dependence of the shear viscosity η on temperature T. In an Arrhenius plot, ln η vs 1/T, a strong liquid shows linear behavior whereas a fragile liquid exhibits an upward curvature [super-Arrhenius (SA) behavior], a situation customarily described by using the Vogel-Fulcher-Tammann law. Here we analyze existing data of the transport coefficients of 84 glass-forming liquids. We show the data are consistent, on decreasing temperature, with the onset of a well-defined dynamical crossover η(×), where η(×) has the same value, η(×) ≈ 10(3) Poise, for all 84 liquids. The crossover temperature, T(×), located well above the calorimetric glass transition temperature T(g), marks significant variations in the system thermodynamics, evidenced by the change of the SA-like T dependence above T(×) to Arrhenius behavior below T(×). We also show that below T(×) the familiar Stokes-Einstein relation D/T ∼ η(-1) breaks down and is replaced by a fractional form D/T ∼ η(-ζ), with ζ ≈ 0.85.

Effect of the glass transition temperature on alpha-amylase activity in a starch matrix.

Science.gov (United States)

Chaudhary, Vinita; Panyoyai, Naksit; Small, Darryl M; Shanks, Robert A; Kasapis, Stefan

2017-02-10

This study optimises a protocol for the estimation of α-amylase activity in a condensed starch matrix in the vicinity of the glass transition region. Enzymatic activity on the vitrified starch system was compared with that of a reference substrate, maltodextrin. The activity was assayed as the rate of release of reducing sugar using a dinitrosalicylic acid procedure. The condensed carbohydrate matrices served the dual purpose of acting as a substrate as well as producing a pronounced effect on the ability to enzymatic hydrolysis. Activation energies were estimated throughout the glass transition region of condensed carbohydrate preparations based on the concept of the spectroscopic shift factor. Results were used to demonstrate a considerable moderation by the mechanical glass transition temperature, beyond the expected linear effect of the temperature dependence, on the reaction rate of starch hydrolysis by α-amylase in comparison with the low-molecular weight chain of maltodextrin. Copyright © 2016. Published by Elsevier Ltd.

Spin-glass transition in disordered terbium

International Nuclear Information System (INIS)

Hauser, J.J.

1985-01-01

While crystalline Tb is a helix antiferromagnet with a Neel temperature of 229 K which becomes ferromagnetic at 222 K, disordered Tb exhibits a spin-glass transition. The spin-glass freezing temperature ranges from 183 to 53 K, the lowest temperatures corresponding to the greatest degree of atomic disorder. These experiments constitute the first evidence for an elemental spin-glass. (author)

Glass transition of anhydrous starch by fast scanning calorimetry.

Science.gov (United States)

Monnier, Xavier; Maigret, Jean-Eudes; Lourdin, Denis; Saiter, Allisson

2017-10-01

By means of fast scanning calorimetry, the glass transition of anhydrous amorphous starch has been measured. With a scanning rate of 2000Ks -1 , thermal degradation of starch prior to the glass transition has been inhibited. To certify the glass transition measurement, structural relaxation of the glassy state has been investigated through physical aging as well as the concept of limiting fictive temperature. In both cases, characteristic enthalpy recovery peaks related to the structural relaxation of the glass have been observed. Thermal lag corrections based on the comparison of glass transition temperatures measured by means of differential and fast scanning calorimetry have been proposed. The complementary investigations give an anhydrous amorphous starch glass transition temperature of 312±7°C. This estimation correlates with previous extrapolation performed on hydrated starches. Copyright © 2017 Elsevier Ltd. All rights reserved.

Glass Transitions and Low-Frequency Dynamics of Room-Temperature Ionic Liquids

International Nuclear Information System (INIS)

Yamamuro, O.; Inamura, Y.; Hayashi, S.; Hamaguchi, H.

2006-01-01

We have measured the heat capacity and neutrion quasi- and inelastic scattering spectra of some salts of 1-butyl-3-methylimidazolium ion bmim+, which is a typical cation of room-temperature ionic liquids, and its derivatives. The heat capacity measurements revealed that the room-temperature ionic liquids have glass transitions as molecular liquids. The temperature dependence of configurational entropy demonstrated that the room-temperature ionic liquids are 'fragile liquids'. Both heat capacity and inelastic neutron scattering data revealed that the glassy phases exhibit large low-energy excitations usually called 'boson peak'. The quasielastic neutron scattering data showed that so-called 'fast process' appears around Tg as in molecular and polymer glasses. The temperature dependence of the self-diffusion coefficient derived from the neutron scattering data indicated that the orientation of bmim+ ions and/or butyl-groups of bmim+ ions is highly disordered and very flexible in an ionic liquid phase

Polymer relaxations in thin films in the vicinity of a penetrant or a temperature induced glass transition

NARCIS (Netherlands)

Ogieglo, Wojciech; Wessling, Matthias; Benes, Nieck Edwin

2014-01-01

The transient properties of thin glassy polymer films in the vicinity of the glass transition are investigated. We compare the differences and similarities between sorption and temperature induced glass transitions, referred to as Pg and Tg, respectively. The experimental technique used is in situ

Determination of the glass transition temperature: methods correlation and structural heterogeneity

OpenAIRE

Hutchinson, John M.

2009-01-01

The definition of the glass transition temperature, Tg, is recalled and its experimental determination by various techniques is reviewed. The diversity of values of Tg obtained by the different methods is discussed, with particular attention being paid to Differential Scanning Calorimetry (DSC) and to dynamic techniques such as Dynamic Mechanical Thermal Analysis (DMTA) and Temperature Modulated DSC (TMDSC). This last technique, TMDSC, in particular, is considered in respect of ways in which ...

Molecular Motion in Polymers: Mechanical Behavior of Polymers Near the Glass-Rubber Transition Temperature.

Science.gov (United States)

Sperling, L. H.

1982-01-01

The temperature at which the onset of coordinated segmental motion begins is called the glass-rubber transition temperature (Tg). Natural rubber at room temperature is a good example of a material above its Tg. Describes an experiment examining the response of a typical polymer to temperature variations above and below Tg. (Author/JN)

Light-scattering study of the glass transition in lubricants

Science.gov (United States)

Alsaad, M. A.; Winer, W. O.; Medina, F. D.; Oshea, D. C.

1977-01-01

The sound velocity of four lubricants has been measured as a function of temperature and pressure using Brillouin scattering. A change in slope of the velocity as a function of temperature or pressure allowed the determination of the glass transition temperature and pressure. The glass transition data were used to construct a phase diagram for each lubricant. The data indicate that the glass transition temperature increased with pressure at a rate which ranged from 120 to 200 C/GPa. The maximum pressure attained was 0.69 GPa and the temperature range was from 25 to 100 C.

Glass transition in thaumatin crystals revealed through temperature-dependent radiation-sensitivity measurements

Energy Technology Data Exchange (ETDEWEB)

Warkentin, Matthew, E-mail: maw64@cornell.edu; Thorne, Robert E. [Physics Department, Cornell University, Ithaca, New York (United States)

2010-10-01

Radiation damage to protein crystals exhibits two regimes of temperature-activated behavior between T = 300 and 100 K, with a crossover at the protein glass transition near 200 K. These results have implications for mechanistic studies of proteins and for structure determination when cooling to T = 100 K creates excessive disorder. The temperature-dependence of radiation damage to thaumatin crystals between T = 300 and 100 K is reported. The amount of damage for a given dose decreases sharply as the temperature decreases from 300 to 220 K and then decreases more gradually on further cooling below the protein-solvent glass transition. Two regimes of temperature-activated behavior were observed. At temperatures above ∼200 K the activation energy of 18.0 kJ mol{sup −1} indicates that radiation damage is dominated by diffusive motions in the protein and solvent. At temperatures below ∼200 K the activation energy is only 1.00 kJ mol{sup −1}, which is of the order of the thermal energy. Similar activation energies describe the temperature-dependence of radiation damage to a variety of solvent-free small-molecule organic crystals over the temperature range T = 300–80 K. It is suggested that radiation damage in this regime is vibrationally assisted and that the freezing-out of amino-acid scale vibrations contributes to the very weak temperature-dependence of radiation damage below ∼80 K. Analysis using the radiation-damage model of Blake and Phillips [Blake & Phillips (1962 ▶), Biological Effects of Ionizing Radiation at the Molecular Level, pp. 183–191] indicates that large-scale conformational and molecular motions are frozen out below T = 200 K but become increasingly prevalent and make an increasing contribution to damage at higher temperatures. Possible alternative mechanisms for radiation damage involving the formation of hydrogen-gas bubbles are discussed and discounted. These results have implications for mechanistic studies of proteins and for

Determination of Material Properties Near the Glass Transition Temperature for an Isogrid Boom

Science.gov (United States)

Blandino, Joseph R.; Woods-Vedeler, Jessica A. (Technical Monitor)

2002-01-01

Experiments were performed and results obtained to determine the temperature dependence of the modulus of elasticity for a thermoplastic isogrid tube. The isogrid tube was subjected to axial tensile loads of 0-100 lbf and strain was measured at room and elevated temperatures of 100, 120, 140, 160, 180, 190, and 200 F. These were based on tube manufacturer specifying an incorrect glass transition temperature of 210 F. Two protocols were used. For the first protocol the tube was brought to temperature and a tensile test performed. The tube was allowed to cool between tests. For the second protocol the tube was ramped to the desired test temperature and held. A tensile test was performed and the tube temperature ramped to the next test temperature. The second protocol spanned the entire test range. The strain rate was constant at 0.008 in/min. Room temperature tests resulted in the determination of an average modulus of 2.34 x 106 Psi. The modulus decreased above 100 F. At 140 F the modulus had decreased by 7.26%. The two test protocols showed good agreement below 160 F. At this point the glass transition temperature had been exceeded. The two protocols were not repeated because the tube failed.

DWPF glass transition temperatures: What they are and why they are important

International Nuclear Information System (INIS)

Marra, S.L.; Jantzen, C.M.; Ramsey, A.A.

1991-01-01

The Defense Waste Processing Facility (DWPF) at the Savannah River Site will immobilize high-level radioactive liquid waste in borosilicate glass. The glass will be poured into stainless steel canisters for eventual disposal in a geologic repository. The Department of Energy has defined a set of requirements for the DWPF canistered waste form which must be met in order to assure compatibility with, and acceptance by, the repository. These requirements are the Waste Acceptance Preliminary Specifications (WAPS). The WAPS require DWPF to report glass transition temperatures for the projected range of compositions. This information will be used by the repository to establish waste package design limits

Local variation of fragility and glass transition temperature of ultra-thin supported polymer films.

Science.gov (United States)

Hanakata, Paul Z; Douglas, Jack F; Starr, Francis W

2012-12-28

Despite extensive efforts, a definitive picture of the glass transition of ultra-thin polymer films has yet to emerge. The effect of film thickness h on the glass transition temperature T(g) has been widely examined, but this characterization does not account for the fragility of glass-formation, which quantifies how rapidly relaxation times vary with temperature T. Accordingly, we simulate supported polymer films of a bead-spring model and determine both T(g) and fragility, both as a function of h and film depth. We contrast changes in the relaxation dynamics with density ρ and demonstrate the limitations of the commonly invoked free-volume layer model. As opposed to bulk polymer materials, we find that the fragility and T(g) do not generally vary proportionately. Consequently, the determination of the fragility profile--both locally and for the film as a whole--is essential for the characterization of changes in film dynamics with confinement.

Chiral-glass transition in a diluted dipolar-interaction Heisenberg system

International Nuclear Information System (INIS)

Zhang Kaicheng; Liu Guibin; Zhu Yan

2011-01-01

Recently, numerical simulations reveal that a spin-glass transition can occur in the three-dimensional diluted dipolar system. By defining the chirality of triple spins in a diluted dipolar Heisenberg spin glass, we study the chiral ordering in the system using parallel tempering algorithm and heat bath method. The finite-size scaling analysis reveals that the system undergoes a chiral-glass transition at finite temperature. - Highlights: → We define the chirality in a diluted dipolar Heisenberg system. → The system undergoes a chiral-glass transition at finite temperature. → We extract the critical exponents of the chiral-glass transition.

Low-Cost, High Glass-Transition Temperature, Thermosetting Polyimide Developed

Science.gov (United States)

Chuang, Kathy C.

1999-01-01

PMR-15 polyimide, developed in the mid-1970's at the NASA Lewis Research Center, is recognized as a state-of-the-art high-temperature resin for composite applications in the temperature range of 500 to 550 F (260 to 288 C). PMR-15 offers easy processing and good property retention at a reasonable cost. For these reasons, it is widely used in both military and commercial aircraft engine components. Traditionally, polyimide composites have been designed for long-term use at 500 to 600 F over thousands of hours. However, new applications in reusable launch vehicles (RLV's) require lightweight materials that can perform for short times (tens of hours) at temperatures between 800 and 1000 F (425 and 538 C). Current efforts at Lewis are focused on raising the use temperature of polyimide composites by increasing the glass-transition temperature of the matrix resins. Achieving this dramatic increase in the upper use temperature without sacrificing polymer and composite processability is a major technical challenge.

Chiral-glass transition and replica symmetry breaking of a three-dimensional Heisenberg spin glass

OpenAIRE

Hukushima, K.; Kawamura, H.

2000-01-01

Extensive equilibrium Monte Carlo simulations are performed for a three-dimensional Heisenberg spin glass with the nearest-neighbor Gaussian coupling to investigate its spin-glass and chiral-glass orderings. The occurrence of a finite-temperature chiral-glass transition without the conventional spin-glass order is established. Critical exponents characterizing the transition are different from those of the standard Ising spin glass. The calculated overlap distribution suggests the appearance ...

Effect of In-Situ Cure on Measurement of Glass Transition Temperatures in High-Temperature Thermosetting Polymers (Briefing Charts)

Science.gov (United States)

2015-05-20

TEMPERATURES IN HIGH-TEMPERATURE THERMOSETTING POLYMERS 5a. CONTRACT NUMBER In-House 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d...temperature thermosetting polymer via dynamic mechanical analysis alone. These difficulties result from the residual cure of samples heated beyond their...98) Prescribed by ANSI Std. 239.18 Effect of In-Situ Cure on Measurement of Glass Transition Temperatures in High-Temperature Thermosetting

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

DEFF Research Database (Denmark)

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

2003-01-01

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

The glass transition in high-density amorphous ice.

Science.gov (United States)

Loerting, Thomas; Fuentes-Landete, Violeta; Handle, Philip H; Seidl, Markus; Amann-Winkel, Katrin; Gainaru, Catalin; Böhmer, Roland

2015-01-01

There has been a long controversy regarding the glass transition in low-density amorphous ice (LDA). The central question is whether or not it transforms to an ultraviscous liquid state above 136 K at ambient pressure prior to crystallization. Currently, the most widespread interpretation of the experimental findings is in terms of a transformation to a superstrong liquid above 136 K. In the last decade some work has also been devoted to the study of the glass transition in high-density amorphous ice (HDA) which is in the focus of the present review. At ambient pressure HDA is metastable against both ice I and LDA, whereas at > 0.2 GPa HDA is no longer metastable against LDA, but merely against high-pressure forms of crystalline ice. The first experimental observation interpreted as the glass transition of HDA was made using in situ methods by Mishima, who reported a glass transition temperature T g of 160 K at 0.40 GPa. Soon thereafter Andersson and Inaba reported a much lower glass transition temperature of 122 K at 1.0 GPa. Based on the pressure dependence of HDA's T g measured in Innsbruck, we suggest that they were in fact probing the distinct glass transition of very high-density amorphous ice (VHDA). Very recently the glass transition in HDA was also observed at ambient pressure at 116 K. That is, LDA and HDA show two distinct glass transitions, clearly separated by about 20 K at ambient pressure. In summary, this suggests that three glass transition lines can be defined in the p-T plane for LDA, HDA, and VHDA.

Numerical study of the glass-glass transition in short-ranged attractive colloids

International Nuclear Information System (INIS)

Zaccarelli, Emanuela; Sciortino, Francesco; Tartaglia, Piero

2004-01-01

We report extensive numerical simulations in the glass region for a simple model of short-ranged attractive colloids, the square well model. We investigate the behaviour of the density autocorrelation function and of the static structure factor in the region of temperatures and packing fractions where a glass-glass transition is expected according to theoretical predictions. We strengthen our observations by studying both waiting time and history dependence of the numerical results. We provide evidence supporting the possibility that activated bond-breaking processes destabilize the attractive glass, preventing the full observation of a sharp glass-glass kinetic transition

A Second Glass Transition in Pressure Collapsed Type II Clathrate Hydrates.

Science.gov (United States)

Andersson, Ove; Häussermann, Ulrich

2018-04-19

Type II clathrate hydrates (CHs) M·17 H 2 O, with M = tetrahydrofuran (THF) or 1,3-dioxolane, are known to collapse, or amorphize, on pressurization to ∼1.3 GPa in the temperature range 77-140 K. On heating at 1 GPa, these pressure-amorphized CH states show a weak, stretched sigmoid-shaped, heat-capacity increase because of a glass transition. Here we use thermal conductivity and heat capacity measurements to show that also type II CH with M = cyclobutanone (CB) collapses on isothermal pressurization and undergoes a similar, weak, glass transition upon heating at 1 GPa. Furthermore, we reveal for both THF CH and CB CH a second, much more pronounced, glass transition at temperatures above the thermally weak glass transition on heating in the 0.2-0.7 GPa range. This result suggests the general occurrence of two glass transitions in water-rich (94 mol %) pressure-collapsed CHs. Because of a large increase in dielectric permittivity concurrently as the weak heat capacity increase, the first glass transition must be due to kinetic unfreezing of water molecules. The thermal features of the second glass transition, measured on isobaric temperature cycling, are typical of a glass-liquid-glass transition, which suggests that pressure-amorphized CHs transform reversibly to liquids.

Mathematical modeling of photoinitiated coating degradation: Effects of coating glass transition temperature and light stabilizers

DEFF Research Database (Denmark)

Kiil, Søren; G.de With, R.A.T.M.Van Benthem

2013-01-01

A mathematical model, describing coating degradation mechanisms of thermoset coatings exposed to ultraviolet radiation and humidity at constant temperature, was extended to simulate the behavior of a coating with a low glass transition temperature. The effects of adding light stabilizers (a UV...

Interactions in a blend of two polymers greatly differing in glass transition temperature

Czech Academy of Sciences Publication Activity Database

Kratochvíl, Jaroslav; Šturcová, Adriana; Sikora, Antonín; Dybal, Jiří

2011-01-01

Roč. 49, č. 14 (2011), s. 1031-1040 ISSN 0887-6266 Institutional research plan: CEZ:AV0Z40500505 Keywords : differential scanning calorimetry (DSC) * fouriertransform infrared spectroscopy (FT-IR) * glass transition temperature Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.531, year: 2011

Material properties and glass transition temperatures of different thermoplastic starches after extrusion processing

NARCIS (Netherlands)

Janssen, Léon P.B.M.; Karman, Andre P.; Graaf, Robbert A. de

Four different starch sources, namely waxy maize, wheat, potato and pea starch were extruded with the plasticizer glycerol, the latter in concentrations of 15, 20 and 25% (w/w). The glass transition temperatures of the resulting thermoplastic products were measured by Dynamic Mechanical Thermal

Mobility restrictions and glass transition behaviour of an epoxy resin under confinement.

Science.gov (United States)

Djemour, A; Sanctuary, R; Baller, J

2015-04-07

Confinement can have a big influence on the dynamics of glass formers in the vicinity of the glass transition. Already 40 to 50 K above the glass transition temperature, thermal equilibration of glass formers can be strongly influenced by the confining substrate. We investigate the linear thermal expansion and the specific heat capacity cp of an epoxy resin (diglycidyl ether of bisphenol A, DGEBA) in a temperature interval of 120 K around the glass transition temperature. The epoxy resin is filled into controlled pore glasses with pore diameters between 4 and 111 nm. Since DGEBA can form H-bonds with silica surfaces, we also investigate the influence of surface silanization of the porous substrates. In untreated substrates a core/shell structure of the epoxy resin can be identified. The glass transition behaviours of the bulk phase and that of the shell phase are different. In silanized substrates, the shell phase disappears. At a temperature well above the glass transition, a second transition is found for the bulk phase - both in the linear expansion data as well as in the specific heat capacity. The cp data do not allow excluding the glass transition of a third phase as being the cause for this transition, whereas the linear expansion data do so. The additional transition temperature is interpreted as a separation between two regimes: above this temperature, macroscopic flow of the bulk phase inside the porous structure is possible to balance the mismatch of thermal expansion coefficients between DGEBA and the substrate. Below the transition temperature, this degree of freedom is hindered by geometrical constraints of the porous substrates. Moreover, this second transition could also be found in the linear expansion data of the shell phase.

Glass transition and thermal expansivity of polystyrene thin films

International Nuclear Information System (INIS)

Inoue, R.; Kanaya, T.; Miyazaki, T.; Nishida, K.; Tsukushi, I.; Shibata, K.

2006-01-01

We have studied glass transition temperature and thermal expansivity of polystyrene thin films supported on silicon substrate using X-ray reflectivity and inelastic neutron scattering techniques. In annealing experiments, we have found that the reported apparent negative expansivity of polymer thin films is caused by unrelaxed structure due to insufficient annealing. Using well-annealed films, we have evaluated glass transition temperature T g and thermal expansivity as a function of film thickness. The glass transition temperature decreases with film thickness and is constant below about 10 nm, suggesting the surface glass transition temperature of 355 K, which is lower than that in bulk. We have also found that the thermal expansivity in the glassy state decreases with film thickness even after annealing. The decrease has been attributed to hardening of harmonic force constant arising from chain confinement in a thin film. This idea has been confirmed in the inelastic neutron scattering measurements

Glass transition and thermal expansivity of polystyrene thin films

Energy Technology Data Exchange (ETDEWEB)

Inoue, R. [Institute for Chemical Research, Kyoto University, Uji, Kyoto-fu 611-0011 (Japan); Kanaya, T. [Institute for Chemical Research, Kyoto University, Uji, Kyoto-fu 611-0011 (Japan)]. E-mail: kanaya@scl.kyoto-u.ac.jp; Miyazaki, T. [Nitto Denko Corporation, 1-1-2 Shimohozumi, Ibaraki, Osaka-fu 567-8680 (Japan); Nishida, K. [Institute for Chemical Research, Kyoto University, Uji, Kyoto-fu 611-0011 (Japan); Tsukushi, I. [Chiba Institute of Technology, Narashino, Chiba-ken 275-0023 (Japan); Shibata, K. [Japan Atomic Energy Research Institute, Tokai, Ibaraki-ken 319-1195 (Japan)

2006-12-20

We have studied glass transition temperature and thermal expansivity of polystyrene thin films supported on silicon substrate using X-ray reflectivity and inelastic neutron scattering techniques. In annealing experiments, we have found that the reported apparent negative expansivity of polymer thin films is caused by unrelaxed structure due to insufficient annealing. Using well-annealed films, we have evaluated glass transition temperature T {sub g} and thermal expansivity as a function of film thickness. The glass transition temperature decreases with film thickness and is constant below about 10 nm, suggesting the surface glass transition temperature of 355 K, which is lower than that in bulk. We have also found that the thermal expansivity in the glassy state decreases with film thickness even after annealing. The decrease has been attributed to hardening of harmonic force constant arising from chain confinement in a thin film. This idea has been confirmed in the inelastic neutron scattering measurements.

Glass-Glass Transitions by Means of an Acceptor-Donor Percolating Electric-Dipole Network

Science.gov (United States)

Zhang, Le; Lou, Xiaojie; Wang, Dong; Zhou, Yan; Yang, Yang; Kuball, Martin; Carpenter, Michael A.; Ren, Xiaobing

2017-11-01

We report the ferroelectric glass-glass transitions in KN (K+/Nb5 +) -doped BaTiO3 ferroelectric ceramics, which have been proved by x-ray diffraction profile and Raman spectra data. The formation of glass-glass transitions can be attributed to the existence of cubic (C )-tetragonal (T )-orthorhombic (O )-rhombohedral (R ) ferroelectric transitions in short-range order. These abnormal glass-glass transitions can perform very small thermal hysteresis (approximately 1.0 K ) with a large dielectric constant (approximately 3000), small remanent polarization Pr , and relative high maximum polarization Pm remaining over a wide temperature range (220-350 K) under an electrical stimulus, indicating the potential applications in dielectric recoverable energy-storage devices with high thermal reliability. Further phase field simulations suggest that these glass-glass transitions are induced by the formation of a percolating electric defect-dipole network (PEDN). This proper PEDN breaks the long-range ordered ferroelectric domain pattern and results in the local phase transitions at the nanoscale. Our work may further stimulate the fundamental physical theory and accelerate the development of dielectric energy-storing devices.

Configurational entropy of polar glass formers and the effect of electric field on glass transition

Energy Technology Data Exchange (ETDEWEB)

Matyushov, Dmitry V., E-mail: dmitrym@asu.edu [Department of Physics and School of Molecular Sciences, Arizona State University, P.O. Box 871504, Tempe, Arizona 85287 (United States)

2016-07-21

A model of low-temperature polar liquids is constructed that accounts for the configurational heat capacity, entropy, and the effect of a strong electric field on the glass transition. The model is based on the Padé-truncated perturbation expansions of the liquid state theory. Depending on parameters, it accommodates an ideal glass transition of vanishing configurational entropy and its avoidance, with a square-root divergent enumeration function at the point of its termination. A composite density-temperature parameter ρ{sup γ}/T, often used to represent combined pressure and temperature data, follows from the model. The theory is in good agreement with the experimental data for excess (over the crystal state) thermodynamics of molecular glass formers. We suggest that the Kauzmann entropy crisis might be a signature of vanishing configurational entropy of a subset of degrees of freedom, multipolar rotations in our model. This scenario has observable consequences: (i) a dynamical crossover of the relaxation time and (ii) the fragility index defined by the ratio of the excess heat capacity and excess entropy at the glass transition. The Kauzmann temperature of vanishing configurational entropy and the corresponding glass transition temperature shift upward when the electric field is applied. The temperature shift scales quadratically with the field strength.

Configurational entropy of polar glass formers and the effect of electric field on glass transition.

Science.gov (United States)

Matyushov, Dmitry V

2016-07-21

A model of low-temperature polar liquids is constructed that accounts for the configurational heat capacity, entropy, and the effect of a strong electric field on the glass transition. The model is based on the Padé-truncated perturbation expansions of the liquid state theory. Depending on parameters, it accommodates an ideal glass transition of vanishing configurational entropy and its avoidance, with a square-root divergent enumeration function at the point of its termination. A composite density-temperature parameter ρ(γ)/T, often used to represent combined pressure and temperature data, follows from the model. The theory is in good agreement with the experimental data for excess (over the crystal state) thermodynamics of molecular glass formers. We suggest that the Kauzmann entropy crisis might be a signature of vanishing configurational entropy of a subset of degrees of freedom, multipolar rotations in our model. This scenario has observable consequences: (i) a dynamical crossover of the relaxation time and (ii) the fragility index defined by the ratio of the excess heat capacity and excess entropy at the glass transition. The Kauzmann temperature of vanishing configurational entropy and the corresponding glass transition temperature shift upward when the electric field is applied. The temperature shift scales quadratically with the field strength.

A thermally tunable inverse opal photonic crystal for monitoring glass transition.

Science.gov (United States)

Sun, Liguo; Xie, Zhuoying; Xu, Hua; Xu, Ming; Han, Guozhi; Wang, Cheng; Bai, Xuduo; Gu, ZhongZe

2012-03-01

An optical method was developed to monitor the glass transition of the polymer by taking advantage of reflection spectrum change of the thermally tunable inverse opal photonic crystal. The thermally tunable photonic bands of the polymer inverse opal photonic crystal were traceable to the segmental motion of macromolecules, and the segmental motion was temperature dependent. By observing the reflection spectrum change of the polystyrene inverse opal photonic crystal during thermal treatment, the glass transition temperature of polystyrene was gotten. Both changes of the position and intensity of the reflection peak were observed during the glass transition process of the polystyrene inverse opal photonic crystal. The optical change of inverse opal photonic crystal was so large that the glass transition temperature could even be estimated by naked eyes. The glass transition temperature derived from this method was consistent with the values measured by differential scanning calorimeter.

Gauge theory of glass transition

International Nuclear Information System (INIS)

Vasin, Mikhail

2011-01-01

A new analytical approach for the description of the glass transition in a frustrated system is suggested. The theory is based on the non-equilibrium dynamics technique, and takes into account the interaction of the local order field with the massive gauge field, which describes frustration-induced plastic deformation. The glass transition is regarded as a phase transition interrupted because of the premature critical slowing-down of one of the degrees of freedom caused by the frustrations. It is shown that freezing of the system appears when the correlation length and relaxation time of the gauge field diverge. The Vogel–Fulcher–Tammann relation for the transition kinetics and the critical exponent for the nonlinear susceptibility, 2.5∼ t correlation function dependence on time, and explains the boson peak appearance on this curve. In addition, the function of the glass transition temperature value with cooling rate is derived; this dependence fully conforms with known experimental data

Characterisation of moisture uptake effects on the glass transitional behaviour of an amorphous drug using modulated temperature DSC.

Science.gov (United States)

Royall, P G; Craig, D Q; Doherty, C

1999-12-01

The purpose of this study was to investigate the depression of the glass transition temperature, T(g), of the protease inhibitor saquinavir in the first heating scan as a function of the quantity of sorbed water by the application of modulated temperature differential scanning calorimetry (MTDSC). Samples of amorphous saquinavir were pretreated under various humidity conditions and the quantity of sorbed water measured by thermogravimetric analysis. MTDSC runs were performed using hermetically and non-hermetically sealed pans in order to determine the glass transition temperature. MTDSC allowed the separation of the glass transition from the enthalpic relaxation, thereby allowing clear visualisation of T(g) for amorphous saquinavir in the first heating scan. The plasticizing effects of water were assessed, with the depression in T(g) related to the mole fraction of water sorbed via the Gordon-Taylor relationship. An expression has been derived which allows estimation of the water content which lowers the T(g) to the storage temperature, thereby considerably increasing the risk of recrystallisation. It is argued that this model may aid prediction of the optimal storage conditions for amorphous drugs.

Effect of sugar addition on glass transition temperatures of cassava starch with low to intermediate moisture contents.

Science.gov (United States)

Figueroa, Yetzury; Guevara, Marvilan; Pérez, Adriana; Cova, Aura; Sandoval, Aleida J; Müller, Alejandro J

2016-08-01

This work studies how sucrose (S) addition modifies the thermal properties of cassava starch (CS). Neat CS and CS-S blends with 4, 6 and 8% sugar contents (CS-S-4%, CS-S-6% and CS-S-8%) were prepared and analyzed by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA), in a wide range of moisture levels (2-20%). In equilibrated samples with moisture contents lower than 10%, twoendothermic steps were observed during first DSC heating scans and two corresponding relaxation maxima in tan δ were detected by DMTA. The first transition, detected at around 45-55°C by both DSC and DMTA, is frequently found in starchy foods, while the second observed at higher temperatures is associated to the glass transition temperature of the blends. At higher moisture contents, only one thermal transition was observed. Samples analyzed immediately after cooling from the melt (i.e., after erasing their thermal history), exhibited a single glass transition temperature, regardless of their moisture content. Addition of sugar promotes water plasticization of CS only at high moisture contents. In the low moisture content range, anti-plasticization was observed for both neat and sugar-added CS samples. Addition of sugar decreases the moisture content needed to achieve the maximum value of the glass transition temperature before plasticization starts. The results of this work may be valuable for the study of texture establishment in low moisture content extruded food products. Copyright © 2016 Elsevier Ltd. All rights reserved.

Raman scattering boson peak and differential scanning calorimetry studies of the glass transition in tellurium-zinc oxide glasses.

Science.gov (United States)

Stavrou, E; Tsiantos, C; Tsopouridou, R D; Kripotou, S; Kontos, A G; Raptis, C; Capoen, B; Bouazaoui, M; Turrell, S; Khatir, S

2010-05-19

Raman scattering and differential scanning calorimetry (DSC) measurements have been carried out on four mixed tellurium-zinc oxide (TeO(2))(1 - x)(ZnO)(x) (x = 0.1, 0.2, 0.3, 0.4) glasses under variable temperature, with particular attention being given to the respective glass transition region. From the DSC measurements, the glass transition temperature T(g) has been determined for each glass, showing a monotonous decrease of T(g) with increasing ZnO content. The Raman study is focused on the low-frequency band of the glasses, the so-called boson peak (BP), whose frequency undergoes an abrupt decrease at a temperature T(d) very close to the respective T(g) values obtained by DSC. These results show that the BP is highly sensitive to dynamical effects over the glass transition and provides a means for an equally reliable (to DSC) determination of T(g) in tellurite glasses and other network glasses. The discontinuous temperature dependence of the BP frequency at the glass transition, along with the absence of such a behaviour by the high-frequency Raman bands (due to local atomic vibrations), indicates that marked changes of the medium range order (MRO) occur at T(g) and confirms the correlation between the BP and the MRO of glasses.

Raman scattering boson peak and differential scanning calorimetry studies of the glass transition in tellurium-zinc oxide glasses

International Nuclear Information System (INIS)

Stavrou, E; Tsiantos, C; Tsopouridou, R D; Kripotou, S; Kontos, A G; Raptis, C; Capoen, B; Bouazaoui, M; Turrell, S; Khatir, S

2010-01-01

Raman scattering and differential scanning calorimetry (DSC) measurements have been carried out on four mixed tellurium-zinc oxide (TeO 2 ) 1-x (ZnO) x (x = 0.1, 0.2, 0.3, 0.4) glasses under variable temperature, with particular attention being given to the respective glass transition region. From the DSC measurements, the glass transition temperature T g has been determined for each glass, showing a monotonous decrease of T g with increasing ZnO content. The Raman study is focused on the low-frequency band of the glasses, the so-called boson peak (BP), whose frequency undergoes an abrupt decrease at a temperature T d very close to the respective T g values obtained by DSC. These results show that the BP is highly sensitive to dynamical effects over the glass transition and provides a means for an equally reliable (to DSC) determination of T g in tellurite glasses and other network glasses. The discontinuous temperature dependence of the BP frequency at the glass transition, along with the absence of such a behaviour by the high-frequency Raman bands (due to local atomic vibrations), indicates that marked changes of the medium range order (MRO) occur at T g and confirms the correlation between the BP and the MRO of glasses.

Slow dynamics and glass transition in simulated free-standing polymer films: a possible relation between global and local glass transition temperatures

International Nuclear Information System (INIS)

Peter, S; Meyer, H; Baschnagel, J; Seemann, R

2007-01-01

We employ molecular dynamics simulations to explore the influence that the surface of a free-standing polymer film exerts on its structural relaxation when the film is cooled toward the glass transition. Our simulations are concerned with the features of a coarse-grained bead-spring model in a temperature regime above the critical temperature T c of mode-coupling theory. We find that the film dynamics is spatially heterogeneous. Monomers at the free surface relax much faster than they would in the bulk at the same temperature T. The fast relaxation of the surface layer continuously turns into bulk-like relaxation with increasing distance y from the surface. This crossover remains smooth for all T, but its range grows on cooling. We show that it is possible to associate a gradient in critical temperatures T c (y) with the gradient in the relaxation dynamics. This finding is in qualitative agreement with experimental results on supported polystyrene (PS) films (Ellison and Torkelson 2003 Nat. Mater. 2 695). Furthermore we show that the y dependence of T c (y) can be expressed in terms of the depression of T c (h)-the global T c for a film of thickness h-if we assume that T c (h) is the arithmetic mean of T c (y) and parameterize the depression of T c (h) by T c (h) = T c /(1+h 0 /h), a formula suggested by Herminghaus et al (2001 Eur. Phys. J. E 5 531) for the reduction of the glass transition temperature in supported PS films. We demonstrate the validity of this formula by comparing our simulation results to results from other simulations and experiments

Ideal glass transitions by random pinning

Science.gov (United States)

Cammarota, Chiara; Biroli, Giulio

2012-01-01

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

CORRELATION OF THE GLASS TRANSITION TEMPERATURE OF PLASTICIZED PVC USING A LATTICE FLUID MODEL

Science.gov (United States)

A model has been developed to describe the composition dependence of the glass transition temperature (Tg) of polyvinyl chloride (PVC) + plasticizer mixtures. The model is based on Sanchez-Lacombe equation of state and the Gibbs-Di Marzio criterion, which states that th...

Discontinuity in Fast Dynamics at the Glass Transition of ortho-Terphenyl.

Science.gov (United States)

Hoffman, David J; Fayer, Michael D

2017-11-16

The dynamics of the molecular glass former ortho-terphenyl through the glass transition were observed with two-dimensional infrared vibrational spectroscopy measurements of spectral diffusion using the small probe molecule phenylselenocyanate. Although the slow diffusive motions were not visible on the experimental time scale, a picosecond-scale exponential relaxation was observed at temperatures from above to well below the glass transition temperature. The characteristic time scale has a smooth temperature dependence from the liquid into the glass phase, but the range of vibrational frequencies the probe samples displayed a discontinuity at the glass transition temperature. Complementary pump-probe experiments associate the observed motion with density fluctuations. The key features of the dynamics are reproduced with a simple corrugated well potential energy surface model. In addition, the temperature dependence of the homogeneous vibrational dephasing was found to have a T 2 functional form, where T is the absolute temperature.

Effect of particle size on the glass transition.

Science.gov (United States)

Larsen, Ryan J; Zukoski, Charles F

2011-05-01

The glass transition temperature of a broad class of molecules is shown to depend on molecular size. This dependency results from the size dependence of the pair potential. A generalized equation of state is used to estimate how the volume fraction at the glass transition depends on the size of the molecule, for rigid molecule glass-formers. The model shows that at a given pressure and temperature there is a size-induced glass transition: For molecules larger than a critical size, the volume fraction required to support the effective pressure due to particle attractions is above that which characterizes the glassy state. This observation establishes the boundary between nanoparticles, which exist in liquid form only as dispersions in low molecular weight solvents and large molecules which form liquids that have viscosities below those characterized by the glassy state.

Temperature Dependence of Arn+ Cluster Backscattering from Polymer Surfaces: a New Method to Determine the Surface Glass Transition Temperature.

Science.gov (United States)

Poleunis, Claude; Cristaudo, Vanina; Delcorte, Arnaud

2018-01-01

In this work, time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to study the intensity variations of the backscattered Ar n + clusters as a function of temperature for several amorphous polymer surfaces (polyolefins, polystyrene, and polymethyl methacrylate). For all these investigated polymers, our results show a transition of the ratio Ar 2 + /(Ar 2 + + Ar 3 + ) when the temperature is scanned from -120 °C to +125 °C (the exact limits depend on the studied polymer). This transition generally spans over a few tens of degrees and the temperature of the inflection point of each curve is always lower than the bulk glass transition temperature (T g ) reported for the considered polymer. Due to the surface sensitivity of the cluster backscattering process (several nanometers), the presented analysis could provide a new method to specifically evaluate a surface transition temperature of polymers, with the same lateral resolution as the gas cluster beam. Graphical abstract ᅟ.

Discontinuous and heterogeneous glass transition behavior of carbohydrate polymer-plasticizer systems.

Science.gov (United States)

Kawai, Kiyoshi; Hagura, Yoshio

2012-07-01

In order to understand the glass transition properties of carbohydrate polymer-plasticizer systems, glass transition temperatures of dextrin-glucose and dextrin-maltose systems were investigated systematically using differential scanning calorimetry. The onset (Tg(on)) and offset (Tg(off)) of the glass transition decreased with increasing plasticizer (glucose or maltose) content, and showed an abrupt depression at certain plasticizer content. The abrupt depression of Tg(off) occurred at higher plasticizer content than that of Tg(on). The glass transition was much broader for intermediate plasticizer content. From the enthalpy relaxation behavior of samples aged at various temperatures, it was found that two different glass transitions occurred contentiously in the broad glass transition. These results suggested that carbohydrate polymer-plasticizer systems can be classified into three regions: the entrapment of the plasticizer by the polymer, the formations of the polymer-plasticizer and plasticizer-rich domains, and the embedment of polymer into the plasticizer. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

Tournier, Robert F.

2018-01-01

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

Unusual Crystallization Behavior Close to the Glass Transition

Science.gov (United States)

Desgranges, Caroline; Delhommelle, Jerome

2018-03-01

Using molecular simulations, we shed light on the mechanism underlying crystal nucleation in metal alloys and unravel the interplay between crystal nucleation and glass transition, as the conditions of crystallization lie close to this transition. While decreasing the temperature of crystallization usually results in a lower free energy barrier, we find an unexpected reversal of behavior for glass-forming alloys as the temperature of crystallization approaches the glass transition. For this purpose, we simulate the crystallization process in two glass-forming Copper alloys, Ag6 Cu4 , which has a positive heat of mixing, and CuZr, characterized by a large negative heat of mixing. Our results allow us to identify this unusual behavior as directly correlated with a nonmonotonic temperature dependence for the formation energy of connected icosahedral structures, which are incompatible with crystalline order and impede the development of the crystal nucleus, leading to an unexpectedly larger free energy barrier at low temperature. This, in turn, promotes the formation of a predominantly closed-packed critical nucleus, with fewer defects, thereby suggesting a new way to control the structure of the crystal nucleus, which is of key importance in catalysis.

DWPF glass transition temperatures - What they are and why they are important

International Nuclear Information System (INIS)

Marra, S.L.; Applewhite-Ramsey, A.L.; Jantzen, C.M.

1991-01-01

The Department of Energy has defined a set of requirements for the DWPF canistered waste form which must be met in order to assure compatibility with, and acceptance by, the first geologic repository. These requirements are the Waste Acceptance Preliminary Specifications (WAPS). The WAPS require DWPF to report glass transition temperatures for the projected range of compositions. This information will be used by the repository to establish waste package design limits

The peculiar behavior of the glass transition temperature of amorphous drug-polymer films coated on inert sugar spheres.

Science.gov (United States)

Dereymaker, Aswin; Van Den Mooter, Guy

2015-05-01

Fluid bed coating has been proposed in the past as an alternative technology for manufacturing of drug-polymer amorphous solid dispersions, or so-called glass solutions. It has the advantage of being a one-step process, and thus omitting separate drying steps, addition of excipients, or manipulation of the dosage form. In search of an adequate sample preparation method for modulated differential scanning calorimetry analysis of beads coated with glass solutions, glass transition broadening and decrease of the glass transition temperature (Tg ) were observed with increasing particle size of crushed coated beads and crushed isolated films of indomethacin (INDO) and polyvinylpyrrolidone (PVP). Substituting INDO with naproxen gave comparable results. When ketoconazole was probed or the solvent in INDO-PVP films was switched to dichloromethane (DCM) or a methanol-DCM mixture, two distinct Tg regions were observed. Small particle sizes had a glass transition in the high Tg region, and large particle sizes had a glass transition in the low Tg region. This particle size-dependent glass transition was ascribed to different residual solvent amounts in the bulk and at the surface of the particles. A correlation was observed between the deviation of the Tg from that calculated from the Gordon-Taylor equation and the amount of residual solvent at the Tg of particles with different sizes. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Neutron- and light-scattering studies of the liquid-to-glass and glass-to-glass transitions in dense copolymer micellar solutions

International Nuclear Information System (INIS)

Chen Weiren; Chen Sowhsin; Mallamace, Francesco; Glinka, Charles J.; Fratini, Emiliano

2003-01-01

Recent mode coupling theory (MCT) calculations show that if a short-range attractive interaction is added to the pure hard sphere system, one may observe a new type of glass originating from the clustering effect (the attractive glass) as a result of the attractive interaction. This is in addition to the known glass-forming mechanism due to the cage effect in the hard sphere system (the repulsive glass). The calculations also indicate that if the range of attraction is sufficiently short compared to the diameter of the particle, within a certain interval of volume fractions where the two glass-forming mechanisms nearly balance each other, varying the external control parameter, the effective temperature, makes the glass-to-liquid-to-glass reentrance and the glass-to-glass transitions possible. Here we present experimental evidence of both transitions, obtained from small-angle neutron-scattering and photon correlation measurements taken from dense L64 copolymer micellar solutions in heavy water. Varying the temperature in certain predicted volume fraction range triggers a sharp transition between these two different types of glass. In particular, according to MCT, there is an end point (called A 3 singularity) of this glass-to-glass transition line, beyond which the long-time dynamics of the two glasses become identical. Our findings confirm this theoretical prediction. Surprisingly, although the Debye-Waller factors, the long-time limit of the coherent intermediate scattering functions, of these two glasses obtained from photon correlation measurements indeed become identical at the predicted volume fraction, they exhibit distinctly different intermediate time relaxation. Furthermore, our experimental results obtained from volume fractions beyond the end point are characterized by the same features as the repulsive glass obtained before the end point. A complete phase diagram giving the boundaries of the structural arrest transitions for L64 micellar system is

Glass heat capacity and its abrupt change in glass transition region

DEFF Research Database (Denmark)

Yue, Yuanzheng; Smedskjær, Morten Mattrup; Mauro, John C.

cover a large range of glass formers from metallic to non-metallic glasses. To conduct this study we convert the units of all the Cp data from J/mol K and J/g K to J/g-atom K. This study will provide insight into the correlations among chemical bonding, microstructure structure, liquid fragility, glass......Glass transition (GT) has been a fascinating, but challenging subject in the condensed matter science over decades. Despite progress in understanding GT, many crucial problems still need to be clarified. One of the problems deals with the microscopic origin of abrupt change of heat capacity (Cp......) around glass transition. Here we study this problem through two approaches. First, we analyze the Cp change with temperature on homologous series of glass formers (i.e., with regular compositional substitution). Second, we do the same on non-homologous systems (e.g. without regular compositional...

How carbon nanotubes affect the cure kinetics and glass transition temperature of their epoxy composites? – A review

Directory of Open Access Journals (Sweden)

2009-09-01

Full Text Available Motivated by the widespread and contradictory results regarding the glass transition temperature of carbon nanotube (CNT/epoxy composites, we reviewed and analyzed the literature results dealing with the effect of unmodified multiwall carbon nanotubes (MWNT on the cure behaviour of an epoxy resin (as a possible source of this discrepancy. The aim of this work was to clarify the effective role of unmodified multiwall carbon nanotubes on the cure kinetics and glass transition temperature (Tg of their epoxy composites. It was found that various authors reported an acceleration effect of CNT. The cure reaction was promoted in its early stage which may be due to the catalyst particles present in the CNT raw material. While SWNT may lead to a decrease of Tg due to their bundling tendency, results reported for MWNT suggested an increased or unchanged Tg of the composites. The present status of the literature does not allow to isolate the effect of MWNT on the Tg due to the lack of a study providing essential information such as CNT purity, glass transition temperature along with the corresponding cure degree.

Effects of molecular weight on the glass transition temperature in Durolon polycarbonate

International Nuclear Information System (INIS)

Miranda, Adelina; Sciani, Valdir

1995-01-01

The effect of variation of the dose rate on degradation mechanism of PC Durolon irradiated with gamma rays was determined trough out intrinsic viscosity and thermal analysis of DSC-type measurements. The results showed a linear relationship between the glass transition temperature and the viscosimetric average molecular weight. From the results it's shown that with an increased of the dose rate it also increases the degradation of the material. (author). 12 refs., 3 figs

Spatial glass transition temperature variations in polymer glass: application to a maltodextrin-water system.

Science.gov (United States)

van Sleeuwen, Rutger M T; Zhang, Suying; Normand, Valéry

2012-03-12

A model was developed to predict spatial glass transition temperature (T(g)) distributions in glassy maltodextrin particles during transient moisture sorption. The simulation employed a numerical mass transfer model with a concentration dependent apparent diffusion coefficient (D(app)) measured using Dynamic Vapor Sorption. The mass average moisture content increase and the associated decrease in T(g) were successfully modeled over time. Large spatial T(g) variations were predicted in the particle, resulting in a temporary broadening of the T(g) region. Temperature modulated differential scanning calorimetry confirmed that the variation in T(g) in nonequilibrated samples was larger than in equilibrated samples. This experimental broadening was characterized by an almost doubling of the T(g) breadth compared to the start of the experiment. Upon reaching equilibrium, both the experimental and predicted T(g) breadth contracted back to their initial value.

A simple method for tuning the glass transition process in inorganic phosphate glasses

OpenAIRE

Fulchiron, Ren?; Belyamani, Imane; Otaigbe, Joshua U.; Bounor-Legar?, V?ronique

2015-01-01

The physical modification of glass transition temperature (Tg ) and properties of materials via blending is a common practice in industry and academia and has a large economic advantage. In this context, simple production of hitherto unattainable new inorganic glass blends from already existing glass compositions via blending raises much hope with the potential to provide new glasses with new and improved properties, that cannot be achieved with classical glass synthesis, for a plethora of ap...

Simultaneous Determination of Glass Transition Temperatures of Several Polymers.

Science.gov (United States)

He, Jiang; Liu, Wei; Huang, Yao-Xiong

2016-01-01

A simple and easy optical method is proposed for the determination of glass transition temperature (Tg) of polymers. Tg was determined using the technique of microsphere imaging to monitor the variation of the refractive index of polymer microsphere as a function of temperature. It was demonstrated that the method can eliminate most thermal lag and has sensitivity about six fold higher than the conventional method in Tg determination. So the determined Tg is more accurate and varies less with cooling/heating rate than that obtained by conventional methods. The most attractive character of the method is that it can simultaneously determine the Tg of several polymers in a single experiment, so it can greatly save experimental time and heating energy. The method is not only applicable for polymer microspheres, but also for the materials with arbitrary shapes. Therefore, it is expected to be broadly applied to different fundamental researches and practical applications of polymers.

Treatments of intrinsic viscosity and glass transition temperature data of poly(2,6-dimethylphenylmethacrylate)

International Nuclear Information System (INIS)

Hamidi, Nasrollah; Massoudi, Ruhullah

2003-01-01

A useful relationship, ln(T g )=ln(T g,∞ )-m[η] -ν , between intrinsic viscosity and glass transition temperature for a series of homologous polymers was obtained by combining the Mark-Houwink-Kuhn-Sakurada (MHKS) relation for intrinsic viscosity and molecular mass, and the Fox-Flory equation for glass transition temperature and number-average molecular mass. This relationship was applied to poly(2,6-dimethylphenylmethacrylate) (PDMPh) in a variety of solvents (ideal to good) such as toluene, tetrahydrofuran/water, tetrahydrofuran, and chlorobenzene systems. The parameter α estimated by this procedure in toluene, tetrahydrofuran/water, tetrahydrofuran, and chlorobenzene systems are 0.50 6 , 0.51 1 , 0.56 7 , and 0.67 3 , respectively which are in agreement with those of Mark-Houwink-Kuhn-Sakurada values by less than 5% differences. The T g,∞ quantity estimated from this equation also is within the standard deviation of that obtained from the Fox-Flory method. The m quantity is increasing as the thermodynamic quality of the solvent improves, therefore, m may be considered as an indicator of coil conformations in a given solvent

Thermodynamic Properties, Sorption Isotherms and Glass Transition Temperature of Cape Gooseberry (Physalis peruviana L.

Directory of Open Access Journals (Sweden)

Jessica López

2014-01-01

Full Text Available Adsorption and desorption isotherms of fresh and dried Cape gooseberry (Physalis peruviana L. were determined at three temperatures (20, 40 and 60 °C using a gravimetric technique. The data obtained were fitted to several models including Guggenheim-Anderson- De Boer (GAB, Brunauer-Emmett-Teller (BET, Henderson, Caurie, Smith, Oswin, Halsey and Iglesias-Chirife. A non-linear least square regression analysis was used to evaluate the models. The Iglesias-Chirife model fitted best the experimental data. Isosteric heat of sorption was also determined from the equilibrium sorption data using the Clausius-Clapeyron equation and was found to decrease exponentially with increasing moisture content. The enthalpy-entropy compensation theory was applied to the sorption isotherms and indicated an enthalpy-controlled sorption process. Glass transition temperature (Tg of Cape gooseberry was also determined by differential scanning calorimetry and modelled as a function of moisture content with the Gordon-Taylor, the Roos and the Khalloufi models, which proved to be excellent tools for predicting glass transition of Cape gooseberry.

Glass transition and crystallization kinetics of a barium borosilicate glass by a non-isothermal method

International Nuclear Information System (INIS)

Lopes, Andreia A. S.; Soares, Roque S.; Lima, Maria M. A.; Monteiro, Regina C. C.

2014-01-01

The glass transition and crystallization kinetics of a glass with a molar composition 60BaO-30B 2 O 3 -10SiO 2 were investigated by differential scanning calorimetry (DSC) under non-isothermal conditions. DSC curves exhibited an endothermic peak associated with the glass transition and two partially overlapped exothermic peaks associated with the crystallization of the glass. The dependence of the glass transition temperature (T g ) and of the maximum crystallization temperature (T p ) on the heating rate was used to determine the activation energy associated with the glass transition (E g ), the activation energy for crystallization (E c ), and the Avrami exponent (n). X-ray diffraction (XRD) revealed that barium borate (β-BaB 2 O 4 ) was the first crystalline phase to be formed followed by the formation of barium silicate (Ba 5 Si 8 O 21 ). The variations of activation energy for crystallization and of Avrami exponent with the fraction of crystallization (χ) were also examined. When the crystallization fraction (χ) increased from 0.1 to 0.9, the value of local activation energy (E c (χ)) decreased from 554 to 458 kJ/mol for the first exothermic peak and from 1104 to 831 kJ/mol for the second exothermic peak. The value determined for the Avrami exponent was near 2 indicating a similar one-dimensional crystallization mechanism for both crystalline phases. This was confirmed by the morphological studies performed by scanning electron microscopy (SEM) on glass samples heat-treated at the first and at the second crystallization temperatures

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

Science.gov (United States)

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

1978-01-01

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

High-Temperature Thermal Diffusivity Measurements of Silicate Glasses

Science.gov (United States)

Pertermann, M.; Hofmeister, A. M.; Whittington, A. G.; Spera, F. J.; Zayac, J.

2005-12-01

Transport of heat in geologically relevant materials is of great interest because of its key role in heat transport, magmatism and volcanic activity on Earth. To better understand the thermal properties of magmatic materials at high temperatures, we measured the thermal diffusivity of four synthetic end-member silicate glasses with the following compositions: albite (NaAlSi3O8), orthoclase (KAlSi3O8), anorthite (CaAl2Si2O8), and diopside (CaMgSi2O6). Thermal diffusivity measurements were conducted with the laser-flash technique and data were acquired from room temperature to a maximum temperature near 1100°C, depending on the glass transition temperature. The presence of sub-mm sized bubbles in one of the orthoclase samples had no discernable effect on measured diffusivities. At room temperature, the three feldspar-type glasses have thermal diffusivity (D) values of 0.58-0.61 mm2/s, whereas the diopside glass has 0.52 mm2/s. With increasing temperature, D decreases by 5-10% (relative) for all samples and becomes virtually constant at intermediate temperatures. At higher temperatures, the anorthite and diopside glasses exhibit significant drops in thermal diffusivity over a 50-100°C interval, correlating with previously published heat capacity changes near the glass transition for these compositions. For anorthite, D (in mm2/s) decreases from 0.48 at 750-860°C to 0.36 at 975-1075°C; for diopside, D changes from 0.42 at 630-750°C to 0.30 at 850-910°C, corresponding to relative drops of 24 and 29%, respectively. Albite and orthoclase glasses do not exhibit this change and also lack significant changes in heat capacity near the glass transition. Instead, D is constant at 400-800°C for albite, and for orthoclase values go through a minimum at 500-600°C before increasing slightly towards 1100°C but it never exceeds the room temperature D. Our data on thermal diffusivity correlate closely with other thermophysical properties. Thus, at least in case of simple

Effect of water content on the glass transition temperature of mixtures of sugars, polymers, and penetrating cryoprotectants in physiological buffer.

Science.gov (United States)

Drake, Andrew C; Lee, Youngjoo; Burgess, Emma M; Karlsson, Jens O M; Eroglu, Ali; Higgins, Adam Z

2018-01-01

Long-term storage of viable mammalian cells is important for applications ranging from in vitro fertilization to cell therapy. Cryopreservation is currently the most common approach, but storage in liquid nitrogen is relatively costly and the requirement for low temperatures during shipping is inconvenient. Desiccation is an alternative strategy with the potential to enable viable cell preservation at more convenient storage temperatures without the need for liquid nitrogen. To achieve stability during storage in the dried state it is necessary to remove enough water that the remaining matrix forms a non-crystalline glassy solid. Thus, the glass transition temperature is a key parameter for design of cell desiccation procedures. In this study, we have investigated the effects of moisture content on the glass transition temperature (Tg) of mixtures of sugars (trehalose or raffinose), polymers (polyvinylpyrrolidone or Ficoll), penetrating cryoprotectants (ethylene glycol, propylene glycol, or dimethyl sulfoxide), and phosphate buffered saline (PBS) solutes. Aqueous solutions were dried to different moisture contents by equilibration with saturated salt solutions, or by baking at 95°C. The glass transition temperatures of the dehydrated samples were then measured by differential scanning calorimetry. As expected, Tg increased with decreasing moisture content. For example, in a desiccation medium containing 0.1 M trehalose in PBS, Tg ranged from about 360 K for a completely dry sample to about 220 K at a water mass fraction of 0.4. Addition of polymers to the solutions increased Tg, while addition of penetrating cryoprotectants decreased Tg. Our results provide insight into the relationship between relative humidity, moisture content and glass transition temperature for cell desiccation solutions containing sugars, polymers and penetrating cryoprotectants.

Characterisation of the glass transition of an amorphous drug using modulated DSC.

Science.gov (United States)

Royall, P G; Craig, D Q; Doherty, C

1998-07-01

The use of modulated differential scanning calorimetry (MDSC) as a novel means of characterising the glass transition of amorphous drugs has been investigated, using the protease inhibitor saquinavir as a model compound. In particular, the effects of measuring variables (temperature cycling, scanning period, heating mode) have been examined. Saquinavir samples of known moisture content were examined using a TA Instruments 2920 MDSC at a heating rate of 2 degrees C/min and an amplitude of +/-0.159 degrees C with a period of 30 seconds. These conditions were used to examine the effects of cycling between - 50 degrees C and 150 degrees C. A range of periods between 20 and 50 seconds were then studied. Isothermal measurements were carried out between 85 degrees C and 120 degrees C using an amplitude of +/-0.159 degrees C with a period of 30 seconds. MDSC showed the glass transition of saquinavir (0.98 +/- 0.05%w/w moisture content) in isolation from the relaxation endotherm to give an apparent glass transition temperature of 107.0 degrees C +/- 0.4 degrees C. Subsequent temperature cycling gave reproducible glass transition temperatures of approximately 105 degrees C for both cooling and heating cycles. The enthalpic relaxation peak observed in the initial heating cycle had an additional contribution from a Tg "shift" effect brought about by the difference in response to the glass transition of the total and reversing heat flow signals. Isothermal studies yield a glass transition at 105.9 degrees C +/- 0.1 degrees C. MDSC has been shown to be capable of separating the glass transition of saquinavir from the relaxation endotherm, thereby facilitating measurement of this parameter without the need for temperature cycling. However, the Tg "shift" effect and the number of modulations through the transition should be taken into account to avoid drawing erroneous conclusions from the experimental data. MDSC has been shown to be an effective method of characterising the glass

Breaking Through the Glass Ceiling: Recent Experimental Approaches to Probe the Properties of Supercooled Liquids near the Glass Transition.

Science.gov (United States)

Smith, R Scott; Kay, Bruce D

2012-03-15

Experimental measurements of the properties of supercooled liquids at temperatures near their glass transition temperatures, Tg, are requisite for understanding the behavior of glasses and amorphous solids. Unfortunately, many supercooled molecular liquids rapidly crystallize at temperatures far above their Tg, making such measurements difficult to nearly impossible. In this Perspective, we discuss some recent alternative approaches to obtain experimental data in the temperature regime near Tg. These new approaches may yield the additional experimental data necessary to test current theoretical models of the dynamical slowdown that occurs in supercooled liquids approaching the glass transition.

Water’s second glass transition

Science.gov (United States)

Amann-Winkel, Katrin; Gainaru, Catalin; Handle, Philip H.; Seidl, Markus; Nelson, Helge; Böhmer, Roland

2013-01-01

The glassy states of water are of common interest as the majority of H2O in space is in the glassy state and especially because a proper description of this phenomenon is considered to be the key to our understanding why liquid water shows exceptional properties, different from all other liquids. The occurrence of water’s calorimetric glass transition of low-density amorphous ice at 136 K has been discussed controversially for many years because its calorimetric signature is very feeble. Here, we report that high-density amorphous ice at ambient pressure shows a distinct calorimetric glass transitions at 116 K and present evidence that this second glass transition involves liquid-like translational mobility of water molecules. This “double Tg scenario” is related to the coexistence of two liquid phases. The calorimetric signature of the second glass transition is much less feeble, with a heat capacity increase at Tg,2 about five times as large as at Tg,1. By using broadband-dielectric spectroscopy we resolve loss peaks yielding relaxation times near 100 s at 126 K for low-density amorphous ice and at 110 K for high-density amorphous ice as signatures of these two distinct glass transitions. Temperature-dependent dielectric data and heating-rate–dependent calorimetric data allow us to construct the relaxation map for the two distinct phases of water and to extract fragility indices m = 14 for the low-density and m = 20–25 for the high-density liquid. Thus, low-density liquid is classified as the strongest of all liquids known (“superstrong”), and also high-density liquid is classified as a strong liquid. PMID:24101518

Glass Transition, Crystallization of Glass-Forming Melts, and Entropy

Directory of Open Access Journals (Sweden)

Jürn W. P. Schmelzer

2018-02-01

Full Text Available A critical analysis of possible (including some newly proposed definitions of the vitreous state and the glass transition is performed and an overview of kinetic criteria of vitrification is presented. On the basis of these results, recent controversial discussions on the possible values of the residual entropy of glasses are reviewed. Our conclusion is that the treatment of vitrification as a process of continuously breaking ergodicity with entropy loss and a residual entropy tending to zero in the limit of zero absolute temperature is in disagreement with the absolute majority of experimental and theoretical investigations of this process and the nature of the vitreous state. This conclusion is illustrated by model computations. In addition to the main conclusion derived from these computations, they are employed as a test for several suggestions concerning the behavior of thermodynamic coefficients in the glass transition range. Further, a brief review is given on possible ways of resolving the Kauzmann paradox and its implications with respect to the validity of the third law of thermodynamics. It is shown that neither in its primary formulations nor in its consequences does the Kauzmann paradox result in contradictions with any basic laws of nature. Such contradictions are excluded by either crystallization (not associated with a pseudospinodal as suggested by Kauzmann or a conventional (and not an ideal glass transition. Some further so far widely unexplored directions of research on the interplay between crystallization and glass transition are anticipated, in which entropy may play—beyond the topics widely discussed and reviewed here—a major role.

High temperature spin-glass-like transition in La0.67Sr0.33MnO3 nanofibers near the Curie point.

Science.gov (United States)

Lu, Ruie; Yang, Sen; Li, Yitong; Chen, Kaiyun; Jiang, Yun; Fu, Bi; Zhang, Yin; Zhou, Chao; Xu, Minwei; Zhou, Xuan

2017-06-28

The glassy transition of superparamagnetic (SPM) (r glass-like (SGL) behavior near the Curie point (T C ), i.e., T 0 = 330 K, in La 0.67 Sr 0.33 MnO 3 (LSMO) nanofibers (NFs) composed of nanoparticles beyond the SPM size (r ≫ r 0 ), resulting in a significant increase of the glass transition temperature. This SGL transition near the T C of bulk LSMO can be explained to be the scenario of locally ordered clusters embedded in a disordered host, in which the assembly of nanoparticles has a magnetic core-shell model driven by surface spin glass. The presence of a surface spin glass of nanoparticles was proved by the Almeida-Thouless line δT f ∝ H 2/3 , exchange bias, and reduced saturation magnetization of the NF system. Composite dynamics were found - that is, both the SPM and the super-spin-glass (SSG) behavior are found in such an NF system. The bifurcation of the zero-field-cooled (ZFC) and field-cooled (FC) magnetization vs. temperature curves at the ZFC peak, and the flatness of FC magnetization involve SSG, while the frequency-dependent ac susceptibility anomaly follows the Vogel-Fulcher law that implies weak dipole interactions of the SPM model. This finding can help us to find a way to search for high temperature spin glass materials.

Radiation-Induced Fluidity and Glass-Liquid Transition in Irradiated Amorphous Materials

International Nuclear Information System (INIS)

Ojovan, M.I.

2009-01-01

This paper describes the fluidity behaviour of continuously irradiated glasses using the Congruent Bond Lattice model in which broken bonds 'configurons' facilitate the flow. Irradiation breaks the bonds creating configurons which at high concentrations provide the transition of material from the glassy to liquid state. An explicit equation of viscosity has been derived which gives results in agreement with experimental data. This equation provides correct viscosity data for non-irradiated materials and shows a significant increase of fluidity in radiation fields. It demonstrates a decrease of activation energy of flow for irradiated glasses. A simple equation for glass-transition temperature was also obtained which shows that irradiated glasses have lower glass transition temperatures and are readily transformed from glassy to liquid state e.g. fluidized in strong radiation fields. (authors)

4-(ALPHA, ALPHA-DIMETHYLBENZYL)PHENYL METHACRYLATE .3. SYNTHESIS, TACTICITY AND GLASS-TRANSITION TEMPERATURES OF ITS POLYMERS

NARCIS (Netherlands)

VANEKENSTEIN, GORA; TAN, YY

Depending on the kind of initiator, anionic Polymerization of 4-(alpha,alpha-dimethylbenzyl)phenyl methacrylate in toluene at -78-degrees-C led either to highly isotactic or predominantly syndiotactic polymers as determined by C-13 NMR spectro copy. The glass transition temperature difference

Quantitative determination of the specific heat and the glass transition of moist samples by temperature modulated differential scanning calorimetry.

Science.gov (United States)

Schubnell, M; Schawe, J E

2001-04-17

In differential scanning calorimetry (DSC), remnant moisture loss in samples often overlaps and distorts other thermal events, e.g. glass transitions. To separate such overlapping processes, temperature modulated DSC (TMDSC) has been widely used. In this contribution we discuss the quantitative determination of the heat capacity of a moist sample from TMDSC measurements. The sample was a spray-dried pharmaceutical compound run in different pans (hermetically-sealed pan, pierced lid pan [50 microm] and open pan). The apparent heat capacity was corrected for the remaining amount of moisture. Using this procedure we could clearly identify the glass transition of the dry and the moist sample. We found that a moisture content of about 6.2% shifts the glass transition by about 50 degrees C.

Shear viscosity of glass-forming melts in the liquid-glass transition region

International Nuclear Information System (INIS)

Sanditov, D. S.

2010-01-01

A new approach to interpreting the hole-activation model of a viscous flow of glass-forming liquids is proposed. This model underlies the development of the concept on the exponential temperature dependence of the free energy of activation of a flow within the range of the liquid-glass transition in complete agreement with available experimental data. The 'formation of a fluctuation hole' in high-heat glass-forming melts is considered as a small-scale low-activation local deformation of a structural network, i.e., the quasi-lattice necessary for the switching of the valence bond, which is the main elementary event of viscous flow of glasses and their melts. In this sense, the hole formation is a conditioned process. A drastic increase in the activation free energy of viscous flow in the liquid-glass transition region is explained by a structural transformation that is reduced to a limiting local elastic deformation of the structural network, which, in turn, originates from the excitation (critical displacement) of a bridging atom like the oxygen atom in the Si-O-Si bridge. At elevated temperatures, as a rule, a necessary amount of excited bridging atoms (locally deformed regions of the structural network) always exists, and the activation free energy of viscous flow is almost independent of temperature. The hole-activation model is closely connected with a number of well-known models describing the viscous flow of glass-forming liquids (the Avramov-Milchev, Nemilov, Ojovan, and other models).

Size-Dependent Brittle-to-Ductile Transition in Silica Glass Nanofibers.

Science.gov (United States)

Luo, Junhang; Wang, Jiangwei; Bitzek, Erik; Huang, Jian Yu; Zheng, He; Tong, Limin; Yang, Qing; Li, Ju; Mao, Scott X

2016-01-13

Silica (SiO2) glass, an essential material in human civilization, possesses excellent formability near its glass-transition temperature (Tg > 1100 °C). However, bulk SiO2 glass is very brittle at room temperature. Here we show a surprising brittle-to-ductile transition of SiO2 glass nanofibers at room temperature as its diameter reduces below 18 nm, accompanied by ultrahigh fracture strength. Large tensile plastic elongation up to 18% can be achieved at low strain rate. The unexpected ductility is due to a free surface affected zone in the nanofibers, with enhanced ionic mobility compared to the bulk that improves ductility by producing more bond-switching events per irreversible bond loss under tensile stress. Our discovery is fundamentally important for understanding the damage tolerance of small-scale amorphous structures.

Glass Transitions in a Monatomic Liquid with Two Glassy States

Science.gov (United States)

Gordon, Andrew; Giovambattista, Nicolas

2014-04-01

We perform out-of-equilibrium molecular dynamics simulations of a monatomic liquid that exhibits liquid and glass polymorphism, with two distinct glasses, low- (LDA) and high-density (HDA) amorphous solids. By performing isobaric heating simulations of LDA and HDA at different pressures, we determine (a) the glass transition temperature of LDA and HDA, TgLDA(P) and TgHDA(P), as well as (b) the corresponding glass-glass transformation temperatures, TLDA-HDA(P) and THDA-LDA(P). It is found that TgLDA(P) is anomalous; i.e., it decreases with increasing pressure, while TgHDA(P) increases with increasing pressure. Interestingly, the TgLDA(P) and TLDA-HDA(P) loci, as well as the TgHDA(P) and THDA-LDA(P) loci, constitute smooth single lines in the P -T plane, suggesting that heating-induced glass-glass and glass transitions are related. We discuss the present results in the context of water experiments and simulations.

Healing of interfaces of high and ultra-high-molecular- weight polystyrene below the bulk glass transition temperature

DEFF Research Database (Denmark)

Boiko, Yuri M.; Lyngaae-Jørgensen, Jørgen

2004-01-01

into contact to themselves below the glass transition temperature T-g of the bulk Tg-bulk, in a lap-shear joint geometry, at a constant healing temperature T-h for a healing time t(h) of 10 min to 24 h. The lap-shear strength sigma of the symmetric HMWPS-HMWPS and UHMWPS-URMWPS interfaces has been measured...

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

Directory of Open Access Journals (Sweden)

Celtek M.

2011-05-01

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

Glass transition and density fluctuations in the fragile glass former orthoterphenyl

International Nuclear Information System (INIS)

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

2001-01-01

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

Kinetically controlled glass transition measurement of organic aerosol thin films using broadband dielectric spectroscopy

Directory of Open Access Journals (Sweden)

Y. Zhang

2018-06-01

Full Text Available Glass transitions from liquid to semi-solid and solid phase states have important implications for reactivity, growth, and cloud-forming (cloud condensation nuclei and ice nucleation capabilities of secondary organic aerosols (SOAs. The small size and relatively low mass concentration of SOAs in the atmosphere make it difficult to measure atmospheric SOA glass transitions using conventional methods. To circumvent these difficulties, we have adapted a new technique for measuring glass-forming properties of atmospherically relevant organic aerosols. Aerosol particles to be studied are deposited in the form of a thin film onto an interdigitated electrode (IDE using electrostatic precipitation. Dielectric spectroscopy provides dipole relaxation rates for organic aerosols as a function of temperature (373 to 233 K that are used to calculate the glass transition temperatures for several cooling or heating rates. IDE-enabled broadband dielectric spectroscopy (BDS was successfully used to measure the kinetically controlled glass transition temperatures of aerosols consisting of glycerol and four other compounds with selected cooling and heating rates. The glass transition results agree well with available literature data for these five compounds. The results indicate that the IDE-BDS method can provide accurate glass transition data for organic aerosols under atmospheric conditions. The BDS data obtained with the IDE-BDS technique can be used to characterize glass transitions for both simulated and ambient organic aerosols and to model their climate effects.

Echoes of the Glass Transition in Athermal Soft Spheres.

Science.gov (United States)

Morse, Peter K; Corwin, Eric I

2017-09-15

Recent theoretical advances have led to the creation of a unified phase diagram for the thermal glass and athermal jamming transitions. This diagram makes clear that, while related, the mode-coupling-or dynamic-glass transition is distinct from the jamming transition, occurring at a finite temperature and significantly lower density than the jamming transition. Nonetheless, we demonstrate a prejamming transition in athermal frictionless spheres which occurs at the same density as the mode-coupling transition and is marked by percolating clusters of locally rigid particles. At this density in both the thermal and athermal systems, individual motions of an extensive number of particles become constrained, such that only collective motion is possible. This transition, which is well below jamming, exactly matches the definition of collective behavior at the dynamical transition of glasses. Thus, we reveal that the genesis of rigidity in both thermal and athermal systems is governed by the same underlying topological transition in their shared configuration space.

Communication: Glass transition and melting lines of an ionic liquid

Science.gov (United States)

Lima, Thamires A.; Faria, Luiz F. O.; Paschoal, Vitor H.; Ribeiro, Mauro C. C.

2018-05-01

The phase diagram of the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesufonyl)imide, [Pyrr1,4][NTf2], was explored by synchroton X-ray diffraction and Raman scattering measurements as a function of temperature and pressure. Glass transition Tg(p) and melting Tm(p) temperatures were obtained from atmospheric pressure up to ca. 2.0 GPa. We found that both the Tg(p) and Tm(p) curves follow essentially the same pressure dependence. The similarity of pressure coefficients, dTg/dp ≈ dTm/dp, is explained within the non-equilibrium thermodynamics approach for the glass transition by assuming that one of the Ehrenfest equations is appropriated for Tg(p), whereas Tm(p) follows the Clausius-Clapeyron equation valid for the first-order transitions. The results highlight that ionic liquids are excellent model systems to address fundamental questions related to the glass transition.

Mechanical failure and glass transition in metallic glasses

International Nuclear Information System (INIS)

Egami, T.

2011-01-01

Research highlights: → We review the recent results of molecular dynamics simulations on metallic glasses. → They show the equivalence of mechanical failure and glass transition. → We discuss the microscopic mechanism behind this equivalence. → We show that the density of defects in metallic glasses is as high as a quarter. → Our concepts about the defect state in glasses need to be changed. - Abstract: The current majority view on the phenomenon of mechanical failure in metallic glasses appears to be that it is caused by the activity of some structural defects, such as free-volumes or shear transformation zones, and the concentration of such defects is small, only of the order of 1%. However, the recent results compel us to revise this view. Through molecular dynamics simulation it has been shown that mechanical failure is the stress-induced glass transition. According to our theory the concentration of the liquid-like sites (defects) is well over 20% at the glass transition. We suggest that the defect concentration in metallic glasses is actually very high, and percolation of such defects causes atomic avalanche and mechanical failure. In this article we discuss the glass transition, mechanical failure and viscosity from such a point of view.

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

Development of DMBZ-15 High-Glass-Transition-Temperature Polyimides as PMR-15 Replacements Given R&D 100 Award

Science.gov (United States)

Chuang, Kathy

2004-01-01

PMR-15, a high-temperature polyimide developed in the mid-1970s at the NASA Lewis Research Center,1 offers the combination of low cost, easy processing, and good high-temperature performance and stability. It has been recognized as the leading polymer matrix resin for carbon-fiber-reinforced composites used in aircraft engine components. The state-of-the-art PMR-15 polyimide composite has a glass-transition temperature (Tg) of 348 C (658 F). Since composite materials must be used at temperatures well below their glass-transition temperature, the long-term use temperatures of PMR-15 composites can be no higher than 288 C (550 F). In addition, PMR-15 is made from methylene dianiline (MDA), a known liver toxin. Concerns about the safety of workers exposed to MDA during the fabrication of PMR-15 components and about the environmental impact of PMR-15 waste disposal have led to the industry-wide implementation of special handling procedures to minimize the health risks associated with this material. These procedures have increased manufacturing and maintenance costs significantly and have limited the use of PMR-15 in commercial aircraft engine components.

Modeling glass transition and aging processes in nanocomposites and polymer thin films

Science.gov (United States)

Pryamitsyn, Victor; Ganesan, Venkat

2010-03-01

We use a lattice kinetic model of glass transition to study the role of confinement and the presence of nano-inclusions. We have studied freely suspended films of glass-formers and its nanocomposites with ``plastifying'' and ``hardening'' nanoparticles. Using our model we determine the thickness and nanoparticle load dependencies of the Kauzmann temperature T0 and the fragility parameter. We found the glass transition temperature increases with the thickness of the film and the volume fraction of ``hardening'' nanoparticles , while Tg decreases with increase in the loading of ``plastifying'' nanoparticles. We found that the isothermal free volume relaxation rate of the nanocomposite thin film, usually referred as an aging, correlates with the glass transition temperature shift. We also studied the relations between our lattice model and Curro's, Kovacs and Struik's phenomenological models of free volume reduction to deduce physical insights into the mechanisms governing aging processes in thin films and nanocomposites.

Electrochemical determination of the glass transition temperature of thin polyelectrolyte brushes at solid-liquid interfaces by impedance spectroscopy.

Science.gov (United States)

Alonso-García, Teodoro; Rodríguez-Presa, María José; Gervasi, Claudio; Moya, Sergio; Azzaroni, Omar

2013-07-16

Devising strategies to assess the glass transition temperature (Tg) of polyelectrolyte assemblies at solid-electrolyte interfaces is very important to understand and rationalize the temperature-dependent behavior of polyelectrolyte films in a wide range of settings. Despite the evolving perception of the importance of measuring Tg under aqueous conditions in thin film configurations, its straightforward measurement poses a challenging situation that still remains elusive in polymer and materials science. Here, we describe a new method based on electrochemical impedance spectroscopy (EIS) to estimate the glass transition temperature of planar polyelectrolyte brushes at solid-liquid interfaces. To measure Tg, the charge transfer resistance (Rct) of a redox probe diffusing through the polyelectrolyte brush was measured, and the temperature corresponding to the discontinuous change in Rct was identified as Tg. Furthermore, we demonstrate that impedance measurements not only facilitate the estimation of Tg but also enable a reliable evaluation of the transport properties of the polymeric interface, i.e., determination of diffusion coefficients, close to the thermal transition. We consider that this approach bridges the gap between electrochemistry and the traditional tools used in polymer science and offers new opportunities to characterize the thermal behavior of complex polymeric interfaces and macromolecular assemblies.

Influence of entanglements on glass transition temperature of polystyrene

Science.gov (United States)

Ougizawa, Toshiaki; Kinugasa, Yoshinori

2013-03-01

Chain entanglement is essential behavior of polymeric molecules and it seems to affect many physical properties such as not only viscosity of melt state but also glass transition temperature (Tg). But we have not attained the quantitative estimation because the entanglement density is considered as an intrinsic value of the polymer at melt state depending on the chemical structure. Freeze-drying method is known as one of the few ways to make different entanglement density sample from dilute solution. In this study, the influence of entanglements on Tg of polystyrene obtained by the freeze-dried method was estimated quantitatively. The freeze-dried samples showed Tg depression with decreasing the concentration of precursor solution due to the lower entanglement density and their depressed Tg would be saturated when the almost no intermolecular entanglement was formed. The molecular weight dependence of the maximum value of Tg depression was discussed.

Effect of γ-radiation on glass transition temperature of Poly(Bisphenol A carbonate) (PC)

International Nuclear Information System (INIS)

Kalkar, A.K.; Kundagol, S.

1988-01-01

Thin films of pure Poly(Bisphenol A carbonate) (PC) were γ-irradiated at room temperature from Co 60 source for varied doses, for the systematic study of γ-radiation on glass transition temperature (Tsub(g)) of PC. It was found that Tsub(g) of PC decreases with increasing doses. Irradiation of γ-rays on PC results in evolution of CO, CO 2 and H 2 from carbonate linkage and methyl group and which results in lowering of average mol.wt. of bul k polymer. Hence, overall increase in free volume increases chain mobility and thus reduces the Tsub(g). (author)

Unique properties associated with normal martensitic transition and strain glass transition – A simulation study

International Nuclear Information System (INIS)

Wang, Dong; Ni, Yan; Gao, Jinghui; Zhang, Zhen; Ren, Xiaobing; Wang, Yunzhi

2013-01-01

Highlights: ► We model the unique properties of strain glass which is different from that of normal martensite. ► We describe the importance of point defects in the formation of strain glass and related properties. ► The role of point defect can be attributed to global transition temperature effect (GTTE) and local field effect (LFE). -- Abstract: The transition behavior and unique properties associated with normal martensitic transition and strain glass transition are investigated by computer simulations using the phase field method. The simulations are based on a physical model that assumes that point defects alter the thermodynamic stability of martensite and create local lattice distortion. The simulation results show that strain glass transition exhibits different properties from those found in normal martensitic transformations. These unique properties include diffuse scattering pattern, “smear” elastic modulus peak, disappearance of heat flow peak and non-ergodicity. These simulation predictions agree well with the experimental observations

Physical stability of drugs after storage above and below the glass transition temperature: Relationship to glass-forming ability.

Science.gov (United States)

Alhalaweh, Amjad; Alzghoul, Ahmad; Mahlin, Denny; Bergström, Christel A S

2015-11-10

Amorphous materials are inherently unstable and tend to crystallize upon storage. In this study, we investigated the extent to which the physical stability and inherent crystallization tendency of drugs are related to their glass-forming ability (GFA), the glass transition temperature (Tg) and thermodynamic factors. Differential scanning calorimetry was used to produce the amorphous state of 52 drugs [18 compounds crystallized upon heating (Class II) and 34 remained in the amorphous state (Class III)] and to perform in situ storage for the amorphous material for 12h at temperatures 20°C above or below the Tg. A computational model based on the support vector machine (SVM) algorithm was developed to predict the structure-property relationships. All drugs maintained their Class when stored at 20°C below the Tg. Fourteen of the Class II compounds crystallized when stored above the Tg whereas all except one of the Class III compounds remained amorphous. These results were only related to the glass-forming ability and no relationship to e.g. thermodynamic factors was found. The experimental data were used for computational modeling and a classification model was developed that correctly predicted the physical stability above the Tg. The use of a large dataset revealed that molecular features related to aromaticity and π-π interactions reduce the inherent physical stability of amorphous drugs. Copyright © 2015 Elsevier B.V. All rights reserved.

Glass transition temperatures of microphase separated semi-interpenetrating polymer networks of polystyrene-inter-poly(cross)-2-ethylhexyl-methacrylate

NARCIS (Netherlands)

de Graaf, L.A.; de Graaf, Leontine A.; Möller, Martin; Moller, M.

1995-01-01

The glass transition temperature of semi-interpenetrating polymer networks (semi-IPNs) of atactic polystyrene (PS) in crosslinked methacrylates was studied by systematic variation of the morphology, that is domain size, continuity and concentration in the domains. Semi-IPNs were prepared from

Calorimetric study of water's two glass transitions in the presence of LiCl

Science.gov (United States)

Ruiz, Guadalupe N.; Amann-Winkel, Katrin; Bove, Livia E.; Corti, Horacio R.

2018-01-01

A DSC study of dilute glassy LiCl aqueous solutions in the water-dominated regime provides direct evidence of a glass-to-liquid transition in expanded high density amorphous (eHDA)-type solutions. Similarly, low density amorphous ice (LDA) exhibits a glass transition prior to crystallization to ice Ic. Both glass transition temperatures are independent of the salt concentration, whereas the magnitude of the heat capacity increase differs. By contrast to pure water, the glass transition endpoint for LDA can be accessed in LiCl aqueous solutions above 0.01 mole fraction. Furthermore, we also reveal the endpoint for HDA's glass transition, solving the question on the width of both glass transitions. This suggests that both equilibrated HDL and LDL can be accessed in dilute LiCl solutions, supporting the liquid–liquid transition scenario to understand water's anomalies. PMID:29442107

Isoviscosity lines and the liquid-glass transition in simple liquids.

Science.gov (United States)

Fomin, Yu D; Brazhkin, V V; Ryzhov, V N

2012-07-01

This article presents the study of the generic behavior of viscosity of liquids based on some simple theoretical models, the soft-spheres and Lennard-Jones systems. The use of these simple models allows us to investigate in detail the viscosity behavior in a wide range of temperatures and pressures including the high-temperature-high-pressure limits. Based on the simulation results, we discuss the shape of isoviscosity lines and analyze the glass transition at high temperatures and high pressures. Despite the fact that the viscosity drastically increases in the limit of high temperatures and high pressures along the melting line, the relaxation time rapidly decreases in this region, and the system becomes further from the glass transition.

Ideal glass transitions in thin films: An energy landscape perspective

Science.gov (United States)

Truskett, Thomas M.; Ganesan, Venkat

2003-07-01

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

An Overview of the Glass Transition Temperature of Synthetic Polymers.

Science.gov (United States)

Beck, Keith R.; And Others

1984-01-01

Presents an overview of the glass-to-rubber transition, what it is, why it is important, and the major factors that influence it. Indicates that this information should be incorporated into chemistry curricula. (JN)

Glass transition and aging in dense suspensions of thermosensitive microgel particles

NARCIS (Netherlands)

Purnomo, E.H; van den Ende, Henricus T.M.; Vanapalli Veera, V.S.A.R.; Vanapalli, Srinivas; Mugele, Friedrich Gunther

2008-01-01

We report a thermosensitive microgel suspension that can be tuned reversibly between the glass state at low temperature and the liquid state at high temperature. Unlike hard spheres, we find that the glass transition for these suspensions is governed by both the volume fraction and the softness of

Glass transition and relaxation processes of polymers studied by positron annihilation

Energy Technology Data Exchange (ETDEWEB)

Uedono, Akira; Tanigawa, Shoichiro [Tsukuba Univ., Ibaraki (Japan). Inst. of Materials Science

1996-10-01

The glass transition and relaxation processes of polymers were studied by the positron annihilation technique. A positron implanted into polymers might annihilate from positronium (Ps) states in open spaces. Ps is a bound state between a positron and an electron, and its nonrelativistic quantum mechanics is practically identical to that of a hydrogen atom. The lifetime of Ps can be associated with the size of the open spaces, and the formation probability of Ps provides information of motions of molecules. Since the glass transition or relaxation processes affect behavior of open spaces, one can study these phenomena through the detection of the open spaces using the positron annihilation technique. In the present paper, we report studies of the glass transition and relaxation processes in polyethylene, polypropylene, and polystyrene by measurements of lifetime spectra of positrons and those of Doppler broadening profiles of the annihilation radiation. For these specimens, by measurements of the lifetime of Ps, {tau}{sub 3}, as a function of temperature, the glass transition temperature, T{sub g}, was determined as an onset temperature of the increase in the temperature coefficient of {tau}{sub 3}. Below T{sub g}, local motions of molecules were detected by measurements of the formation probability of Ps. The positron annihilation as a tool for the characterization of polymers was discussed. (author). 51 refs.

Experimental and computational prediction of glass transition temperature of drugs.

Science.gov (United States)

Alzghoul, Ahmad; Alhalaweh, Amjad; Mahlin, Denny; Bergström, Christel A S

2014-12-22

Glass transition temperature (Tg) is an important inherent property of an amorphous solid material which is usually determined experimentally. In this study, the relation between Tg and melting temperature (Tm) was evaluated using a data set of 71 structurally diverse druglike compounds. Further, in silico models for prediction of Tg were developed based on calculated molecular descriptors and linear (multilinear regression, partial least-squares, principal component regression) and nonlinear (neural network, support vector regression) modeling techniques. The models based on Tm predicted Tg with an RMSE of 19.5 K for the test set. Among the five computational models developed herein the support vector regression gave the best result with RMSE of 18.7 K for the test set using only four chemical descriptors. Hence, two different models that predict Tg of drug-like molecules with high accuracy were developed. If Tm is available, a simple linear regression can be used to predict Tg. However, the results also suggest that support vector regression and calculated molecular descriptors can predict Tg with equal accuracy, already before compound synthesis.

Low-temperature photoluminescence in chalcogenide glasses doped with rare-earth ions

Energy Technology Data Exchange (ETDEWEB)

Kostka, Petr, E-mail: petr.kostka@irsm.cas.cz [Institute of Rock Structure and Mechanics AS CR, V Holešovičkách 41, 182 09 Praha 8 (Czech Republic); Zavadil, Jiří [Institute of Photonics and Electronics AS CR, Chaberská 57, 182 51 Praha 8, Kobylisy (Czech Republic); Iovu, Mihail S. [Institute of Applied Physics, Academy of Sciences of Moldova, Str. Academiei 5, MD-28 Chisinau, Republic of Moldova (Moldova, Republic of); Ivanova, Zoya G. [Institute of Solid State Physics, Bulgarian Academy of Sciences, 1784 Sofia (Bulgaria); Furniss, David; Seddon, Angela B. [Mid-Infrared Photonics Group, George Green Institute for Electromagnetics Research, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)

2015-11-05

Sulfide and oxysulfide bulk glasses Ga-La-S-O, Ge-Ga-S and Ge-Ga-As-S doped, or co-doped, with various rare-earth (RE{sup 3+}) ions are investigated for their room temperature transmission and low-temperature photoluminescence. Photoluminescence spectra are collected by using external excitation into the Urbach tail of the fundamental absorption edge of the host-glass. The low-temperature photoluminescence spectra are dominated by the broad-band luminescence of the host glass, with superimposed relatively sharp emission bands due to radiative transitions within 4f shells of RE{sup 3+} ions. In addition, the dips in the host-glass luminescence due to 4f-4f up-transitions of RE{sup 3+} ions are observed in the Ge-Ga-S and Ge-Ga-As-S systems. These superimposed narrow effects provide a direct experimental evidence of energy transfer between the host glass and respective RE{sup 3+} dopants. - Highlights: • An evidence of energy transfer from host-glass to doped-in RE ions is presented. • Energy transfer is manifested by dips in host-glass broad-band luminescence. • This channel of energy transfer is documented on selected RE doped sulfide glasses. • Photoluminescence spectra are dominated by broad band host-glass luminescence. • Presence of RE ions is manifested by superimposed narrow 4f-4f transitions.

Mobility of supercooled liquid toluene, ethylbenzene, and benzene near their glass transition temperatures investigated using inert gas permeation.

Science.gov (United States)

May, R Alan; Smith, R Scott; Kay, Bruce D

2013-11-21

We investigate the mobility of supercooled liquid toluene, ethylbenzene, and benzene near their respective glass transition temperatures (Tg). The permeation rate of Ar, Kr, and Xe through the supercooled liquid created when initially amorphous overlayers are heated above their glass transition temperature is used to determine the diffusivity. Amorphous benzene crystallizes at temperatures well below its Tg, and as a result, the inert gas underlayer remains trapped until the onset of benzene desorption. In contrast, for toluene and ethylbenzene the onset of inert gas permeation is observed at temperatues near Tg. The inert gas desorption peak temperature as a function of the heating rate and overlayer thickness is used to quantify the diffusivity of supercooled liquid toluene and ethylbenzene from 115 to 135 K. In this temperature range, diffusivities are found to vary across 5 orders of magnitude (∼10(-14) to 10(-9) cm(2)/s). The diffusivity data are compared to viscosity measurements and reveal a breakdown in the Stokes-Einstein relationship at low temperatures. However, the data are well fit by the fractional Stokes-Einstein equation with an exponent of 0.66. Efforts to determine the diffusivity of a mixture of benzene and ethylbenzene are detailed, and the effect of mixing these materials on benzene crystallization is explored using infrared spectroscopy.

From boiling point to glass transition temperature: transport coefficients in molecular liquids follow three-parameter scaling.

Science.gov (United States)

Schmidtke, B; Petzold, N; Kahlau, R; Hofmann, M; Rössler, E A

2012-10-01

The phenomenon of the glass transition is an unresolved problem in condensed matter physics. Its prominent feature, the super-Arrhenius temperature dependence of the transport coefficients, remains a challenge to be described over the full temperature range. For a series of molecular glass formers, we combined τ(T) collected from dielectric spectroscopy and dynamic light scattering covering a range 10(-12) s < τ(T) < 10(2) s. Describing the dynamics in terms of an activation energy E(T), we distinguish a high-temperature regime characterized by an Arrhenius law with a constant activation energy E(∞) and a low-temperature regime for which E(coop)(T) ≡ E(T)-E(∞) increases exponentially while cooling. A scaling is introduced, specifically E(coop)(T)/E(∞) [proportionality] exp[-λ(T/T(A)-1)], where λ is a fragility parameter and T(A) a reference temperature proportional to E(∞). In order to describe τ(T) still the attempt time τ(∞) has to be specified. Thus, a single interaction parameter E(∞) describing the high-temperature regime together with λ controls the temperature dependence of low-temperature cooperative dynamics.

Determination of the Glass-Transition Temperature of GRPS and CFRPS Using a Torsion Pendulum in Regimes of Freely Damped Vibrations and Quasi-Stastic Torsion of Specimens

Science.gov (United States)

Startsev, V. O.; Lebedev, M. P.; Molokov, M. V.

2018-03-01

A method to measure the glass-transition temperature of polymers and polymeric matrices of composite materials with the help of an inverse torsion pendulum over a wide range of temperatures is considered combining the method of free torsional vibrations and a quasi-static torsion of specimens. The glass-transition temperature Tg of a KMKS-1-80. T10 fiberglass, on increasing the frequency of freely damped torsional vibrations from 0.7 to 9.6 Hz, was found to increase from 132 to 140°C. The value of Tg of these specimens, determined by measuring the work of their torsion through a small fixed angle was 128.6°C ± 0.8°C. It is shown that the use of a torsion pendulum allows one to determine the glass-transition temperature of polymeric or polymer matrices of PCMs in dynamic and quasi-static deformation regimes of specimens.

The extent of the glass transition from molecular simulation revealing an overcrank effect.

Science.gov (United States)

Godey, François; Fleury, Alexandre; Ghoufi, Aziz; Soldera, Armand

2018-02-15

A deep understanding of the transition between rubber and amorphous state characterized by a glass transition temperature, T g , is still a source of discussions. In this work, we highlight the role of molecular simulation in revealing explicitly this temperature dependent behavior. By reporting the specific volume, the thermal expansion coefficient and the heat capacity versus the temperature, we actually show that the glass transition domain extends to a greater range of temperature, compared with experiments. This significant enlargement width is due to the fast cooling rate, and actually explains the difficulty to locate T g . This result is the manifestation of an overcranking effect used by high-speed cameras to reveal slow-motion. Accordingly, atomistic simulation offers the significant opportunity to show that the transition from the rubber state to the glass phase should be detailed in terms of the degrees of freedom freeze. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Magnetization relaxation in spin glasses above transition point

International Nuclear Information System (INIS)

Zajtsev, I.A.; Minakov, A.A.; Galonzka, R.R.

1988-01-01

Magnetization relaxation of Cd 0.6 Zn 0.4 Cr 2 Se 4 and Cd 0.6 Mn 0.4 Te monocrystalline samples with T g =21 K and T g =12 K respectively and magnetic colloid is investigated. It is shown that magnetization inexponential relaxation detected experimentally in spin and dipole glasses is essentially higher than T g temperature transition. It is found that at temperatures higher than T g the essential difference is observed in behaviour of spin glasses with different Z and disorder types

Thermodynamic consequences of the kinetic nature of the glass transition

Science.gov (United States)

Koperwas, Kajetan; Grzybowski, Andrzej; Tripathy, Satya N.; Masiewicz, Elzbieta; Paluch, Marian

2015-01-01

In this paper, we consider the glass transition as a kinetic process and establish one universal equation for the pressure coefficient of the glass transition temperature, dTg/dp, which is a thermodynamic characteristic of this process. Our findings challenge the common previous expectations concerning key characteristics of the transformation from the liquid to the glassy state, because it suggests that without employing an additional condition, met in the glass transition, derivation of the two independent equations for dTg/dp is not possible. Hence, the relation among the thermodynamic coefficients, which could be equivalent to the well-known Prigogine-Defay ratio for the process under consideration, cannot be obtained. Besides, by comparing the predictions of our universal equation for dTg/dp and Ehrenfest equations, we find the aforementioned supplementary restriction, which must be met to use the Prigogine-Defay ratio for the glass transition. PMID:26657017

Pressure-controlled nucleation and growth in Zr41Ti14Cu12.5Ni10Be22.5 bulk metallic glass close to and beyond glass transition temperature

International Nuclear Information System (INIS)

Pan Mingxiang; Yao Yushu; Zhao Deqian; Zhuang Yanxin; Wang Weihua

2002-01-01

By high-pressure annealing close to and beyond glass transition temperature, the behavior of nucleation and growth of crystals in Zr 41 Ti 14 Cu 12.5 Ni 10 Be 22.5 bulk metallic glass (BMG) is investigated. The experimental results indicate that exerting a high pressure during annealing can markedly decrease the nucleation temperature of the BMG. The growth rate of crystals first increases and then decreases with increase of annealing pressure. The effect of pressure on nucleation and growth of crystals is phenomenologically explained

Glass transition near the free surface studied by synchrotron radiation

Energy Technology Data Exchange (ETDEWEB)

Sikorski, M.

2008-06-15

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

Glass transition near the free surface studied by synchrotron radiation

International Nuclear Information System (INIS)

Sikorski, M.

2008-06-01

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

An investigation into the effects of residual water on the glass transition temperature of polylactide microspheres using modulated temperature DSC.

Science.gov (United States)

Passerini, N; Craig, D Q

2001-05-18

The objective of the study was to ascertain residual water levels in polylactide and polylactide-co-glycolide microspheres prepared using the solvent evaporation technique and to investigate the effects of that water on the glass transitional behaviour of the microspheres. Microspheres were prepared from polylactic acid (PLA) and polylactide-co-glycolide (PLGA) 50:50 and 75:25 using a standard solvent evaporation technique. The glass transition was measured as a function of drying conditions using modulated temperature DSC. The microspheres were found to contain very low levels of dichloromethane, while residual water levels of up to circa 3% w/w were noted after freeze or oven drying, these levels being higher for microspheres containing higher glycolic acid levels. The residual water was found to lower the T(g) following the Gordon-Taylor relationship. The data indicate that the microparticles may retain significant water levels following standard preparation and drying protocols and that this drying may markedly lower the T(g) of the spheres.

Direct investigations of deformation and yield induced structure transitions in polyamide 6 below glass transition temperature with WAXS and SAXS

DEFF Research Database (Denmark)

Guo, Huilong; Wang, Jiayi; Zhou, Chengbo

2015-01-01

Deformation and yield induced structure transitions of polyamide 6 (PA6) were detected with the combination of the wide- and small-angle X-ray scattering (WAXS and SAXS) at 30 degrees C below glass transition temperature (T-g) of PA6. During deformation, gamma-alpha phase transition was found...... at elastic stage. The concentrated stress in crystals at elastic stage provided adequate energy for the direct gamma-alpha phase transition under T-g. The force to promote the gamma-phase into a phase directly is insufficient at the yield stage and a transient phase as a compromise was formed. The transient...... phase was confirmed by DSC measurements and assisted the gamma-alpha phase transition indirectly. The gamma-phase slips into incomplete fragments at yield point, and the parts along tensile direction are responsible for the formation of transient phase. The gamma-fragments after yield is oriented...

Oxide glass to high temperature ceramic superconductors - a novel route

International Nuclear Information System (INIS)

Chaudhuri, B.K.; Som, K.K.

1992-01-01

Recently it has been discovered that many of transition metal oxide (TMO) glasses like Bi-Sr-Ca-Cu-O, Y-Ba-Cu-O, Bi-Pb-Sr-Ca-Cu-O etc. can be directly converted to the corresponding high temperature superconducting phases by properly annealing the respective glasses. In this review recent developements in this field are summarised. The structural, electrical, dielectrical, magnetic, optical, and other properties of these new type of (TMO) glass systems have been elucidated comparing them with the corresponding results of already known (TMO) glasses which do not become superconductors on annealing above their glass transition temperatures (T g ). The electrical properties of this novel glass system have been analysed with reference to the various existing theoretical models based on polaron hopping conduction mechanism. The electrical, magnetic, and other properties of the respective superconductors obtained from their corresponding glass phases by annealing above (T g ) and the possibility of drawing wires, ribbons etc. from these glass matrices and then converting them to their high T c superconducting phases have also been discussed. (author). 107 refs., 32 figs., 5 tabs

Ideal glass transitions in thin films: An energy landscape perspective

OpenAIRE

Truskett, Thomas M.; Ganesan, Venkat

2003-01-01

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

Inward Cationic Diffusion and Percolation Transition in Glass-Ceramics

DEFF Research Database (Denmark)

Smedsklaer, Morten Mattrup; Yue, Yuanzheng; Mørup, Steen

2010-01-01

We show the quantitative correlation between the degree of crystallization and the cationic diffusion extent in iron-containing diopside glass–ceramics at the glass transition temperature. We find a critical degree of crystallization, above which the diffusion extent sharply drops with the degree...... of crystallization. Below the critical value, the diffusion extent decreases only slightly with the degree of crystallization. No cationic diffusion is observed in the fully crystalline materials. The critical value might be associated with a percolation transition from an interconnected to a disconnected glass...

Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing.

Science.gov (United States)

Kim, Chae Un; Tate, Mark W; Gruner, Sol M

2015-09-22

Observation of theorized glass-to-liquid transitions between low-density amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-to-liquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-to-liquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water.

Glass-to-cryogenic-liquid transitions in aqueous solutions suggested by crack healing

Science.gov (United States)

Kim, Chae Un; Tate, Mark W.; Gruner, Sol M.

2015-01-01

Observation of theorized glass-to-liquid transitions between low-density amorphous (LDA) and high-density amorphous (HDA) water states had been stymied by rapid crystallization below the homogeneous water nucleation temperature (∼235 K at 0.1 MPa). We report optical and X-ray observations suggestive of glass-to-liquid transitions in these states. Crack healing, indicative of liquid, occurs when LDA ice transforms to cubic ice at 160 K, and when HDA ice transforms to the LDA state at temperatures as low as 120 K. X-ray diffraction study of the HDA to LDA transition clearly shows the characteristics of a first-order transition. Study of the glass-to-liquid transitions in nanoconfined aqueous solutions shows them to be independent of the solute concentrations, suggesting that they represent an intrinsic property of water. These findings support theories that LDA and HDA ice are thermodynamically distinct and that they are continuously connected to two different liquid states of water. PMID:26351671

Predict the glass transition temperature and plasticization of β-cyclodextrin/water binary system by molecular dynamics simulation.

Science.gov (United States)

Zhou, Guohui; Zhao, Tianhai; Wan, Jie; Liu, Chengmei; Liu, Wei; Wang, Risi

2015-01-12

The glass transition temperature, diffusion behavior and plasticization of β-cyclodextrin (β-CD), and three amorphous β-CD/water mixtures (3%, 5% and 10% [w/w] water, respectively) were investigated by molecular dynamics simulation, which were performed using Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies (COMPASS) force field and isothermal-isobaric ensembles. The specific volumes of four amorphous cells were obtained as a function of temperature. The glass transition temperatures (T(g)) were estimated to be 334.25 K, 325.12 K, 317.32 K, and 305.41 K for amorphous β-CD containing 0%, 3%, 5% and 10% w/w water, respectively, which compares well with the values observed in published literature. The radial distribution function was computed to elucidate the intermolecular interactions between amorphous β-CD and water, which acts as a plasticizer. These results indicate that the hydrogen bond interactions of oxygen in hydroxyl ions was higher than oxygen in acetal groups in β-CD amorphous mixtures with that in water, due to less accessibility of ring oxygens to the surrounding water molecules. The mobility of water molecules was investigated over various temperature ranges, including the rubbery and glassy phases of the β-CD/water mixtures, by calculating the diffusion coefficients and the fractional free volume. In β-CD amorphous models, the higher mobility of water molecules was observed at temperatures above Tg, and almost no change was observed at temperatures below T(g). Copyright © 2014 Elsevier Ltd. All rights reserved.

Fragile-to-fragile liquid transition at Tg and stable-glass phase nucleation rate maximum at the Kauzmann temperature TK

International Nuclear Information System (INIS)

Tournier, Robert F.

2014-01-01

An undercooled liquid is unstable. The driving force of the glass transition at T g is a change of the undercooled-liquid Gibbs free energy. The classical Gibbs free energy change for a crystal formation is completed including an enthalpy saving. The crystal growth critical nucleus is used as a probe to observe the Laplace pressure change Δp accompanying the enthalpy change −V m ×Δp at T g where V m is the molar volume. A stable glass–liquid transition model predicts the specific heat jump of fragile liquids at T≤T g , the Kauzmann temperature T K where the liquid entropy excess with regard to crystal goes to zero, the equilibrium enthalpy between T K and T g , the maximum nucleation rate at T K of superclusters containing magic atom numbers, and the equilibrium latent heats at T g and T K . Strong-to-fragile and strong-to-strong liquid transitions at T g are also described and all their thermodynamic parameters are determined from their specific heat jumps. The existence of fragile liquids quenched in the amorphous state, which do not undergo liquid–liquid transition during heating preceding their crystallization, is predicted. Long ageing times leading to the formation at T K of a stable glass composed of superclusters containing up to 147 atom, touching and interpenetrating, are evaluated from nucleation rates. A fragile-to-fragile liquid transition occurs at T g without stable-glass formation while a strong glass is stable after transition

Acrylate oligomers in ultraviolet cured PSA's glass transition, molecular weight versus peel strength

International Nuclear Information System (INIS)

Miller, H.C.

1999-01-01

Typically those not skilled in the art relate Glass Transition Temperature to Pressure Sensitive Adhesives. You need a low Tg material to prepare good pressure sensitive adhesives. This report deals with a wide range acrylate terminated oligomers in a standard formulation. Molecular weight, chemical structure variations are examined versus the Glass Transition of the oligomers and final peel strength. Each formulated adhesive will require unique oligomer properties to reach one hundred newtons per 100 millimeters (5.71 pounds per square inch) peel strength. Excellent peel strengths may be obtained with oligomer molecular weight ranging from six thousand to one thousand molecular weight and glass transition temperatures ranging from minus seventy four degrees centigrade up to thirteen degrees centigrade

[Glass transition of Chinese medicine extract powder and its application].

Science.gov (United States)

Luo, Xiao-Jian; Liu, Hui; Liang, Hong-Bo; Xiong, Lei; Rao, Xiao-Yong; Xie, Yin; He, Yan

2017-01-01

Glass transition theory is an important theory in polymer science, which is used to characterize the physical properties. It refers to the transition of amorphous polymer from the glassy state to the rubber state due to heating or the transition from rubber state to glassy state due to cooling. In this paper, the glassy state and glass transition of food and the similar relationship between the composition of Chinese medicine extract powder and food ingredients were described; the determination method for glass transition temperature (Tg) of Chinese medicine extract powder was established and its main influencing factors were analyzed. Meanwhile, the problems in drying process, granulation process and Chinese medicine extract powder and solid preparation storage were analyzed and investigated based on Tg, and then the control strategy was put forward to provide guidance for the research and production of Chinese medicine solid preparation. Copyright© by the Chinese Pharmaceutical Association.

Effect of thermal history on mechanical properties of polyetheretherketone below the glass transition temperature

Science.gov (United States)

Cebe, Peggy; Chung, Shirley Y.; Hong, Su-Don

1987-01-01

The effect of thermal history on the tensile properties of polyetheretherketone neat resin films was investigated at different test temperatures (125, 25, and -100) using four samples: fast-quenched amorphous (Q); quenched, then crystallized at 180 C (C180); slowly cooled (for about 16 h) from the melt (SC); and air-cooled (2-3 h) from the melt (AC). It was found that thermal history significantly affects the tensile properties of the material below the glass transition. Fast quenched amorphous films were most tough, could be drawn to greatest strain before rupture, and undergo densification during necking; at the test temperature of -100 C, these films had the best ultimate mechanical properties. At higher temperatures, the semicrystalline films AC and C180 had properties that compared favorably with the Q films. The SC films exhibited poor mechanical properties at all test temperatures.

Transition from Arrhenius to non-Arrhenius temperature dependence of structural relaxation time in glass-forming liquids: continuous versus discontinuous scenario.

Science.gov (United States)

Popova, V A; Surovtsev, N V

2014-09-01

The temperature dependences of α relaxation time τ(α)(T) of three glass-forming liquids (salol, o-terphenyl, and α-picoline) were investigated by a depolarized light scattering technique. A detailed description of τ(α)(T) near T(A), the temperature of the transition from the Arrhenius law at high temperatures to a non-Arrhenius behavior of τ(α)(T) at lower temperatures, was done. It was found that this transition is quite sharp. If the transition is described as switching from the Arrhenius law to the Vogel-Fulcher-Tammann law, it occurs within the temperature range of about 15 K or less. Most of the known expressions for τ(α)(T) cannot describe this sharp transition. Our analysis revealed that this transition can be described either as a discontinuous transition in the spirit of the frustration-limited domain theory [D. Kivelson, G. Tarjus, X. Zhao, and S. A. Kivelson, Phys. Rev. E 53, 751 (1996)], implying a phase transition, or by a phenomenological expression recently suggested [B. Schmidtke, N. Petzold, R. Kahlau, M. Hofmann, and E. A. Rössler, Phys. Rev. E 86, 041507 (2012)], where the activation energy includes the term depending exponentially on temperature.

Using Dielectric Relaxation Spectroscopy to Characterize the Glass Transition Time of Polydextrose.

Science.gov (United States)

Buehler, Martin G; Kindle, Michael L; Carter, Brady P

2015-06-01

Dielectric relaxation spectroscopy was used to characterize the glass transition time, tg , of polydextrose, where the glass transition temperature, Tg , and water activity, aw (relative humidity), were held constant during polydextrose relaxation. The tg was determined from a shift in the peak frequency of the imaginary capacitance spectrum with time. It was found that when the peak frequency reaches 30 mHz, polydextrose undergoes glass transition. Glass transition time, tg , is the time for polydextrose to undergo glass transition at a specific Tg and aw . Results lead to a modified state diagram, where Tg is depressed with increasing aw . This curve forms a boundary: (a) below the boundary, polydextrose does not undergo glass transition and (b) above the boundary, polydextrose rapidly undergoes glass transition. As the boundary curve is specified by a tg value, it can assist in the selection of storage conditions. An important point on the boundary curve is at aw = 0, where Tg0 = 115 °C. The methodology can also be used to calculate the stress-relaxation viscosity of polydextrose as a function of Tg and aw , which is important when characterizing the flow properties of polydextrose initially in powder form. © 2015 Institute of Food Technologists®

Reorientational dynamics in molecular liquids as revealed by dynamic light scattering: from boiling point to glass transition temperature.

Science.gov (United States)

Schmidtke, B; Petzold, N; Kahlau, R; Rössler, E A

2013-08-28

We determine the reorientational correlation time τ of a series of molecular liquids by performing depolarized light scattering experiments (double monochromator, Fabry-Perot interferometry, and photon correlation spectroscopy). Correlation times in the range 10(-12) s-100 s are compiled, i.e., the full temperature interval between the boiling point and the glass transition temperature T(g) is covered. We focus on low-T(g) liquids for which the high-temperature limit τ ≅ 10(-12) s is easily accessed by standard spectroscopic equipment (up to 440 K). Regarding the temperature dependence three interpolation formulae of τ(T) with three parameters each are tested: (i) Vogel-Fulcher-Tammann equation, (ii) the approach recently discussed by Mauro et al. [Proc. Natl. Acad. Sci. U.S.A. 106, 19780 (2009)], and (iii) our approach decomposing the activation energy E(T) in a constant high temperature value E∞ and a "cooperative part" E(coop)(T) depending exponentially on temperature [Schmidtke et al., Phys. Rev. E 86, 041507 (2012)]. On the basis of the present data, approaches (i) and (ii) are insufficient as they do not provide the correct crossover to the high-temperature Arrhenius law clearly identified in the experimental data while approach (iii) reproduces the salient features of τ(T). It allows to discuss the temperature dependence of the liquid's dynamics in terms of a E(coop)(T)/E∞ vs. T/E∞ plot and suggests that E∞ controls the energy scale of the glass transition phenomenon.

Thermodynamics and kinetics of the glass transition: A generic geometric approach

International Nuclear Information System (INIS)

Gutzow, I.; Ilieva, D.; Babalievski, F.; Yamakov, V.

2000-01-01

A generic phenomenological theory of the glass transition is developed in the framework of a quasilinear formulation of the thermodynamics of irreversible processes. Starting from one of the basic principles of this science in its approximate form given by de Donder's equation, after a change of variables the temperature dependence of the structural parameter ξ(T), the thermodynamic potentials ΔG(tilde sign)(T), the thermodynamic functions and the time of molecular relaxation τ of vitrifying systems is constructed. In doing so, a new effect in the ΔG(tilde sign)(T) course is observed. The analysis of the higher derivatives of the thermodynamic potential, and especially the nullification of the second derivative of the configurational specific heats ΔC(tilde sign) p (T) of the vitrifying liquid defines glass transition temperature T(tilde sign) g and leads directly to the basic dependence of glass transition kinetics: the Frenkel-Kobeko-Reiner equation. The conditions guaranteeing the fulfillment of this equation specify the temperature dependence of the activation energy U(T,ξ(tilde sign)) for viscous flow and give a natural differentiation of glass formers into fragile and strong liquids. The effect of thermal prehistory on the temperature dependence of both thermodynamic functions and kinetic coefficients is established by an appropriate separation of de Donder's equation. (c) 2000 American Institute of Physics

Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

Science.gov (United States)

Giovambattista, Nicolas; Loerting, Thomas; Lukanov, Boris R.; Starr, Francis W.

2012-01-01

Water has multiple glassy states, often called amorphous ices. Low-density (LDA) and high-density (HDA) amorphous ice are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation connects to a first-order liquid-liquid phase transition (LLPT) above the glass transition temperature Tg. Direct experimental evidence of the LLPT is challenging to obtain, since the LLPT occurs at conditions where water rapidly crystallizes. In this work, we explore the implications of a LLPT on the pressure dependence of Tg(P) for LDA and HDA by performing computer simulations of two water models – one with a LLPT, and one without. In the absence of a LLPT, Tg(P) for all glasses nearly coincide. When there is a LLPT, different glasses exhibit dramatically different Tg(P) which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario including a LLPT. PMID:22550566

EFFECTS OF TRITIUM GAS EXPOSURE ON THE GLASS TRANSITION TEMPERATURE OF EPDM ELASTOMER AND ON THE CONDUCTIVITY OF POLYANILINE

Energy Technology Data Exchange (ETDEWEB)

Clark, E; Marie Kane, M

2008-12-12

Four formulations of EPDM (ethylene-propylene diene monomer) elastomer were exposed to tritium gas initially at one atmosphere and ambient temperature for between three and four months in closed containers. Material properties that were characterized include density, volume, mass, appearance, flexibility, and dynamic mechanical properties. The glass transition temperature was determined by analysis of the dynamic mechanical property data per ASTM standards. EPDM samples released significant amounts of gas when exposed to tritium, and the glass transition temperature increased by about 3 C. during the exposure. Effects of ultraviolet and gamma irradiation on the surface electrical conductivity of two types of polyaniline films are also documented as complementary results to planned tritium exposures. Future work will determine the effects of tritium gas exposure on the electrical conductivity of polyaniline films, to demonstrate whether such films can be used as a sensor to detect tritium. Surface conductivity was significantly reduced by irradiation with both gamma rays and ultraviolet light. The results of the gamma and UV experiments will be correlated with the tritium exposure results.

Vortex-glass transition in three dimensions

International Nuclear Information System (INIS)

Reger, J.D.; Tokuyasu, T.A.; Young, A.P.; Fisher, M.P.A.

1991-01-01

We investigate the possibility of a vortex-glass transition in a disordered type-II superconductor in a magnetic field in three dimensions by numerical studies of a simplified model. Monte Carlo simulations at finite temperature and domain-wall renormalization-group calculations at T=0 indicate that d=3 is just above the lower critical dimension d l , though the possibility that d l =3 cannot be definitely ruled out. A comparison is made with XY and Ising spin glasses. The (effective) correlation-length exponent ν and dynamical exponent z are in fairly good agreement with experiment

Low-temperature transitions in cod and tuna determined by differential scanning calorimetry

DEFF Research Database (Denmark)

Jensen, Kristina Nedenskov; Jørgensen, Bo; Nielsen, Jette

2003-01-01

Differential scanning calorimetry measurements have revealed different thermal transitions in cod and tuna samples. Transition temperatures detected Lit -11degreesC, -15degreesC and -21degreesC were highly dependent on the annealing temperature. In tuna muscle an additional transition was observed...... at -72degreesC. This transition appeared differently than the thermal events observed at higher temperatures, as it spanned a broad temperature interval of 25degreesC. The transition was comparable to low-temperature glass transitions reported in protein-rich systems. No transition at this low...... temperature was detected in cod samples. The transitions observed at higher temperatures (-11degreesC to -21degreesC) may possibly stein from a glassy matrix containing muscle proteins. However, the presence of a glass transition at - 11degreesC was in disagreement with the low storage stability at -18degrees...

Spin glass transition in canonical AuFe alloys: A numerical study

International Nuclear Information System (INIS)

Zhang, Kai-Cheng; Li, Yong-Feng; Liu, Gui-Bin; Zhu, Yan

2012-01-01

Although spin glass transitions have long been observed in diluted magnetic alloys, e.g. AuFe and CuMn alloys, previous numerical studies are not completely consistent with the experiment results. The abnormal critical exponents of the alloys remain still puzzling. By employing parallel tempering algorithm with finite-size scaling analysis, we investigated the phase transitions in canonical AuFe alloys. Our results strongly support that spin glass transitions occur at finite temperatures in the alloys. The calculated critical exponents agree well with those obtained from experiments. -- Highlights: ► By simulation we investigated the abnormal critical exponents observed in canonical SG alloys. ► The critical exponents obtained from our simulations agree well with those measured from experiments. ► Our results strongly support that RKKY interactions lead to SG transitions at finite temperatures.

Primary crystallization in Al-rich metallic glasses at unusually low temperatures

International Nuclear Information System (INIS)

Bokeloh, J.; Boucharat, N.; Roesner, H.; Wilde, G.

2010-01-01

The initial stage of the primary crystallization reaction and the glass transition of the marginal metallic glass Al 89 Y 6 Fe 5 were investigated by conventional differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC), microcalorimetry, X-ray diffraction (XRD) and transmission electron microscopy. A sharp onset of the primary crystallization was found by microcalorimetry and XRD studies at temperatures which were 120 deg. C below the primary crystallization peak observed in conventional DSC. A systematic MDSC study of annealed samples revealed a wide spectrum of glass transition onsets, which show a strong dependence on the annealing conditions. In addition, the glass transition onsets can be linked to the initial stage of the primary crystallization. The spectrum of glass transition onsets observed is discussed with respect to the occurrence of phase separation preceding the nucleation and growth of dendritic aluminium nanocrystals.

Pair distribution function and its relation to the glass transition in an amorphous alloy

International Nuclear Information System (INIS)

Basak, S.; Clarke, R.; Nagel, S.R.

1979-01-01

Data for the pair distribution function g (r) are presented as a function of temperature for amorphous Nb/sub 0.4/Ni/sub 0.6/. We show, based on a simple model, that g (r) varies linearly with T over a wide temperature range in the glass as was found empirically by Wendt and Abraham. We also find that in our glass the behavior of g (r) near the glass transition is, within experimental error, similar to what they found in their Monte Carlo calculation. We interpret the deviation from linearity at the glass transition as due to the onset of diffusive motion of the atoms

Pressure dependence of glass transition in As2Te3 glass.

Science.gov (United States)

Ramesh, K

2014-07-24

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

Analyses of glass transition phenomena by solving differential equation with delay effect

International Nuclear Information System (INIS)

Takeuchi, A.; Inoue, A.

2007-01-01

A linear differential equation for the analyses of glass transition phenomena has been proposed by taking into account the delay effect due to the change in transportation of atoms near the glass transition temperature (T g ). Under the condition maintaining the order of the differential equation as the second, the non-linear differential equation proposed by Van Den Beukel and Sietsma is modified to obtain the analytic solution for a linear equation by introducing the following points: the delay effect which is described with a term of Mackey-Glass model, a concept of effective free volume (x fe eff ) and its concentration expression (C fe eff ) which correspond to the equilibrium, and an additional term associated with C fe eff . In analyzing the linear equation, Doyle's p-function was used for the integral of reaction rate with respect to temperature (T). It is found that the linear equation proposed in the present study can describe the changes in free volume (x) with increasing temperature in the dx/dT-T chart, the sharp increase in free volume at T g , and over shooting phenomena of free volume slightly above the T g , as experimentally in thermal analyses for metallic glasses. The linear solution obtained in the present study is of great importance for the analyses of the glass transition because the change in free volume with increasing temperature on heating is described with fundamental functions

Magnetic properties of 3d-transition metal and rare earth fluoride glasses

International Nuclear Information System (INIS)

Renard, J.P.; Dupas, C.; Velu, E.; Jacobini, C.; Fonteneau, G.; Lucas, J.

1981-01-01

The ac susceptibility of fluoride glasses in the ternary systems PbF 2 -MnF 2 -FeF 3 , ThF 4 -BaF 2 -MnF 2 , ZnF 2 -BaF 2 -RF 3 (R = Dy-Ho) has been studied down to 0.3 K. The susceptibility of rare earth glasses exhibits a broad maximum strongly dependent on the measuring frequency ν while a spin glass transition with a sharp susceptibility cusp nearly independent on ν is observed in 3d-transition metal glasses. Magnetic after effects are observed below the spin freezing temperature. (orig.)

Glass transition temperature of polymer nano-composites with polymer and filler interactions

Science.gov (United States)

Hagita, Katsumi; Takano, Hiroshi; Doi, Masao; Morita, Hiroshi

2012-02-01

We systematically studied versatile coarse-grained model (bead spring model) to describe filled polymer nano-composites for coarse-grained (Kremer-Grest model) molecular dynamics simulations. This model consists of long polymers, crosslink, and fillers. We used the hollow structure as the filler to describe rigid spherical fillers with small computing costs. Our filler model consists of surface particles of icosahedra fullerene structure C320 and a repulsive force from the center of the filler is applied to the surface particles in order to make a sphere and rigid. The filler's diameter is 12 times of beads of the polymers. As the first test of our model, we study temperature dependence of volumes of periodic boundary conditions under constant pressures through NPT constant Andersen algorithm. It is found that Glass transition temperature (Tg) decrease with increasing filler's volume fraction for the case of repulsive interaction between polymer and fillers and Tg weakly increase for attractive interaction.

A simple method for tuning the glass transition process in inorganic phosphate glasses

Science.gov (United States)

Fulchiron, René; Belyamani, Imane; Otaigbe, Joshua U.; Bounor-Legaré, Véronique

2015-02-01

The physical modification of glass transition temperature (Tg) and properties of materials via blending is a common practice in industry and academia and has a large economic advantage. In this context, simple production of hitherto unattainable new inorganic glass blends from already existing glass compositions via blending raises much hope with the potential to provide new glasses with new and improved properties, that cannot be achieved with classical glass synthesis, for a plethora of applications such as computers screens, glass-to-metal seals, and storage materials for nuclear wastes. Here, we demonstrate that blends of the specific glass compositions studied are miscible in all proportions, an unreported phenomenon in hard condensed matter like glass. Interestingly, excellent agreement was found between the obtained data and calculated Tgs from theoretical equations (Supplementary information) for predicting the composition dependence of Tg for miscible blends with weak but significant specific interactions between the blend components. That this blending method is at present not applied to inorganic glasses reflects the fact that water and chemically resistant phosphate glasses with relatively low Tgs have become available only recently.

Thermal history of Hawaiian pāhoehoe lava crusts at the glass transition: implications for flow rheology and emplacement

Science.gov (United States)

Gottsmann, Joachim; Harris, Andrew J. L.; Dingwell, Donald B.

2004-12-01

We have investigated the thermal history of glassy pāhoehoe crusts across their glass transition. Ten different samples obtained between 1993 and 2003 from the active flow field of the Pu'u 'O'o-Kupaianaha eruption on Hawaii (USA) have been analysed using relaxation geospeedometry. This method employs differential scanning calorimetry to quantify the enthalpic relaxation of the glass to monitor the natural time-temperature (t-T) path followed by the melt during cooling across its glass transition. Cooling rates across the glass transition interval (at 1000- 900 K) have been found to vary between 8 and 140 K/min. The associated glass transition temperatures are up to 400 K, lower than previously anticipated by others. Melt viscosities at the glass transition for these crusts range from 10 9.4 to 10 10.7 Pa s. We have compared the t-T paths quantified via relaxation geospeedometry with those obtained from direct measurements on the active flow field. The calorimetrically determined cooling rates are consistent with either simple cooling from eruption temperatures to temperatures below the glass transition or more complex cooling paths, including periods of reheating and short-term annealing within the glass transition interval. By quantifying the relaxation times associated with these contrasting cooling histories, we show that secondary vesiculation of pāhoehoe flow crusts may be favoured by complex, nonlinear t-T paths within the glass transition. These constraints also allow us to evaluate the time scales associated with the crystallisation and inflation of flow lobes at the glass transition for different pāhoehoe lava flow types. Our results provide important quantifications of rheological parameters at the lower temperature range of viscoelastic deformation in basaltic lava flows. As such, the results may be helpful in refining models for the generation of continental flood basalt flows, as well as models of basaltic lava flow propagation for hazard

Quantum percolation phase transition and magnetoelectric dipole glass in hexagonal ferrites

Science.gov (United States)

Rowley, S. E.; Vojta, T.; Jones, A. T.; Guo, W.; Oliveira, J.; Morrison, F. D.; Lindfield, N.; Baggio Saitovitch, E.; Watts, B. E.; Scott, J. F.

2017-07-01

Hexagonal ferrites not only have enormous commercial impact (£2 billion/year in sales) due to applications that include ultrahigh-density memories, credit-card stripes, magnetic bar codes, small motors, and low-loss microwave devices, they also have fascinating magnetic and ferroelectric quantum properties at low temperatures. Here we report the results of tuning the magnetic ordering temperature in PbF e12 -xG axO19 to zero by chemical substitution x . The phase transition boundary is found to vary as TN˜(1-x /xc ) 2 /3 with xc very close to the calculated spin percolation threshold, which we determine by Monte Carlo simulations, indicating that the zero-temperature phase transition is geometrically driven. We find that this produces a form of compositionally tuned, insulating, ferrimagnetic quantum criticality. Close to the zero-temperature phase transition, we observe the emergence of an electric dipole glass induced by magnetoelectric coupling. The strong frequency behavior of the glass freezing temperature Tm has a Vogel-Fulcher dependence with Tm finite, or suppressed below zero in the zero-frequency limit, depending on composition x . These quantum-mechanical properties, along with the multiplicity of low-lying modes near the zero-temperature phase transition, are likely to greatly extend applications of hexaferrites into the realm of quantum and cryogenic technologies.

Structure-to-glass transition temperature relationships in high temperature stable condensation polyimides

Science.gov (United States)

Alston, W. B.; Gratz, R. F.

1985-01-01

The presence of a hexafluoroisopropylidene (6F) connecting group in aryl dianhydrides used to prepare aromatic condensation polyimides provides high glass transition temperature (T sub g) polyimides with excellent thermo-oxidative stability. The purpose of this study was to determine if a trifluorophenyl-ethylidene (3F) connecting group would have a similar effect on the T sub g of aromatic condensation polyimides. A new dianhydride containing the 3F connecting group was synthesized. This dianhydride and an aromatic diamine also containing the 3F connecting group were used together and in various combinations with known diamines or known dianhydrides, respectively, to prepare new 3F containing condensation polyimides. Known polyimides, including some with the 6F connecting linkage, were also prepared for comparison purposes. The new 3F containing polymers and the comparison polymers were prepared by condensation polymerization via the traditional amic-acid polymerization method in N,N-dimethylacetamide solvent. The solutions were characterized by determining their inherent viscosities and then were thermally converted into polyimide films under nitrogen atmosphere at 300 to 500 C, usually 350 C. The T sub g's of the films and resin discs were then determined by thermomechanical analysis and were correlated as a function of the final processing temperatures of the films and resin discs. The results showed that similarities existed in the T sub g's depending on the nature of the connecting linkage in the monomers used to prepare the condensation polyimides.

Bonding at Compatible and Incompatible Amorphous Interfaces of Polystyrene and Poly(Methyl Methacrylate) Below the Glass Transition Temperature

DEFF Research Database (Denmark)

Boiko, Yuri M.; Lyngaae-Jørgensen, Jørgen

2004-01-01

Films of high-molecular-weight amorphous polystyrene (PS, M-w = 225 kg/mol, M-w/M-n = 3, T-g-bulk = 97degreesC, where T-g-bulk is the glass transition temperature of the bulk sample) and poly(methyl methacrylate) (PMMA, M-w = 87 kg/mol, M-w/M-n = 2, Tg-bulk = 109degreesC) were brought into contact...

Dynamic thermal expansivity of liquids near the glass transition

DEFF Research Database (Denmark)

Niss, Kristine; Gundermann, Ditte; Christensen, Tage Emil

2012-01-01

Based on previous works on polymers by Bauer et al. [ Phys. Rev. E 61 1755 (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704) in the ......Based on previous works on polymers by Bauer et al. [ Phys. Rev. E 61 1755 (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704...... the liquid contracts when cooling from room temperature down to around the glass-transition temperature, which is relevant when measuring on a molecular liquid rather than a polymer....

Establishing Relationship between Process Parameters and Temperature during High Speed End Milling of Soda Lime Glass

Science.gov (United States)

Nasima Bagum, Mst.; Konneh, Mohamed; Yeakub Ali, Mohammad

2018-01-01

In glass machining crack free surface is required in biomedical and optical industry. Ductile mode machining allows materials removal from brittle materials in a ductile manner rather than by brittle fracture. Although end milling is a versatile process, it has not been applied frequently for machining soda lime glass. Soda lime glass is a strain rate and temperature sensitive material; especially around glass transition temperature Tg, ductility increased and strength decreased. Hence, it is envisaged that the generated temperature by high-speed end milling (HSEM) could be brought close to the glass transition temperature, which promote ductile machining. In this research, the objective is to investigate the effect of high speed machining parameters on generated temperature. The cutting parameters were optimized to generate temperature around glass transition temperature of soda lime using response surface methodology (RSM). Result showed that the most influencing process parameter is feed rate followed by spindle speed and depth of cut to generate temperature. Confirmation test showed that combination of spindle speed 30,173 rpm, feed rate 13.2 mm/min and depth of cut 37.68 µm generate 635°C, hence ductile chip removal with machined surface Ra 0.358 µm was possible to achieve.

Linking rigidity transitions with enthalpic changes at the glass transition and fragility: insight from a simple oscillator model.

Science.gov (United States)

Micoulaut, Matthieu

2010-07-21

A low temperature Monte Carlo dynamics of a Keating-like oscillator model is used to study the relationship between the nature of network glasses from the viewpoint of rigidity, the thermal reversibility during the glass transition and the strong-fragile behaviour of glass-forming liquids. The model shows that a Phillips optimal glass formation with minimal enthalpic changes is obtained under a cooling/annealing cycle when the system is optimally constrained by the harmonic interactions, i.e. when it is isostatically rigid. For these peculiar systems with a nearly reversible glass transition, the computed activation energy for relaxation time shows also a minimum, which demonstrates that isostatically rigid glasses are strong (Arrhenius-like) glass-forming liquids. Experiments on chalcogenide and oxide glass-forming liquids are discussed under this new perspective and confirm the theoretical prediction for chalcogenide network glasses whereas limitations of the approach appear for weakly interacting (non-covalent, ionic) systems.

Density crosslink study of gamma irradiated LDPE predicted by gel-fraction, swelling and glass transition temperature characterization

International Nuclear Information System (INIS)

Cardoso, Elisabeth C.L.; Scagliusi, Sandra R.; Moraes, Guilherme F.; Ono, Lilian S.; Parra, D.F.; Lugao, Ademar B.

2011-01-01

Experimental results showed that the crosslink density of polymeric stocks may be predicted from values of gel content based on the reactive portion of the stocks, that is, exclusive of plasticizers and fillers. Where entanglements may be neglected, the crosslink density is directly proportional to functions of the gel and sol contents. In order to predict the behavior of carbon-chain polymers exposed to ionizing radiation, an empirical rule can be used. According to this rule, polymers containing a hydrogen atom at each carbon atom predominantly undergo crosslinking. During irradiation, chain scission occurs simultaneously and competitively with crosslinking, the end result being determined by the ratio of the yields of the two reactions. The ratio of crosslinking to scission depends basically on factors including total irradiation dose, dose rate and the presence of oxygen. The glass transition temperature (Tg), temperature below which the polymer segments do not have sufficient energy to move past one another, marks the onset of segmental mobility for a polymer. Properties such as melt index, melt strength, crystallinity, glass transition, gel fraction, swelling ratio and elasticity modulus were assessed in LDPE (2.6 g.10 min -1 melt index) gamma irradiated within a 10, 15, 20 and 30 kGy and results obtained were further discussed prior conclusion. (author)

Interplay of the Glass Transition and the Liquid-Liquid Phase Transition in Water

Science.gov (United States)

Giovambattista, Nicolas

2013-03-01

Most liquids can form a single glass or amorphous state when cooled sufficiently fast (in order to prevent crystallization). However, there are a few substances that are relevant to scientific and technological applications which can exist in at least two different amorphous states, a property known as polyamorphism. Examples include silicon, silica, and in particular, water. In the case of water, experiments show the existence of a low-density (LDA) and high-density (HDA) amorphous ice that are separated by a dramatic, first-order like phase transition. It has been argued that the LDA-HDA transformation evolves into a first-order liquid-liquid phase transition (LLPT) at temperatures above the glass transition temperature Tg. However, obtaining direct experimental evidence of the LLPT has been challenging since the LLPT occurs at conditions where water rapidly crystallizes. In this talk, I will (i) discuss the general phenomenology of polyamorphism in water and its implications, and (ii) explore the effects of a LLPT on the pressure dependence of Tg(P) for LDA and HDA. Our study is based on computer simulations of two water models - one with a LLPT (ST2 model), and one without (SPC/E model). In the absence of a LLPT, Tg(P) for all glasses nearly coincide. Instead, when there is a LLPT, different glasses exhibit dramatically different Tg(P) loci which are directly linked with the LLPT. Available experimental data for Tg(P) are only consistent with the scenario that includes a LLPT (ST2 model) and hence, our results support the view that a LLPT may exist for the case of water.

Protein Internal Dynamics Associated With Pre-System Glass Transition Temperature Endothermic Events: Investigation of Insulin and Human Growth Hormone by Solid State Hydrogen/Deuterium Exchange.

Science.gov (United States)

Fang, Rui; Grobelny, Pawel J; Bogner, Robin H; Pikal, Michael J

2016-11-01

Lyophilized proteins are generally stored below their glass transition temperature (T g ) to maintain long-term stability. Some proteins in the (pure) solid state showed a distinct endotherm at a temperature well below the glass transition, designated as a pre-T g endotherm. The pre-T g endothermic event has been linked with a transition in protein internal mobility. The aim of this study was to investigate the internal dynamics of 2 proteins, insulin and human growth hormone (hGH), both of which exhibit the pre-T g endothermic event with onsets at 50°C-60°C. Solid state hydrogen/deuterium (H/D) exchange of both proteins was characterized by Fourier transform infrared spectroscopy over a temperature range from 30°C to 80°C. A distinct sigmoidal transition in the extent of H/D exchange had a midpoint of 56.1 ± 1.2°C for insulin and 61.7 ± 0.9°C for hGH, suggesting a transition to greater mobility in the protein molecules at these temperatures. The data support the hypothesis that the pre-T g event is related to a transition in internal protein mobility associated with the protein dynamical temperature. Exceeding the protein dynamical temperature is expected to activate protein internal motion and therefore may have stability consequences. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Excitation Chains at the Glass Transition

International Nuclear Information System (INIS)

Langer, J. S.

2006-01-01

The excitation-chain theory of the glass transition, proposed in an earlier publication, predicts diverging, super-Arrhenius relaxation times and, via a similarly diverging length scale, suggests a way of understanding the relations between dynamic and thermodynamic properties of glass-forming liquids. I argue here that critically large excitation chains play a role roughly analogous to that played by critical clusters in the droplet model of vapor condensation. Unlike a first-order condensation point in a vapor, the glass transition is not a conventional phase transformation, and may not be a thermodynamic transition at all

Fragility Variation of Lithium Borate Glasses Studied by Temperature-Modulated DSC

Science.gov (United States)

Matsuda, Yu; Fukawa, Yasuteru; Kawashima, Mitsuru; Kojima, Seiji

2008-02-01

The fragility of lithium borate glass system has been investigated by Temperature-Modulated Differential Scanning Calorimetry (TMDSC). The frequency and temperature dependences of dynamic specific heat have been observed in the vicinity of a glass transition temperature Tg. It is shown that the value of the fragility index m can be determined from the temperature dependence of the α-relaxation times observed by TMDSC, when the raw phase angle is properly corrected. The composition dependence of the fragility has been also discussed.

Low-density to high-density transition in Ce75Al23Si2 metallic glass

International Nuclear Information System (INIS)

Zeng, Q S; Lou, H B; Gong, Y; Wang, X D; Jiang, J Z; Fang, Y Z; Wu, F M; Yang, K; Li, A G; Yan, S; Yu, X H; Lathe, C

2010-01-01

Using in situ high-pressure x-ray diffraction (XRD), we observed a pressure-induced polyamorphic transition from the low-density amorphous (LDA) state to the high-density amorphous (HDA) state in Ce 75 Al 23 Si 2 metallic glass at about 2 GPa and 300 K. The thermal stabilities of both LDA and HDA metallic glasses were further investigated using in situ high-temperature and high-pressure XRD, which revealed different pressure dependences of the onset crystallization temperature (T x ) between them with a turning point at about 2 GPa. Compared with Ce 75 Al 25 metallic glass, minor Si doping shifts the onset polyamorphic transition pressure from 1.5 to 2 GPa and obviously stabilizes both LDA and HDA metallic glasses with higher T x and changes their slopes dT x /dP. The results obtained in this work reveal another polyamorphous metallic glass system by minor alloying (e.g. Si), which could modify the transition pressure and also properties of LDA and HDA metallic glasses. The minor alloying effect reported here is valuable for the development of more polyamorphous metallic glasses, even multicomponent bulk metallic glasses with modified properties, which will trigger more investigations in this field and improve our understanding of polyamorphism and metallic glasses.

Crystallization kinetics, glass transition kinetics, and thermal stability of Se70-xGa30Inx (x=5, 10, 15, and 20) semiconducting glasses

International Nuclear Information System (INIS)

Imran, Mousa M.A.

2011-01-01

Crystallization and glass transition kinetics of Se 70-x Ga 30 In x (x=5, 10, 15, and 20) semiconducting chalcogenide glasses were studied under non-isothermal condition using a Differential Scanning Calorimeter (DSC). DSC thermograms of the samples were recorded at four different heating rates 5, 10, 15, and 20 K/min. The variation of the glass transition temperature (T g ) with the heating rate (β) was used to calculate the glass transition activation energy (E t ) using two different models. Meanwhile, the variation of the peak temperature of crystallization (T p ) with β was utilized to deduce the crystallization activation energy (E c ) using Kissinger, Augis-Bennet, and Takhor models. Results reveal that E t decreases with increasing In content, while both T g and E c exhibit the opposite behavior, and the crystal growth occurs in one dimension. The variation of these thermal parameters with the average coordination number was also discussed, and the results were interpreted in terms of the type of bonding that In makes with Se. Assessment of thermal stability and glass forming ability (GFA) was carried out on the basis of some quantitative criteria and the results indicate that thermal stability is enhanced while the crystallization rate is reduced with the addition of In to Se-Ga glass. -- Research highlights: → Addition of In to Se-Ga glass decreases the glass transition activation energy. → The crystallization rate in Se-Ga-In glass is reduced as In content increases. → The crystal growth in Se-Ga-In glass occurs in one dimension. → Thermal properties of Se-Ga-In glass indicate a shift in Phillips-Thorpe threshold.

Glass transition memorized by the enthalpy-entropy compensation in the shear thinning of supercooled metallic liquids

Science.gov (United States)

Zhang, Meng; Liu, Lin

2018-06-01

To unravel the true nature of glass transition, broader insights into glass forming have been gained by examining the stress-driven glassy systems, where strong shear thinning, i.e. a reduced viscosity under increasing shear rate, is encountered. It is argued that arbitrarily small stress-driven shear rates would ‘melt’ the glass and erase any memory of its thermal history. In this work, we report a glass transition memorized by the enthalpy-entropy compensation in strongly shear-thinned supercooled metallic liquids, which coincides with the thermal glass transition in both the transition temperature and the activation Gibbs free energy. Our findings provide distinctive insights into both glass forming and shear thinning, and enrich current knowledge on the ubiquitous enthalpy-entropy compensation empirical law in condensed matter physics.

Dynamic thermal expansivity of liquids near the glass transition.

Science.gov (United States)

Niss, Kristine; Gundermann, Ditte; Christensen, Tage; Dyre, Jeppe C

2012-04-01

Based on previous works on polymers by Bauer et al. [Phys. Rev. E 61, 1755 (2000)], this paper describes a capacitative method for measuring the dynamical expansion coefficient of a viscous liquid. Data are presented for the glass-forming liquid tetramethyl tetraphenyl trisiloxane (DC704) in the ultraviscous regime. Compared to the method of Bauer et al., the dynamical range has been extended by making time-domain experiments and by making very small and fast temperature steps. The modeling of the experiment presented in this paper includes the situation in which the capacitor is not full because the liquid contracts when cooling from room temperature down to around the glass-transition temperature, which is relevant when measuring on a molecular liquid rather than a polymer.

The influence of gamma radiation on the molecular weight and glass transition of PLLA and HAp/PLLA nanocomposite

International Nuclear Information System (INIS)

Milicevic, D.; Trifunovic, S.; Dojcilovic, J.; Ignjatovic, N.; Suljovrujic, E.

2010-01-01

The influence of gamma radiation on the molecular weight and glass transition behaviour of poly-L-lactide (PLLA) and hydroxyapatite/poly-L-lactide (HAp/PLLA) nanocomposite has been studied. Since PLLA exposed to high-energy radiation in the presence of air is prone to chain scission reactions and large degradation, changes in molecular weight were obtained by gel permeation chromatography (GPC). Alterations in the glass transition behaviour were investigated by differential scanning calorimetry (DSC). The apparent activation energy (ΔH*) for glass transition was determined on the basis of the heating rate dependence of the glass transition temperature (T g ). Our findings support the fact that chain scission is the main reason for the decrease of T g and ΔH* with the absorbed dose. Furthermore, more intensive chain scission degradation of PLLA was observed in HAp/PLLA and can only be ascribed to the presence of HAp nanoparticles. Consequently, initial differences in the glass transition temperature and/or apparent activation energy of PLLA and HAp/PLLA became more pronounced with absorbed dose. This study reveals that radiation-induced changes in molecular weight and glass transition temperature occur in a predictable and fairly accurate manner. Therefore, gamma radiation can be used not only for sterilization but also for tailoring desirable end-use properties of these biomaterials.

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.

Fuel Pellets from Wheat Straw: The Effect of Lignin Glass Transition and Surface Waxes on Pelletizing Properties

DEFF Research Database (Denmark)

Stelte, Wolfgang; Clemons, Craig; Holm, Jens K.

2012-01-01

and a high concentration of hydrophobic waxes on its outer surface that may limit the pellet strength. The present work studies the impact of the lignin glass transition on the pelletizing properties of wheat straw. Furthermore, the effect of surface waxes on the pelletizing process and pellet strength...... are investigated by comparing wheat straw before and after organic solvent extraction. The lignin glass transition temperature for wheat straw and extracted wheat straw is determined by dynamic mechanical thermal analysis. At a moisture content of 8%, transitions are identified at 53°C and 63°C, respectively....... Pellets are pressed from wheat straw and straw where the waxes have been extracted from. Two pelletizing temperatures were chosen—one below and one above the glass transition temperature of lignin. The pellets compression strength, density, and fracture surface were compared to each other. Pellets pressed...

Characterization of the hidden glass transition of amorphous cyclomaltoheptaose.

Science.gov (United States)

Tabary, Nicolas; Mahieu, Aurélien; Willart, Jean-François; Dudognon, Emeline; Danède, Florence; Descamps, Marc; Bacquet, Maryse; Martel, Bernard

2011-10-18

An amorphous solid of cyclomaltoheptaose (β-cyclodextrin, β-CD) was formed by milling its crystalline form using a high-energy planetary mill at room temperature. The glass transition of this amorphous solid was found to occur above the thermal degradation point of the material preventing its direct observation and thus its full characterization. The corresponding glass transition temperature (T(g)) and the ΔC(p) at T(g) have, however, been estimated by extrapolation of T(g) and ΔC(p) of closely related amorphous compounds. These compounds include methylated β-CD with different degrees of substitution and molecular alloys obtained by co-milling β-CD and methylated β-CD (DS 1.8) at different ratios. The physical characterization of the amorphous states have been performed by powder X-ray diffraction and differential scanning calorimetry, while the chemical integrity of β-CD upon milling was checked by NMR spectroscopy and mass spectrometry. Copyright © 2011 Elsevier Ltd. All rights reserved.

Connection between slow and fast dynamics of molecular liquids around the glass transition

DEFF Research Database (Denmark)

Niss, Kristine; Dalle-Ferrier, Cecile; Frick, Bernhard

2010-01-01

The mean-square displacement (MSD) was measured by neutron scattering at various temperatures and pressures for a number of molecular glass-forming liquids. The MSD is invariant along the glass-transition line at the pressure studied, thus establishing an “intrinsic” Lindemann criterion for any...

Liquid-liquid phase transition and glass transition in a monoatomic model system.

Science.gov (United States)

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

2010-01-01

We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses.

Liquid-Liquid Phase Transition and Glass Transition in a Monoatomic Model System

Directory of Open Access Journals (Sweden)

Nicolas Giovambattista

2010-12-01

Full Text Available We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses.

Water sorption and glass transition of amorphous sugars containing BSA

Energy Technology Data Exchange (ETDEWEB)

Imamura, K.; Suzuki, T.; Tatsumichi, T.; Kirii, S.; Okazaki, M. [Kyoto Univ., Kyoto (Japan). Dept. of Chemical Engineering

2000-08-01

Water sorption and glass transition of four amorphous sugars (lactose, maltose, sucrose, and trehalose) containing bovine serum albumin (BSA) are investigated. Freeze-dried sugar-BSA samples equilibrated at several water activities ranging from 0 to 0.43 were prepared. Moisture content and glass transition temperature (T{sub g}) were measured. For the all sugars, it is found that BSA lowers T{sub g} at low water activity, and raises it at high water activity. It is also found that the difference between T{sub g} of the sugar-BSA samples and that of the corresponding amorphous sugar samples (T{sub g0}) depends mainly on T{sub g0}. (author)

Moisture sorption isotherms and glass transition temperature of elecampe (Inula helenium L.) and burdock (Arctium lappa L.) roots at 25°C.

Science.gov (United States)

Cervenka, L; Kubínová, J; Juszczak, L; Witczak, M

2012-02-01

Sorption isotherms of elecampe (Inula helenium L.) and burdock (Arctium lappa L.) root samples were obtained at 25 °C. Elecampe exhibited hysteresis loop in the range of 0.35-0.90 a(w) , whereas burdock roots showed significant differences between adsorption and desorption isotherms from 0.65 to 0.80 a(w) . Blahovec-Yanniotis was considered to give the best fit over the whole range of a(w) tested. Various parameters describing the properties of sorbed water derived from GAB, Henderson and Blahovec-Yanniotis models have been discussed. Differential scanning calorimetric method was used to measure the glass transition temperature (T (g)) of root samples in relation to water activity. The safe moisture content was determined in 12.01 and 14.96 g/100 g d. b. for burdock and elecampe root samples at 25 °C, respectively. Combining the T (g) line with sorption isotherm in one plot, it was found that the glass transition temperature concept overestimated the temperature stability for both root samples.

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Analytical evidence for the absence of spin glass transition on self-dual lattices

International Nuclear Information System (INIS)

Ohzeki, Masayuki; Nishimori, Hidetoshi

2009-01-01

We show strong evidence for the absence of a finite-temperature spin glass transition for the random-bond Ising model on self-dual lattices. The analysis is performed by an application of duality relations, which enables us to derive a precise but approximate location of the multicritical point on the Nishimori line. This method can be systematically improved to presumably give the exact result asymptotically. The duality analysis, in conjunction with the relationship between the multicritical point and the spin glass transition point for the symmetric distribution function of randomness, leads to the conclusion of the absence of a finite-temperature spin glass transition for the case of symmetric distribution. The result is applicable to the random-bond Ising model with ±J or Gaussian distribution and the Potts gauge glass on the square, triangular and hexagonal lattices as well as the random three-body Ising model on the triangular and the Union-Jack lattices and the four-dimensional random plaquette gauge model. This conclusion is exact provided that the replica method is valid and the asymptotic limit of the duality analysis yields the exact location of the multicritical point. (fast track communication)

Molecular relaxation behavior and isothermal crystallization above glass transition temperature of amorphous hesperetin.

Science.gov (United States)

Shete, Ganesh; Khomane, Kailas S; Bansal, Arvind Kumar

2014-01-01

The purpose of this paper was to investigate the relaxation behavior of amorphous hesperetin (HRN), using dielectric spectroscopy, and assessment of its crystallization kinetics above glass transition temperature (Tg ). Amorphous HRN exhibited both local (β-) and global (α-) relaxations. β-Relaxation was observed below Tg , whereas α-relaxation prominently emerged above Tg . β-Relaxation was found to be of Johari-Goldstein type and was correlated with α-process by coupling model. Secondly, isothermal crystallization experiments were performed at 363 K (Tg + 16.5 K), 373 K (Tg + 26.5 K), and 383 K (Tg + 36.5 K). The kinetics of crystallization, obtained from the normalized dielectric strength, was modeled using the Avrami model. Havriliak-Negami (HN) shape parameters, αHN and αHN .βHN , were analyzed during the course of crystallization to understand the dynamics of amorphous phase during the emergence of crystallites. HN shape parameters indicated that long range (α-like) were motions affected to a greater extent than short range (β-like) motions during isothermal crystallization studies at all temperature conditions. The variable behavior of α-like motions at different isothermal crystallization temperatures was attributed to evolving crystallites with time and increase in electrical conductivity with temperature. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Thermalization calorimetry: A simple method for investigating glass transition and crystallization of supercooled liquids

DEFF Research Database (Denmark)

Jakobsen, Bo; Sanz, Alejandro; Niss, Kristine

2016-01-01

and their crystallization, e.g., for locating the glass transition and melting point(s), as well as for investigating the stability against crystallization and estimating the relative change in specific heat between the solid and liquid phases at the glass transition......We present a simple method for fast and cheap thermal analysis on supercooled glass-forming liquids. This “Thermalization Calorimetry” technique is based on monitoring the temperature and its rate of change during heating or cooling of a sample for which the thermal power input comes from heat...

Structural influence of mixed transition metal ions on lithium bismuth borate glasses

Science.gov (United States)

Yadav, Arti; Dahiya, Manjeet S.; Hooda, A.; Chand, Prem; Khasa, S.

2017-08-01

Lithium bismuth borate glasses containing mixed transition metals having composition 7CoO·23Li2O·20Bi2O3·50B2O3 (CLBB), 7V2O5·23Li2O·20Bi2O3·50B2O3 (VLBB) and x(2CoO·V2O5)·(30 - x)Li2O·20Bi2O3·50B2O3 (x = 0.0 (LBB) and x = 2.0, 5.0, 7.0, 10.0 mol% (CVLBB1-4)) are synthesized via melt quench route. The synthesized compositions are investigated for their physical properties using density (D) and molar volume (Vm), thermal properties by analyzing DSC/TG thermo-graphs, structural properties using IR absorption spectra in the mid-IR range and optical properties using UV-Vis-NIR spectroscopy. The Electron Paramagnetic Resonance (EPR) spectra of vanadyl and cobalt ion have been analyzed to study compositional effects on spin-Hamiltonian parameters. The non linear variations in physical properties depict a strong structural influence of Co/V- oxides on the glassy matrix. The compositional variations in characteristic temperatures (glass transition temperature Tg, glass crystallization temperature Tp and glass melting temperature Tm) reveals that Tg for glass samples CLBB is relatively less than that of pure lithium bismuth borate (LBB) glass sample wherein Tg for sample VLBB is higher than that of LBB. The increase in Tg (as compared with LBB) with an enhanced substitution of mixed transition metal oxides (2CoO·V2O5) shows a progressive structure modification of bismuth borate matrix. These predictions are very well corroborated by corresponding compositional trends of Tp and Tm. FTIR studies reveal that Co2+& VO2+ ions lead to structural rearrangements through the conversion of three-coordinated boron into four coordinated boron and thereby reducing number of non-bridging oxygen atoms. Bismuth is found to exist in [BiO6] octahedral units only, whereas boroxol rings are not present in the glass network. The theoretical values of optical basicity (Λth) and corresponding oxide ion polarizability (αo2-) have also been calculated to investigate oxygen covalency of

Noise as a Probe of Ising Spin Glass Transitions

Science.gov (United States)

Chen, Zhi; Yu, Clare

2009-03-01

Noise is ubiquitous and and is often viewed as a nuisance. However, we propose that noise can be used as a probe of the fluctuations of microscopic entities, especially in the vicinity of a phase transition. In recent work we have used simulations to show that the noise increases in the vicinity of phase transitions of ordered systems. We have recently turned our attention to noise near the phase transitions of disordered systems. In particular, we are studying the noise near Ising spin glass transitions using Monte Carlo simulations. We monitor the system as a function of temperature. At each temperature, we obtain the time series of quantities characterizing the properties of the system, i.e., the energy and magnetization. We look at different quantities, such as the noise power spectrum and the second spectrum of the noise, to analyze the fluctuations.

Thermal expansion accompanying the glass-liquid transition and crystallization

Directory of Open Access Journals (Sweden)

M. Q. Jiang

2015-12-01

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

Influence of low-temperature annealing on magnetic properties of (Nd0.625Ni0.375)85Al15 metallic glass

International Nuclear Information System (INIS)

Xu Feng; Wang Zhiming; Chen Guang; Jiang Jianzhong; Du Youwei

2008-01-01

After a review of the selection process of (Nd 0.625 Ni 0.375 ) 85 Al 15 as a metallic glass with a relatively high glass-forming ability, we investigate the influences of its phase transitions by duplicating the heating process of the isochronal thermal analysis with low-temperature annealings. The structure, thermal stability and magnetic properties are characterized. And the influences on magnetic properties are particularly discussed with emphasis. Both the annealing processes, to the glass-transition temperature and to the onset temperature of crystallization, bring about a higher coercivity of the sample and a higher freezing temperature of the spin-glass-state. For the sample annealed to the onset temperature of crystallization, the influence is quite obvious and is ascribed to the formation of ferrimagnetic Nd 7 Ni 3 phase, as detected by XRD. For the sample annealed to the glass-transition temperature, the indistinct influence is further identified with the analysis of the frequency dependence of the spin-glass-state, and it is mainly attributed to the change of the short-range order in the amorphous matrix

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

Science.gov (United States)

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

2017-10-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2009-01-21

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

A novel approach for analyzing glass-transition temperature vs. composition patterns: application to pharmaceutical compound+polymer systems.

Science.gov (United States)

Kalogeras, Ioannis M

2011-04-18

In medicine, polymer-based materials are commonly used as excipients of poorly water-soluble drugs. The success of the encapsulation, as well as the physicochemical stability of the products, is often reflected on their glass transition temperature (T(g)) vs. composition (w) dependencies. The shape of the T(g)(w) patterns is critically influenced by polymer's molecular mass, drug molecule's shape and molecular volume, the type and degree of shielding of hydrogen-bonding capable functional groups, as well as aspects of the preparation process. By altering mixture's T(g) the amorphous solid form of the active ingredient may be retained at ambient or body temperatures, with concomitant improvements in handling, solubility, dissolution rate and oral bioavailability. Given the importance of the problem, the glass transitions observed in pharmaceutical mixtures have been extensively analyzed, aiming to appraise the state of mixing and intermolecular interactions. Here, accumulated experimental information on related systems is re-evaluated and comparably discussed under the light of a more effective and system-inclusive T(g)(w) equation. The present analysis indicates that free volume modifications and conformational changes of the macromolecular chains dominate, over enthalpic effects of mixing, in determining thermal characteristics and crystallization inhibition/retardation. Moreover, hydrogen-bonding and ion-dipole heterocontacts--although favorable of a higher degree of mixing--appear less significant compared to the steric hindrances and the antiplasticization proffered by the higher viscosity component. Copyright © 2011 Elsevier B.V. All rights reserved.

Hydration of Rhyolitic Glasses: Comparison Between High- and Low-Temperature Processes

Science.gov (United States)

Anovitz, L.; Fayek, M.; Cole, D. R.; Carter, T.

2012-12-01

While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is more obscure. Comparisons between high- and low-temperature diffusive studies suggest that several factors play an important role under lower-temperatures conditions that are not significant at higher temperatures. Surface concentrations, which equilibrate quickly at high temperature, change far more slowly as temperatures decrease, and may not equilibrate at room temperature for hundreds or thousands of years. Coupled with temperature-dependent diffusion coefficients this complicates calculation of diffusion profiles as a function of time. A key factor in this process appears to be the inability of "self-stress", caused by the in-diffusing species, to relax at lower temperatures, a result expected below the glass transition. Regions of the glass hydrated at low temperatures are strongly optically anisotropic, and preliminary calculations suggest that the magnitude of stress involved may be very high. On the microstuctural scale, extrapolations of high-temperature FTIR data to lower temperatures suggests there should be little or no hydroxyl present in glasses "hydrated" at low temperatures. Analyses of both block and powder samples suggest that this is generally true in the bulk of the hydrated glass, excluding hydroxyl groups that formed during the initial cooling of the melt. However, hydroxyl do groups appear to be present at the glass surface, where both SIMS and neutron reflectometry data suggest hydration levels may be higher than projected from the bulk of the glass. Isotopic exchange experiments also suggest that bonding is relatively weak, as hydration water exchanges readily with the enviroment. All of these observations lead to the conclusion that the observed stress is due to the presence of interstructural, rather than bonded, water. This likely explains the

Thermalization calorimetry: A simple method for investigating glass transition and crystallization of supercooled liquids

Directory of Open Access Journals (Sweden)

Bo Jakobsen

2016-05-01

Full Text Available We present a simple method for fast and cheap thermal analysis on supercooled glass-forming liquids. This “Thermalization Calorimetry” technique is based on monitoring the temperature and its rate of change during heating or cooling of a sample for which the thermal power input comes from heat conduction through an insulating material, i.e., is proportional to the temperature difference between sample and surroundings. The monitored signal reflects the sample’s specific heat and is sensitive to exo- and endothermic processes. The technique is useful for studying supercooled liquids and their crystallization, e.g., for locating the glass transition and melting point(s, as well as for investigating the stability against crystallization and estimating the relative change in specific heat between the solid and liquid phases at the glass transition.

Prediction of the Formulation Dependence of the Glass Transition Temperature for Amine-Epoxy Copolymers Using a Quantitative Structure-Property Relationship Based on the AM1 Method

National Research Council Canada - National Science Library

Morrill, Jason

2004-01-01

A designer Quantitative Structure-Property Relationsbip (QSPR) based upon molecular properties calculated using the AM1 semi-empirical quantum mechanical metbod was developed to predict the glass transition temperature (Tg...

Temperature dependent charge transport studies across thermodynamic glass transition in P3HT:PCBM bulk heterojunction: insight from J-V and impedance spectroscopy

Science.gov (United States)

Sarkar, Atri; Rahaman, Abdulla Bin; Banerjee, Debamalya

2018-03-01

Temperature dependent charge transport properties of P3HT:PCBM bulk heterojunction are analysed by dc and ac measurements under dark conditions across a wide temperature range of 110-473 K, which includes the thermodynamic glass transition temperature (Tg ˜320 K) of the system. A change from Ohmic conduction to space charge limited current conduction at higher (⩾1.2 V) applied bias voltages above  ⩾200 K is observed from J-V characteristics. From capacitance-voltage (C-V) measurement at room temperature, the occurrence of a peak near the built-in voltage is observed below the dielectric relaxation frequency, originating from the competition between drift and diffusion driven motions of charges. Carrier concentration (N) is calculated from C-V measurements taken at different temperatures. Room temperature mobility values at various applied bias voltages are in accordance with that obtained from transient charge extraction by linearly increasing voltage measurement. Sample impedance is measured over five decades of frequency across temperature range by using lock-in detection. This data is used to extract temperature dependence of carrier mobility (μ), and dc conductivity (σ_dc ) which is low frequency extrapolation of ac conductivity. An activation energy of  ˜126 meV for the carrier hopping process at the metal-semiconductor interface is estimated from temperature dependence of σ_dc . Above T g, μ levels off to a constant value, whereas σ_dc starts to decrease after a transition knee at T g that can be seen as a combined effect of changes in μ and N. All these observed changes across T g can be correlated to enhanced polymer motion above the glass transition.

Microstructure and Rheology near an Attractive Colloidal Glass Transition

International Nuclear Information System (INIS)

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

2006-01-01

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

Origin of broad NIR photoluminescence in bismuthate glass and Bi-doped glasses at room temperature

Energy Technology Data Exchange (ETDEWEB)

Peng, Mingying; Zollfrank, Cordt; Wondraczek, Lothar [Lehrstuhl fuer Glas und Keramik, WW3, Friedrich Alexander Universitaet Erlangen-Nuernberg, Martensstrasse 5, D-91058 Erlangen (Germany)], E-mail: mingying.peng@ww.uni-erlangen.de, E-mail: lothar.wondraczek@ww.uni-erlangen.de

2009-07-15

Bi-doped glasses with broadband photoluminescence in the near-infrared (NIR) spectral range are presently receiving significant consideration for potential applications in telecommunications, widely tunable fiber lasers and spectral converters. However, the origin of NIR emission remains disputed. Here, we report on NIR absorption and emission properties of bismuthate glass and their dependence on the melting temperature. Results clarify that NIR emission occurs from the same centers as it does in Bi-doped glasses. The dependence of absorption and NIR emission of bismuthate glasses on the melting temperature is interpreted as thermal dissociation of Bi{sub 2}O{sub 3} into elementary Bi. Darkening of bismuthate glass melted at 1300 deg. C is due to the agglomeration of Bi atoms. The presence of Bi nanoparticles is confirmed by transmission electron microscopy, high-resolution energy dispersive x-ray spectroscopy and element distribution mapping. By adding antimony oxide as an oxidation agent to the glass, NIR emission centers can be eliminated and Bi{sup 3+} is formed. By comparing with atomic spectral data, absorption bands at {approx}320 , {approx}500 , 700 , 800 and 1000 nm observed in Bi-doped glasses are assigned to Bi{sup 0} transitions {sup 4}S{sub 3/2}{yields}{sup 2}P{sub 3/2}, {sup 4}S{sub 3/2}{yields}{sup 2}P{sub 1/2}, {sup 4}S{sub 3/2}{yields}{sup 2}D{sub 5/2}, {sup 4}S{sub 3/2}{yields}{sup 2}D{sub 3/2}(2) and {sup 4}S{sub 3/2}{yields}{sup 2}D{sub 3/2}(1), respectively, and broadband NIR emission is assigned to the transition {sup 2}D{sub 3/2}(1){yields}{sup 4}S{sub 3/2}.

Temperature-stress phase diagram of strain glass Ti48.5Ni51.5

International Nuclear Information System (INIS)

Wang, Y.; Ren, X.; Otsuka, K.; Saxena, A.

2008-01-01

The temperature and stress dependence of the properties of a recently discovered strain glass Ti 48.5 Ni 51.5 , which is a glass of frozen local lattice strains, was investigated systematically. It was found that the ideal freezing temperature (T 0 ) of the strain glass decreases with increasing stress. When the stress exceeds a critical value σ c (T), the pseudo-B2 strain glass transforms into B19' martensite. However, the stress-strain behavior associated with such a stress-induced transition showed a crossover at a crossover temperature T CR , which is ∼20 K below T 0 . Above T CR , the sample showed superelastic behavior; however, below T CR , the sample demonstrated plastic behavior. More interestingly, the σ c vs. temperature relation for unfrozen strain glass obeys the Clausius-Clapyeron relationship, whereas that for frozen strain glass disobeys this universal thermodynamic law. A phenomenological explanation is provided for all the phenomena observed, and it is shown that all the anomalous effects come from the broken ergodicity of the glass system and a temperature-dependent relative stability of the martensitic phase. Based on experimental observations, a temperature-stress phase diagram is constructed for this strain glass, which may serve as a guide map for understanding and predicting the properties of strain glass

The effective complex permittivity stability in filled polymer nanocomposites studied above the glass transition temperature

Directory of Open Access Journals (Sweden)

Elhaouzi F.

2018-01-01

Full Text Available The temperature effecton the dielectric response of nanocomposite at low frequencies range is reported. The investigated samples are formed by a semi-crystalline ethylene-co-butyl acrylate (EBA polymer filled with three concentrations of the dispersed conducting carbon black (CB nanoparticles. The temperature dependence of the complex permittivity has been analyzedabove the glass transition temperature of the neat polymer matrix Tg=-75°C. For all CB concentrations, the dielectric spectra follow a same trend in frequency range 100-106Hz. More interestingly, the stability of the effective complex permittivity ɛ=ɛ' -iɛ'' with the temperature range of 10-70°C is explored. While the imaginary part of the complex permittivity ɛ'' exhibits a slight decreasewith temperature, the real part ɛ' shows a significant reduction especially for high loading samples. The observed dielectric response may be related to the breakup of the three-dimensional structurenetwork formed by the aggregation of CB particles causing change at the interfaceEBA-CB.This interface is estimated bythe volume fraction of constrained polymer chain according to loss tangent data of dynamic mechanical analysis.

Effects of dynamic heterogeneity and density scaling of molecular dynamics on the relationship among thermodynamic coefficients at the glass transition

International Nuclear Information System (INIS)

Koperwas, K.; Grzybowski, A.; Grzybowska, K.; Wojnarowska, Z.; Paluch, M.

2015-01-01

In this paper, we define and experimentally verify thermodynamic characteristics of the liquid-glass transition, taking into account a kinetic origin of the process. Using the density scaling law and the four-point measure of the dynamic heterogeneity of molecular dynamics of glass forming liquids, we investigate contributions of enthalpy, temperature, and density fluctuations to spatially heterogeneous molecular dynamics at the liquid-glass transition, finding an equation for the pressure coefficient of the glass transition temperature, dTg/dp. This equation combined with our previous formula for dTg/dp, derived solely from the density scaling criterion, implies a relationship among thermodynamic coefficients at Tg. Since this relationship and both the equations for dTg/dp are very well validated using experimental data at Tg, they are promising alternatives to the classical Prigogine-Defay ratio and both the Ehrenfest equations in case of the liquid-glass transition

Effects of dynamic heterogeneity and density scaling of molecular dynamics on the relationship among thermodynamic coefficients at the glass transition

Energy Technology Data Exchange (ETDEWEB)

Koperwas, K., E-mail: kkoperwas@us.edu.pl; Grzybowski, A.; Grzybowska, K.; Wojnarowska, Z.; Paluch, M. [Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice (Poland); Silesian Center for Education and Interdisciplinary Research, 75 Pulku Piechoty 1A, 41-500 Chorzow (Poland)

2015-07-14

In this paper, we define and experimentally verify thermodynamic characteristics of the liquid-glass transition, taking into account a kinetic origin of the process. Using the density scaling law and the four-point measure of the dynamic heterogeneity of molecular dynamics of glass forming liquids, we investigate contributions of enthalpy, temperature, and density fluctuations to spatially heterogeneous molecular dynamics at the liquid-glass transition, finding an equation for the pressure coefficient of the glass transition temperature, dTg/dp. This equation combined with our previous formula for dTg/dp, derived solely from the density scaling criterion, implies a relationship among thermodynamic coefficients at Tg. Since this relationship and both the equations for dTg/dp are very well validated using experimental data at Tg, they are promising alternatives to the classical Prigogine-Defay ratio and both the Ehrenfest equations in case of the liquid-glass transition.

The physics of the colloidal glass transition.

Science.gov (United States)

Hunter, Gary L; Weeks, Eric R

2012-06-01

As one increases the concentration of a colloidal suspension, the system exhibits a dramatic increase in viscosity. Beyond a certain concentration, the system is said to be a colloidal glass; structurally, the system resembles a liquid, yet motions within the suspension are slow enough that it can be considered essentially frozen. For several decades, colloids have served as a valuable model system for understanding the glass transition in molecular systems. The spatial and temporal scales involved allow these systems to be studied by a wide variety of experimental techniques. The focus of this review is the current state of understanding of the colloidal glass transition, with an emphasis on experimental observations. A brief introduction is given to important experimental techniques used to study the glass transition in colloids. We describe features of colloidal systems near and in glassy states, including increases in viscosity and relaxation times, dynamical heterogeneity and ageing, among others. We also compare and contrast the glass transition in colloids to that in molecular liquids. Other glassy systems are briefly discussed, as well as recently developed synthesis techniques that will keep these systems rich with interesting physics for years to come.

The physics of the colloidal glass transition

International Nuclear Information System (INIS)

Hunter, Gary L; Weeks, Eric R

2012-01-01

As one increases the concentration of a colloidal suspension, the system exhibits a dramatic increase in viscosity. Beyond a certain concentration, the system is said to be a colloidal glass; structurally, the system resembles a liquid, yet motions within the suspension are slow enough that it can be considered essentially frozen. For several decades, colloids have served as a valuable model system for understanding the glass transition in molecular systems. The spatial and temporal scales involved allow these systems to be studied by a wide variety of experimental techniques. The focus of this review is the current state of understanding of the colloidal glass transition, with an emphasis on experimental observations. A brief introduction is given to important experimental techniques used to study the glass transition in colloids. We describe features of colloidal systems near and in glassy states, including increases in viscosity and relaxation times, dynamical heterogeneity and ageing, among others. We also compare and contrast the glass transition in colloids to that in molecular liquids. Other glassy systems are briefly discussed, as well as recently developed synthesis techniques that will keep these systems rich with interesting physics for years to come. (review article)

Modern aspects of the kinetic theory of glass transition

International Nuclear Information System (INIS)

Tropin, T V; Aksenov, V L; Schmelzer, J W

2016-01-01

This paper reviews glass transition kinetics models that are developed to describe the formation of structural (for example, covalent and metallic) glasses, as well as to account for the transition of a polymer to a solid glassy state. As the two approaches most frequently used over the last decade to model the glass transition, the Tool–Narayanaswamy–Moynihan model and the Adam–Gibbs theory of glass transition are described together with examples of their applications. Also discussed are entropy-based approaches that rely on irreversible thermodynamics methods originated in the work of De Donder, Mandelstam, and Leontovich. The actual problems that arise in applying these methods and the prospects of their development are discussed. A brief overview of statistical glass transition models is given, including the mode-coupling and energy-landscape theories. (reviews of topical problems)

Formation of bulk metallic glasses in the Fe-M-Y-B (M = transition metal) system

Energy Technology Data Exchange (ETDEWEB)

Huang, X.M. [International Center for New-Structured Materials (ICNSM) and Laboratory of New-Structured Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Chang, C.T. [Institute for Material Research, Tohoku University, Sendai 980-8577 (Japan); Chang, Z.Y.; Wang, X.D.; Cao, Q.P. [International Center for New-Structured Materials (ICNSM) and Laboratory of New-Structured Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Shen, B.L.; Inoue, A. [Institute for Material Research, Tohoku University, Sendai 980-8577 (Japan); Jiang, J.Z. [International Center for New-Structured Materials (ICNSM) and Laboratory of New-Structured Materials, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China)], E-mail: jiangjz@zju.edu.cn

2008-07-28

In this work, quaternary Fe{sub 72-x}M{sub x}Y{sub 6}B{sub 22} (M = Ni, Co and Mo) bulk metallic glasses (BMGs) have been developed. It is found that a fully amorphous Fe{sub 68}Mo{sub 4}Y{sub 6}B{sub 22} cylindrical rod with 6.5 mm in diameter can be prepared by copper mold injection. These alloys have a high glass transition temperature of about 900 K with high fracture strengths up to about 3 GPa although they are still brittle. Magnetic measurements reveal that they are ferromagnetic at ambient temperature with low coercive force of about 2 A/m, saturation magnetization of about 0.7 T and effective permeability of about 7000 at 100 kHz. The newly developed Fe-based quaternary alloys exhibit excellent combination properties: superior glass forming ability (GFA), high glass transition temperature, and soft magnetic properties, which could have potential applications in electronic industries. Furthermore, the effect of Mo addition on GFA in the Fe-Y-B BMG system has been discussed compared with those of Ni and Co additions.

Short range structural models of the glass transition temperatures and densities of 0.5Na2S + 0.5[xGeS2 + (1 - x)PS5/2] mixed glass former glasses.

Science.gov (United States)

Bischoff, Christian; Schuller, Katherine; Martin, Steve W

2014-04-03

The 0.5Na2S + 0.5[xGeS2 + (1 - x)PS5/2] mixed glass former (MGF) glass system exhibits a nonlinear and nonadditive negative change in the Na(+) ion conductivity as one glass former, PS5/2, is exchanged for the other, GeS2. This behavior, known as the mixed glass former effect (MGFE), is also manifest in a negative deviation from the linear interpolation of the glass transition temperatures (T(g)) of the binary end-member glasses, x = 0 and x = 1. Interestingly, the composition dependence of the densities of these ternary MGF glasses reveals a slightly positive MGFE deviation from a linear interpolation of the densities of the binary end-member glasses, x = 0 and x = 1. From our previous studies of the structures of these glasses using IR, Raman, and NMR spectroscopies, we find that a disproportionation reaction occurs between PS7/2(4-) and GeS3(2-) units into PS4(3-) and GeS5/2(1-) units. This disproportionation combined with the formation of Ge4S10(4-) anions from GeS5/2(1-) groups leads to the negative MGFE in T(g). A best-fit model of the T(g)s of these glasses was developed to quantify the amount of GeS5/2(1-) units that form Ge4S10(4-) molecular anions in the ternary glasses (∼ 5-10%). This refined structural model was used to develop a short-range structural model of the molar volumes, which shows that the slight densification of the ternary glasses is due to the improved packing efficiency of the germanium sulfide species.

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

DEFF Research Database (Denmark)

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

1994-01-01

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

The length and time scales of water's glass transitions

Science.gov (United States)

Limmer, David T.

2014-06-01

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

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

Science.gov (United States)

Limmer, David T

2014-06-07

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

Impact of medium-range order on the glass transition in liquid Ni-Si alloys

Science.gov (United States)

Lü, Y. J.; Entel, P.

2011-09-01

We study the thermophysical properties and structure of liquid Ni-Si alloys using molecular dynamics simulations. The liquid Ni-5% and 10%Si alloys crystallize to form the face-centered cubic (Ni) at 900 and 850 K, respectively, and the glass transitions take place in Ni-20% and 25%Si alloys at about 700 K. The temperature-dependent self-diffusion coefficients and viscosities exhibit more pronounced non-Arrhenius behavior with the increase of Si content before phase transitions, indicating the enhanced glass-forming ability. These appearances of thermodynamic properties and phase transitions are found to closely relate to the medium-range order clusters with the defective face-centered cubic structure characterized by both local translational and orientational order. This locally ordered structure tends to be destroyed by the addition of more Si atoms, resulting in a delay of nucleation and even glass transition instead.

Thermal stress modification in regenerated fiber Bragg grating via manipulation of glass transition temperature based on CO₂-laser annealing.

Science.gov (United States)

Lai, Man-Hong; Lim, Kok-Sing; Gunawardena, Dinusha S; Yang, Hang-Zhou; Chong, Wu-Yi; Ahmad, Harith

2015-03-01

In this work, we have demonstrated thermal stress relaxation in regenerated fiber Bragg gratings (RFBGs) by using direct CO₂-laser annealing technique. After the isothermal annealing and slow cooling process, the Bragg wavelength of the RFBG has been red-shifted. This modification is reversible by re-annealing and rapid cooling. It is repeatable with different cooling process in the subsequent annealing treatments. This phenomenon can be attributed to the thermal stress modification in the fiber core by means of manipulation of glass transition temperature with different cooling rates. This finding in this investigation is important for accurate temperature measurement of RFBG in dynamic environment.

Spin glass transition in a thin-film NiO/permalloy bilayer

Science.gov (United States)

Ma, Tianyu; Urazhdin, Sergei

2018-02-01

We experimentally study magnetization aging in a thin-film NiO/permalloy bilayer. Aging characteristics are nearly independent of temperature below the exchange bias blocking temperature TB, but rapidly vary above it. The dependence on the magnetic history qualitatively changes across TB. The observed behaviors are consistent with the spin glass transition at TB, with significant implications for magnetism and magnetoelectronic phenomena in antiferromagnet/ferromagnet bilayers.

The kinetic glass transition of the Zr46.75Ti8.25Cu7.5Ni10Be27.5 bulk metallic glass former-supercooled liquids on a long time scale

International Nuclear Information System (INIS)

Busch, R.; Johnson, W.L.

1998-01-01

Viscosity and enthalpy relaxation from the amorphous state into the supercooled liquid state was investigated in the bulk metallic glass forming Zr 46.75 Ti 8.25 Cu 7.5 Ni 10 Be 27.5 alloy below the calorimetric glass transition. At different temperatures, the viscosities relax into states that obey the same Vogel endash Fulcher endash Tammann relation as the data obtained at higher temperatures in the supercooled liquid. Enthalpy recovery experiments after relaxation in the same temperature range show that the enthalpy of the material reaches values that also corresponds to the supercooled liquid state. The glass relaxes into a metastable supercooled liquid state, if it is observed on a long time scale. Equilibration is possible far below the calorimetric glass transition and very likely even below the isentropic temperature. copyright 1998 American Institute of Physics

Peculiar thermal points during B2O3 transition from liquid to glass-like state

International Nuclear Information System (INIS)

Bartenev, G.M.; Lomovskoj, V.A.

1992-01-01

Relaxation transitions in glass-like B 2 O 3 were studied by dynamic methods in vacuum in the temperature range of 70-1070 K and frequency range of 10 -4 -1.2·10 6 Hz. The standard temperature of glass formation is T g =493 K and it corresponds to the standard frequency 5.3·10 -4 Hz. Above T g two special temperature points - T K and T F , position of which does not depend on the frequency, are observed

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

Science.gov (United States)

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

2018-03-01

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

Cluster glass transition in Ca2-xLaxMnO4

International Nuclear Information System (INIS)

Manaka, H.; Mishima, K.; Okuda, T.

2007-01-01

We performed linear and nonlinear AC magnetic susceptibility measurements on Ca 2-x La x MnO 4 (x=0.03,0.07,0.10, and 0.14). In such manganites, coexistence or competition brings about various phenomena. We focus on a cluster glass state consisting of ferromagnetic clusters within an antiferromagnetic matrix because the coexistence of the ferromagnetic double exchange interaction and the antiferromagnetic superexchange interaction is closely associated with phase separation. As a result, temperature (T) dependence of a linear susceptibility (X 0 ' (T)) exhibits a sharp peak for x=0.03, and these peaks become broad with increasing x. The X 0 ' (T) curves for x=0.07 and 0.10 show a typical frequency dependence around the peaks, suggesting a cluster (spin) glass transition. Furthermore, a nonlinear susceptibility (X 2 ' (T)) for x=0.10 exhibits successive transitions: the ferromagnetic transition in each cluster occurs at ∼108K and the antiferromagnetic transition between the ferromagnetic clusters occurs at ∼89K. From the X 0 ' (T) and X 2 ' (T) curves for various values of x, we found the existence of the ferromagnetic clusters within the antiferromagnetic matrix, and the cluster glass state was realized for 0.07=< x=<0.14

Thermal expansion of amorphous Zr65Al7.5Cu17.5Ni10 in the vicinity of the glass transition

International Nuclear Information System (INIS)

Geier, N.; Weiss, M.; Moske, M.; Samwer, K.

2000-01-01

The thermal expansion of non-crystalline Zr 65 Al 7.5 Cu 17.5 Ni 10 has been studied in the range of the glass transition and in the undercooled liquid using a dilatometric device. The measuring technique used permits reliable experimental results up to 40 K above the glass transition temperature. The linear thermal expansion coefficient obtained is almost constant in the glassy state with a value of 8.0 x 10 -6 K -1 . It discontinuously increases at the glass transition temperature yielding a value of 20.0 x 10 -6 K -1 in the undercooled liquid. The results are compared with specific heat measurements of the amorphous material in this temperature range and are interpreted in the framework of a cluster model. (orig.)

Low-density to high-density transition in Ce{sub 75}Al{sub 23}Si{sub 2} metallic glass

Energy Technology Data Exchange (ETDEWEB)

Zeng, Q S; Lou, H B; Gong, Y; Wang, X D; Jiang, J Z [International Center for New-Structured Materials, Zhejiang University, Hangzhou 310027 (China); Fang, Y Z; Wu, F M [College of Mathematics, Physics and Information Engineering, Zhejiang Normal University, Jinhua 321004, Zhejiang (China); Yang, K; Li, A G; Yan, S; Yu, X H [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201203 (China); Lathe, C, E-mail: qiaoshizeng@gmail.co, E-mail: jiangjz@zju.edu.c [HASYLAB am DESY, Notkestrasse 85, Hamburg D-22603 (Germany)

2010-09-22

Using in situ high-pressure x-ray diffraction (XRD), we observed a pressure-induced polyamorphic transition from the low-density amorphous (LDA) state to the high-density amorphous (HDA) state in Ce{sub 75}Al{sub 23}Si{sub 2} metallic glass at about 2 GPa and 300 K. The thermal stabilities of both LDA and HDA metallic glasses were further investigated using in situ high-temperature and high-pressure XRD, which revealed different pressure dependences of the onset crystallization temperature (T{sub x}) between them with a turning point at about 2 GPa. Compared with Ce{sub 75}Al{sub 25} metallic glass, minor Si doping shifts the onset polyamorphic transition pressure from 1.5 to 2 GPa and obviously stabilizes both LDA and HDA metallic glasses with higher T{sub x} and changes their slopes dT{sub x}/dP. The results obtained in this work reveal another polyamorphous metallic glass system by minor alloying (e.g. Si), which could modify the transition pressure and also properties of LDA and HDA metallic glasses. The minor alloying effect reported here is valuable for the development of more polyamorphous metallic glasses, even multicomponent bulk metallic glasses with modified properties, which will trigger more investigations in this field and improve our understanding of polyamorphism and metallic glasses.

Evidence for reentrant spin glass behavior in transition metal substituted Co-Ga alloys near critical concentration

Science.gov (United States)

Yasin, Sk. Mohammad; Srinivas, V.; Kasiviswanathan, S.; Vagadia, Megha; Nigam, A. K.

2018-04-01

In the present study magnetic and electrical transport properties of transition metal substituted Co-Ga alloys (near critical cobalt concentration) have been investigated. Analysis of temperature and field dependence of dc magnetization and ac susceptibility (ACS) data suggests an evidence of reentrant spin glass (RSG) phase in Co55.5TM3Ga41.5 (TM = Co, Cr, Fe, Cu). The magnetic transition temperatures (TC and Tf) are found to depend on the nature of TM element substitution with the exchange coupling strength Co-Fe > Co-Co > Co-Cu > Co-Cr. From magnetization dynamics precise transition temperatures for the glassy phases are estimated. It is found that characteristic relaxation times are higher than that of spin glasses with minimal spin-cluster formation. The RSG behavior has been further supported by the temperature dependence of magnetotransport studies. From the magnetic field and substitution effects it has been established that the magnetic and electrical transport properties are correlated in this system.

The liquid-glass-jamming transition in disordered ionic nanoemulsions.

Science.gov (United States)

Braibanti, Marco; Kim, Ha Seong; Şenbil, Nesrin; Pagenkopp, Matthew J; Mason, Thomas G; Scheffold, Frank

2017-11-08

In quenched disordered out-of-equilibrium many-body colloidal systems, there are important distinctions between the glass transition, which is related to the onset of nonergodicity and loss of low-frequency relaxations caused by crowding, and the jamming transition, which is related to the dramatic increase in elasticity of the system caused by the deformation of constituent objects. For softer repulsive interaction potentials, these two transitions become increasingly smeared together, so measuring a clear distinction between where the glass ends and where jamming begins becomes very difficult or even impossible. Here, we investigate droplet dynamics in concentrated silicone oil-in-water nanoemulsions using light scattering. For zero or low NaCl electrolyte concentrations, interfacial repulsions are soft and longer in range, this transition sets in at lower concentrations, and the glass and the jamming regimes are smeared. However, at higher electrolyte concentrations the interactions are stiffer, and the characteristics of the glass-jamming transition resemble more closely the situation of disordered elastic spheres having sharp interfaces, so the glass and jamming regimes can be distinguished more clearly.

Temperature effects on waste glass performance

International Nuclear Information System (INIS)

Mazer, J.J.

1991-02-01

The temperature dependence of glass durability, particularly that of nuclear waste glasses, is assessed by reviewing past studies. The reaction mechanism for glass dissolution in water is complex and involves multiple simultaneous reaction proceeded, including molecular water diffusion, ion exchange, surface reaction, and precipitation. These processes can change in relative importance or dominance with time or changes in temperature. The temperature dependence of each reaction process has been shown to follow an Arrhenius relationship in studies where the reaction process has been isolated, but the overall temperature dependence for nuclear waste glass reaction mechanisms is less well understood, Nuclear waste glass studies have often neglected to identify and characterize the reaction mechanism because of difficulties in performing microanalyses; thus, it is unclear if such results can be extrapolated to other temperatures or reaction times. Recent developments in analytical capabilities suggest that investigations of nuclear waste glass reactions with water can lead to better understandings of their reaction mechanisms and their temperature dependences. Until a better understanding of glass reaction mechanisms is available, caution should be exercised in using temperature as an accelerating parameter. 76 refs., 1 tab

Glass transition of repulsive charged rods (fd-viruses).

Science.gov (United States)

Kang, Kyongok

2014-05-14

It has recently been shown that suspensions of long and thin charged fibrous viruses (fd) form a glass at low ionic strengths. The corresponding thick electric double layers give rise to long-ranged repulsive electrostatic interactions, which lead to caging and structural arrest at concentrations far above the isotropic-nematic coexistence region. Structural arrest and freezing of the orientational texture are found to occur at the same concentration. In addition, various types of orientational textures are equilibrated below the glass transition concentration, ranging from a chiral-nematic texture with a large pitch (of about 100 μm), an X-pattern, and a tightly packed domain texture, consisting of helical domains with a relatively small pitch (of about 10 μm) and twisted boundaries. The dynamics of both particles as well as the texture are discussed, below and above the glass transition. Dynamic light scattering correlation functions exhibit two dynamical modes, where the slow mode is attributed to the elasticity of helical domains. On approach of the glass-transition concentration, the slow mode increases in amplitude, while as the amplitudes of the fast and slow mode become equal at the glass transition. Finally, interesting features of the "transient" behaviors of charged fd-rod glass are shown as the initial caging due to structural arrest, the propagation of flow originating from stress release, and the transition to the final metastable glass state. In addition to the intensity correlation function, power spectra are presented as a function of the waiting time, at the zero-frequency limit that may access to the thermal anomalities in a charged system.

The ferromagnetic-spin glass transition in PdMn alloys: symmetry breaking of ferromagnetism and spin glass studied by a multicanonical method.

Science.gov (United States)

Kato, Tomohiko; Saita, Takahiro

2011-03-16

The magnetism of Pd(1-x)Mn(x) is investigated theoretically. A localized spin model for Mn spins that interact with short-range antiferromagnetic interactions and long-range ferromagnetic interactions via itinerant d electrons is set up, with no adjustable parameters. A multicanonical Monte Carlo simulation, combined with a procedure of symmetry breaking, is employed to discriminate between the ferromagnetic and spin glass orders. The transition temperature and the low-temperature phase are determined from the temperature variation of the specific heat and the probability distributions of the ferromagnetic order parameter and the spin glass order parameter at different concentrations. The calculation results reveal that only the ferromagnetic phase exists at x glass phase exists at x > 0.04, and that the two phases coexist at intermediate concentrations. This result agrees semi-quantitatively with experimental results.

Finite-size effects on the vortex-glass transition in thin YBa2Cu3O7-δ films

International Nuclear Information System (INIS)

Woeltgens, P.J.M.; Dekker, C.; Koch, R.H.; Hussey, B.W.; Gupta, A.

1995-01-01

Nonlinear current-voltage characteristics have been measured at high magnetic fields in YBa 2 Cu 3 O 7-δ films of a thickness t ranging from 3000 down to 16 A. Critical-scaling analyses of the data for the thinner films (t≤400 A) reveal deviations from the vortex-glass critical scaling appropriate for three-dimensional (3D) systems. This is argued to be a finite-size effect. At large current densities J, the vortices are probed at length scales smaller than the film thickness, i.e., 3D vortex-glass behavior is observed. At low J by contrast, the vortex excitations involve typical length scales exceeding the film thickness, resulting in 2D behavior. Further evidence for this picture is found directly from the 3D vortex-glass correlation length, which, upon approach of the glass transition temperature, appears to level off at the film thickness. The results indicate that a vortex-glass phase transition does occur at finite temperature in 3D systems, but not in 2D systems. In the latter an onset of 2D correlations occurs towards zero temperature. This is demonstrated in our thinnest film (16 A), which, in a magnetic field, displays a 2D vortex-glass correlation length which critically diverges at zero temperature

Substrate effects on photoluminescence and low temperature phase transition of methylammonium lead iodide hybrid perovskite thin films

Science.gov (United States)

Shojaee, S. A.; Harriman, T. A.; Han, G. S.; Lee, J.-K.; Lucca, D. A.

2017-07-01

We examine the effects of substrates on the low temperature photoluminescence (PL) spectra and phase transition in methylammonium lead iodide hybrid perovskite (CH3NH3PbI3) thin films. Structural characterization at room temperature with X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy indicated that while the chemical structure of films deposited on glass and quartz was similar, the glass substrate induced strain in the perovskite films and suppressed the grain growth. The luminescence response and phase transition of the perovskite thin films were studied by PL spectroscopy. The induced strain was found to affect both the room temperature and low temperature PL spectra of the hybrid perovskite films. In addition, it was found that the effects of the glass substrate inhibited a tetragonal to orthorhombic phase transition such that it occurred at lower temperatures.

Temperature measurement of flat glass edge during grinding and effect of wheel and workpiece speeds

International Nuclear Information System (INIS)

Moussa, Tala; Garnier, Bertrand; Peerhossaini, Hassan

2017-01-01

Flat glass temperature at the vicinity of the grinding wheel during grinding can become very high and reach that of the glass transition (typically around 550–600 °C). In such cases, the mechanical strength of glass is greatly affected and the grinding process cannot be carried out properly. Hence, thermal phenomena must be managed by adjusting the machining parameters to avoid overheating. For this purpose, it is very important to be able to measure the glass temperature, especially at the grinding interface. However, measuring the interfacial glass temperature is difficult and none of the existing methods for metal grinding is adequate for glass grinding. This work shows a novel temperature method that uses constantan and copper strips on both sides of the glass plates; thermoelectric contact being provided by the metallic binder of diamond particles in the grinding wheel. This new technique allows the measurement of the glass edge temperature during the wheel displacement around the glass plate. The experimental results show an average glass edge temperature between 300 and 600 °C depending on the value of the machining parameters such as work speed, wheel speed, depth of cut and water coolant flow rate. As this new thermal instrumentation is rather intrusive, glass temperature biases were analysed using a 3D heat transfer model with a moving source. Model computations performed using finite elements show that the temperature biases are less than 70 °C, which is smaller than the standard deviation of the glass edge temperatures measured during grinding. (paper)

Effect of ion irradiation on tensile ductility, strength and fictive temperature in metallic glass nanowires

International Nuclear Information System (INIS)

Magagnosc, D.J.; Kumar, G.; Schroers, J.; Felfer, P.; Cairney, J.M.; Gianola, D.S.

2014-01-01

Ion irradiation of thermoplastically molded Pt 57.5 Cu 14.3 Ni 5.7 P 22.5 metallic glass nanowires is used to study the relationship between glass structure and tensile behavior across a wide range of structural states. Starting with the as-molded state of the glass, ion fluence and irradiated volume fraction are systematically varied to rejuvenate the glass, and the resulting plastic behavior of the metallic glass nanowires probed by in situ mechanical testing in a scanning electron microscope. Whereas the as-molded nanowires exhibit high strength, brittle-like fracture and negligible inelastic deformation, ion-irradiated nanowires show tensile ductility and quasi-homogeneous plastic deformation. Signatures of changes to the glass structure owing to ion irradiation as obtained from electron diffraction are subtle, despite relatively large yield strength reductions of hundreds of megapascals relative to the as-molded condition. To reconcile changes in mechanical behavior with glass properties, we adapt previous models equating the released strain energy during shear banding to a transit through the glass transition temperature by incorporating the excess enthalpy associated with distinct structural states. Our model suggests that ion irradiation increases the fictive temperature of our glass by tens of degrees – the equivalent of many orders of magnitude change in cooling rate. We further show our analytical description of yield strength to quantitatively describe literature results showing a correlation between severe plastic deformation and hardness in a single glass system. Our results highlight not only the capacity for room temperature ductile plastic flow in nanoscaled metallic glasses, but also processing strategies capable of glass rejuvenation outside of the realm of traditional thermal treatments

Fundamental considerations in the effect of molecular weight on the glass transition of the gelatin/cosolute system.

Science.gov (United States)

Jiang, Bin; Kasapis, Stefan; Kontogiorgos, Vassilis

2012-05-01

Four molecular fractions of gelatin produced by alkaline hydrolysis of collagen were investigated in the presence of cosolute to record the mechanical properties of the glass transition in high-solid preparations. Dynamic oscillatory and stress relaxation moduli in shear were recorded from 40°C to temperatures as low as -60°C. The small-deformation behavior of these linear polymers was separated by the method of reduced variables into a basic function of time alone and a basic function of temperature alone. The former allowed the reduction of isothermal runs into a master curve covering 17 orders of magnitude in the time domain. The latter follows the passage from the rubbery plateau through the glass transition region to the glassy state seen in the variation of shift factor, a(T) , as a function of temperature. The mechanical glass transition temperature (T(g) ) is pinpointed at the operational threshold of the free volume theory and the predictions of the reaction rate theory. Additional insights into molecular dynamics are obtained via the coupling model of cooperativity, which introduces the concept of coupling constant or interaction strength of local segmental motions that govern structural relaxation at the vicinity of T(g) . The molecular weight of the four gelatin fractions appears to have a profound effect on the transition temperature or coupling constant of vitrified matrices, as does the protein chemistry in relation to that of amorphous synthetic polymers or gelling polysaccharides. © 2011 Wiley Periodicals, Inc.

Evidence for two spin-glass transitions with magnetoelastic and magnetoelectric couplings in the multiferroic (B i1 -xB ax) (F e1 -xT ix ) O3 system

Science.gov (United States)

Kumar, Arun; Kaushik, S. D.; Siruguri, V.; Pandey, Dhananjai

2018-03-01

For disordered Heisenberg systems with small single ion anisotropy (D ), two spin-glass (SG) transitions below the long-range ordered (LRO) phase transition temperature (Tc) have been predicted theoretically for compositions close to the percolation threshold. Experimental verification of these predictions is still controversial for conventional spin glasses. We show that multiferroic spin-glass systems can provide a unique platform for verifying these theoretical predictions via a study of change in magnetoelastic and magnetoelectric couplings, obtained from an analysis of diffraction data, at the spin-glass transition temperatures (TSG). Results of macroscopic (dc M (H , T ), M(t ), ac susceptibility [χ (ω, T )], and specific heat (Cp)) and microscopic (x-ray and neutron scattering) measurements are presented on disordered BiFe O3 , a canonical Heisenberg system with small single ion anisotropy, which reveal appearance of two spin-glass phases, SG1 and SG2, in coexistence with the LRO phase below the Almeida-Thouless (A-T) and Gabey-Toulouse (G-T) lines. It is shown that the temperature dependence of the integrated intensity of the antiferromagnetic (AFM) peak shows dips with respect to the Brillouin function behavior around the SG1 and SG2 transition temperatures. The temperature dependence of the unit cell volume departs from the Debye-Grüneisen behavior below the SG1 transition and the magnitude of departure increases significantly with decreasing temperature up to the electromagnon driven transition temperature below which a small change of slope occurs followed by another similar change of slope at the SG2 transition temperature. The ferroelectric polarization also changes significantly at the two spin-glass transition temperatures. These results, obtained using microscopic techniques, clearly demonstrate that the SG1 and SG2 transitions occur on the same magnetic sublattice and are intrinsic to the system. We also construct a phase diagram showing all

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.

Observation on Surface Change of Fragile Glass: Temperature - Time Dependence Studied by X-Ray Reflectivity

International Nuclear Information System (INIS)

Kikkawa, Hiroyuki; Kitahara, Amane; Takahashi, Isao

2004-01-01

The structural change of a fragile glass surface close to the glass transition temperature Tg is studied by using X-ray reflectivity. Measurements were performed on surfaces of maltitol, which is a typical polyalcohol fragile glass with Tg = 320K. Upon both heating and cooling, we find the following features which are also noticed in silicate glass surfaces: (i) On heating, the surface morphology indicates a variation at temperatures below Tg; (ii) A drastic increase in surface roughness occurs at a temperature about 333K on heating, which is 13K higher than Tg; (iii) During the cooling of the sample, formation of a low-density surface layer (3nm at 293K) is observed. Prior to the crystallization, nm - μm sized domains were grown at the surface, which might not be reported for other glasses

Spherical 2+p spin-glass model: An exactly solvable model for glass to spin-glass transition

International Nuclear Information System (INIS)

Crisanti, A.; Leuzzi, L.

2004-01-01

We present the full phase diagram of the spherical 2+p spin-glass model with p≥4. The main outcome is the presence of a phase with both properties of full replica symmetry breaking phases of discrete models, e.g., the Sherrington-Kirkpatrick model, and those of one replica symmetry breaking. This phase has a finite complexity which leads to different dynamic and static properties. The phase diagram is rich enough to allow the study of different kinds of glass to spin glass and spin glass to spin glass phase transitions

Thermal lens and interferometric method for glass transition and thermo physical properties measurements in Nd2O3 doped sodium zincborate glass.

Science.gov (United States)

Astrath, N G C; Steimacher, A; Rohling, J H; Medina, A N; Bento, A C; Baesso, M L; Jacinto, C; Catunda, T; Lima, S M; Karthikeyan, B

2008-12-22

In this work the time resolved thermal lens method is combined with interferometric technique, the thermal relaxation calorimetry, photoluminescence and lifetime measurements to determine the thermo physical properties of Nd(2)O(3) doped sodium zincborate glass as a function of temperature up to the glass transition region. Thermal diffusivity, thermal conductivity, fluorescence quantum efficiency, linear thermal expansion coefficient and thermal coefficient of electronic polarizability were determined. In conclusion, the results showed the ability of thermal lens and interferometric methods to perform measurements very close to the phase transition region. These techniques provide absolute values for the measured physical quantities and are advantageous when low scan rates are required.

Inelastic neutron scattering from glass formers

International Nuclear Information System (INIS)

Buchenau, U.

1997-01-01

Neutron spectra below and above the glass transition temperature show a pronounced difference between strong and fragile glass formers in Angell's fragility scheme. The strong anharmonic increase of the inelastic scattering with increasing temperature in fragile substances is absent in the strongest glass former SiO 2 . That difference is reflected in the temperature dependence of Brillouin sound velocities above the glass transition. Coherent inelastic neutron scattering data indicate a mixture of sound waves and local modes at the low frequency boson peak. A relation between the fragility and the temperature dependence of the transverse hypersound velocity at the glass temperature is derived. (author)

Relaxations in spin glasses: Similarities and differences from ordinary glasses

International Nuclear Information System (INIS)

Ngai, K.L.; Rajagopal, A.K.; Huang, C.Y.

1984-01-01

Relaxation phenomena have become a major concern in the physics of spin glasses. There are certain resemblances of these relaxation properties to those of ordinary glasses. In this work, we compare the relaxation properties of spin glasses near the freezing temperature with those of glasses near the glass transition temperature. There are similarities between the two types of glasses. Moreover, the relaxation properties of many glasses and spin glasses are in conformity with two coupled ''universality'' relations predicted by a recent model of relaxations in condensed matter

NMR signature of evolution of ductile-to-brittle transition in bulk metallic glasses.

Science.gov (United States)

Yuan, C C; Xiang, J F; Xi, X K; Wang, W H

2011-12-02

The mechanical properties of monolithic metallic glasses depend on the structures at atomic or subnanometer scales, while a clear correlation between mechanical behavior and structures has not been well established in such amorphous materials. In this work, we find a clear correlation of (27)Al NMR isotropic shifts with a microalloying induced ductile-to-brittle transition at ambient temperature in bulk metallic glasses, which indicates that the (27)Al NMR isotropic shift can be regarded as a structural signature to characterize plasticity for this metallic glass system. The study provides a compelling approach for investigating and understanding the mechanical properties of metallic glasses from the point of view of electronic structure. © 2011 American Physical Society

TOPEM DSC study of glass transition region of polyurethane cationomers

International Nuclear Information System (INIS)

Pielichowska, Kinga; Król, Piotr; Król, Bożena; Pagacz, Joanna

2012-01-01

Highlights: ► TOPEM DSC method was employed to investigate the glass transition (T g ) region of fluorinated polyurethane cationomers. ► Introduction of fluorine compounds significantly changes thermal behaviour of cationomers in the T g region of hard segments. ► Introduction of fluorine compound leads to changes of the slope in activation diagram of glass transition. - Abstract: In this paper TOPEM DSC method was employed to investigate the glass transition region of fluorinated polyurethane cationomers. Fluorinated polyurethane cationomers have been synthesised in the reaction of MDI with poly(ethylene glycol) (600) and butane1,4-diol or N-methyl- or N-butyldiethanolamine and 2,2,3,3-tetrafluoro-1,4-butanediol. Better rigidity was found for generally amorphous cationomer coats. It was found that introduction of fluorine compound changes thermal behaviour of polyurethane cationomers as well as leads to changes in the slope in activation diagram profiles of glass transition in comparison to polyuretahene cationomer without fluorine compound. Application of TOPEM DSC allows to obtain more information concerning frequency dependence of glass transition region and thermodynamical stability of polyurethane structures.

High-temperature Brillouin scattering study of haplogranitic glasses and liquids: Effects of F, K, Na and Li on Tg and elastic properties

Science.gov (United States)

Manghnani, M. H.; Hushur, A.; Williams, Q. C.; Dingwell, D. B.

2010-12-01

The density, compressibility and viscosity of silicate melts are important in understanding the thermodynamic and fluid dynamic properties of magmatic systems. Knowledge of the compressibility of silicate melts at 1 bar is an important component in the construction of accurate pressure-volume-temperature equations of state. In light of this, the velocity (nVp, Vp, Vs) and refractive index n of four anhydrous haplogranitic glasses and liquids with similar alkali abundances, but different cations, are measured at high temperature by Brillouin scattering spectroscopy through the glass transition temperature (Tg) in both platelet and back scattering geometry. The compositions of four haplogranites are 5 wt% of the components Li2O, Na2O, K2O and F each added to a base of haplogranitic (HPG8) composition. The glass transition temperature Tg of different haplogranite samples at the GHz frequency of the Brillouin probe are determined from the change in slope of the temperature-dependent longitudinal or transverse sound velocity. HPG8-Li5 has the lowest glass transition temperature (466°C), while HPG8-K5 has the highest glass transition temperature (575°C). Our Brillouin results, when compared with DSC measurements, show lower Tg values. This raises the possibility of a role of either heating rates or a frequency dependence of the glass transition in explaining the discrepancies in Tg values derived from the two methods. The sound velocity (nVp, Vp, Vs) shows markedly different temperature dependences (including differences in sign) below Tg depending on their different alkali contents. The unrelaxed elastic moduli of three haplogranitic glasses with added Li2O, Na2O and F components have been obtained as a function of temperature. The unrelaxed bulk modulus, shear modulus and Poisson’s ratio show strong compositional dependences at ambient temperature. On heating, The K initially decreases with increasing temperature up to ~ 135°C, then increases up to Tg, and then

Comment on 'Spherical 2+p spin-glass model: An analytically solvable model with a glass-to-glass transition'

International Nuclear Information System (INIS)

Krakoviack, V.

2007-01-01

Guided by old results on simple mode-coupling models displaying glass-glass transitions, we demonstrate, through a crude analysis of the solution with one step of replica symmetry breaking (1RSB) derived by Crisanti and Leuzzi for the spherical s+p mean-field spin glass [Phys. Rev. B 73, 014412 (2006)], that the phase behavior of these systems is not yet fully understood when s and p are well separated. First, there seems to be a possibility of glass-glass transition scenarios in these systems. Second, we find clear indications that the 1RSB solution cannot be correct in the full glassy phase. Therefore, while the proposed analysis is clearly naive and probably inexact, it definitely calls for a reassessment of the physics of these systems, with the promise of potentially interesting developments in the theory of disordered and complex systems

Effect of composition and temperature on the second harmonic generation in silver phosphate glasses

Science.gov (United States)

Konidakis, I.; Psilodimitrakopoulos, S.; Kosma, K.; Lemonis, A.; Stratakis, E.

2018-01-01

We herein employ nonlinear laser imaging microscopy to explicitly study the dynamics of second harmonic generation (SHG) in silver iodide phosphate glasses. While glasses of this family have gained extensive scientific attention over the years due to their superior conducting properties, considerably less attention has been paid to their unique nonlinear optical characteristics. In the present study, firstly, it is demonstrated that SHG signal intensity is enhanced upon increasing silver content due to the random formation of silver microstructures within the glass network. Secondly, the SHG temperature dynamics were explored near the glass transition temperature (Tg) regime, where significant glass relaxation phenomena occur. It is found that heating towards the Tg improves the SHG efficiency, whereas above Tg, the capacity of glasses to generate second harmonic radiation is drastically suppressed. The novel findings of this work are considered important in terms of the potential employment of these glasses for the realization of advanced photonic applications like optical-switches and wavelength conversion devices.

Fragility of chalcogenide glass in relation to characteristic temperature T0/Tg

Science.gov (United States)

Shaker, A. M.; Shanker Rao, T.; Lilly Shanker Rao, T.; Venkataraman, K.

2018-03-01

The present study reports the mutual relationship between the fragility index m and the characteristic temperature T0/Tg. The fragility of the chalcogenide amorphous glass of Ge10Se50Te40 is calculated by utilizing glass transition temperature (Tg) measured by DSC (Differential Scanning Calorimetry) at different heating rates (β) in the range 5 to 20 K/min. Vogel-Fulcher-Tammann (VFT) equation is fitted to the data of Tg. In addition to the VFT method, three other methods are also used to evaluate m. The fragility index m of the Ge10Se50Te40 system showed the trend of decrease with increasing heating rate but remained stable around 22 for the heating rate 10 K/min. The value of m for the glass is near the lower limit (m ≈ 16) this indicates the alloy is a strong glass forming material in accordance of Angell’s interpretation of fragility. The calculated values of characteristic temperature T0/Tg is very close to 1 which also indicates that clearly the system is most fragile.

Cubic to tetragonal phase transition of Tm3+ doped nanocrystals in oxyfluoride glass ceramics

International Nuclear Information System (INIS)

Li, Yiming; Fu, Yuting; Shi, Yahui; Zhang, Xiaoyu; Yu, Hua; Zhao, Lijuan

2016-01-01

Tm 3+ ions doped β-PbF 2 nanocrystals in oxyfluoride glass ceramics with different doping concentrations and thermal temperatures are prepared by a traditional melt-quenching and thermal treatment method to investigate the structure and the phase transition of Tm 3+ doped nanocrystals. The structures are characterized by X-ray diffraction Rietveld analysis and confirmed with numerical simulation. The phase transitions are proved further by the emission spectra. Both of the doping concentration and thermal temperature can induce an O h to D 4h site symmetry distortion and a cubic to tetragonal phase transition. The luminescence of Tm 3+ doped nanocrystals at 800 nm was modulated by the phase transition of the surrounding crystal field

Self-bonding in an amorphous polymer below the glass transition

DEFF Research Database (Denmark)

Boiko, Yuri M.; Bach, Anders; Lyngaae-Jørgensen, Jørgen

2004-01-01

was found to develop with (th)1/2 at Th = Tg-bulk - 33 °C (where Tg-bulk is the glass-transition temperature of the bulk sample), and log G was found to develop with 1/Th at Tg-bulk - 43 °C Th Tg-bulk - 23 °C. The smallest measured value of G = 1.4 J/m2 was at least one order of magnitude larger than...

A molecular dynamics approach for predicting the glass transition temperature and plasticization effect in amorphous pharmaceuticals.

Science.gov (United States)

Gupta, Jasmine; Nunes, Cletus; Jonnalagadda, Sriramakamal

2013-11-04

The objectives of this study were as follows: (i) To develop an in silico technique, based on molecular dynamics (MD) simulations, to predict glass transition temperatures (Tg) of amorphous pharmaceuticals. (ii) To computationally study the effect of plasticizer on Tg. (iii) To investigate the intermolecular interactions using radial distribution function (RDF). Amorphous sucrose and water were selected as the model compound and plasticizer, respectively. MD simulations were performed using COMPASS force field and isothermal-isobaric ensembles. The specific volumes of amorphous cells were computed in the temperature range of 440-265 K. The characteristic "kink" observed in volume-temperature curves, in conjunction with regression analysis, defined the Tg. The MD computed Tg values were 367 K, 352 K and 343 K for amorphous sucrose containing 0%, 3% and 5% w/w water, respectively. The MD technique thus effectively simulated the plasticization effect of water; and the corresponding Tg values were in reasonable agreement with theoretical models and literature reports. The RDF measurements revealed strong hydrogen bond interactions between sucrose hydroxyl oxygens and water oxygen. Steric effects led to weak interactions between sucrose acetal oxygens and water oxygen. MD is thus a powerful predictive tool for probing temperature and water effects on the stability of amorphous systems during drug development.

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

International Nuclear Information System (INIS)

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

2006-01-01

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

Effect of alkali content on AC conductivity of borate glasses containing two transition metals

International Nuclear Information System (INIS)

Kashif, I.; Rahman, Samy A.; Soliman, A.A.; Ibrahim, E.M.; Abdel-Khalek, E.K.; Mostafa, A.G.; Sanad, A.M.

2009-01-01

Sodium borate glasses containing iron and molybdenum ions with the total concentration of transition ions constant and gradual substitution of sodium oxide (network modifier) by borate oxide (network former) was prepared. Densities, molar volume, DC and AC conductivities are measured. The trends of these properties are attributed to changes in the glass network structure. Their DC and AC conductivity increased with increasing NaO concentration. The increase of AC conductivity of sodium borate glasses is attributed to the chemical composition and the hopping mechanism of conduction. Measurements of the dielectric constant (ε) and dielectric loss (tan δ) as a function of frequency (50 Hz-100 kHz) and temperature (RT-600 K) indicate that the increase in dielectric constant and loss (ε and tan δ) values with increasing sodium ion content could be attributed to the assumption that Fe and Mo ions tend to assume network-forming position in the glass compositions studied. The variation of the value of frequency exponent s for all glass samples as the function of temperature at a definite frequency indicates that the value of s decreases with increasing the temperature which agrees with the correlated barrier-hopping (CBH) model.

Temperature Effects on Aluminoborosilicate Glass and Melt Structure

Science.gov (United States)

Wu, J.; Stebbins, J. F.

2008-12-01

Quantitative determination of the atomic-scale structure of multi-component oxide melts, and the effects of temperature on them, is a complex problem. Ca- and Na- aluminoborosilicates are especially interesting, not only because of their major role in widespread technical applications (flat-panel computer displays, fiber composites, etc.), but because the coordination environments of two of their main network cations (Al3+ and B3+) change markedly with composition and temperature is ways that may in part be analogous to processes in silicate melts at high pressures in the Earth. Here we examine a series of such glasses with different cooling rates, chosen to evaluate the role modifier cation field strength (Ca2+ vs. Na+) and of non-bridging oxygen (NBO) content. To explore the effects of fictive temperature, fast quenched and annealed samples were compared. We have used B-11 and Al-27 MAS NMR to measure the different B and Al coordinations and calculated the contents of non-bridging oxygens (NBO). Lower cooling rates increase the fraction of [4]B species in all compositions. The conversion of [3]B to [4]B is also expected to convert NBO to bridging oxygens, which should affect thermodynamic properties such as configurational entropy and configurational heat capacity. For four compositions with widely varying compositions and initial NBO contents, analysis of the speciation changes with the same, simple reaction [3]B = [4]B + NBO yields similar enthalpy values of 25±7 kJ/mol. B-11 triple quantum MAS NMR allows as well the proportions of [3]B boroxol ring and non-ring sites to be determined, and reveals more [3]B boroxol ring structures present in annealed (lower temperature) glasses. In situ, high-temperature MAS NMR spectra have been collected on one of the Na-aluminoborosilicate and on a sodium borate glass at 14.1 T. The exchange of boron between the 3- and 4-coordinated sites is clearly observed well above the glass transition temperatures, confirming the

Annealing effect reversal by water sorption-desorption and heating above the glass transition temperature-comparison of properties.

Science.gov (United States)

Saxena, A; Jean, Y C; Suryanarayanan, R

2013-08-05

Our objective is to compare the physical properties of materials obtained from two different methods of annealing reversal, that is, water sorption-desorption (WSD) and heating above glass transition temperature (HAT). Trehalose was annealed by storing at 100 °C for 120 h. The annealing effect was reversed either by WSD or HAT, and the resulting materials were characterized by differential scanning calorimetry (DSC), water sorption studies, and positron annihilation spectroscopy (PAS). While the products obtained by the two methods of annealing reversal appeared to be identical by conventional characterization methods, they exhibited pronounced differences in their water sorption behavior. Positron annihilation spectroscopy (PAS), by measuring the fractional free volume changes in the processed samples, provided a mechanistic explanation for the differences in the observed behavior.

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.

Transitions in aqueous solutions of sucrose at subzero temperatures

Czech Academy of Sciences Publication Activity Database

Sikora, Antonín; Dupanov, V. O.; Kratochvíl, Jaroslav; Zámečník, J.

2007-01-01

Roč. 46, č. 1 (2007), s. 71-85 ISSN 0022-2348 R&D Projects: GA ČR(CZ) GA522/04/0384 Institutional research plan: CEZ:AV0Z40500505 Keywords : aqueous sucrose solutions * subzero temperature * glass transitions Subject RIV: BJ - Thermodynamics Impact factor: 0.809, year: 2007

TIME-TEMPERATURE-TRANSFORMATION DIAGRAMS FOR THE SLUDGE BATCH 3 - FRIT 418 GLASS SYSTEM

International Nuclear Information System (INIS)

Billings, A.; Edwards, Tommy

2009-01-01

As a part of the Waste Acceptance Product Specifications (WAPS) for Vitrified High-Level Waste Forms defined by the Department of Energy - Office of Environmental Management, the phase stability must be determined for each of the projected high-level waste (HLW) types at the Savannah River Site (SRS). Specifically, WAPS 1.4.1 requires the glass transition temperature (Tg) to be defined and time-temperature-transformation (TTT) diagrams to be developed. The Tg of a glass is an indicator of the approximate temperature where the supercooled liquid converts to a solid on cooling or conversely, where the solid begins to behave as a viscoelastic solid on heating. A TTT diagram identifies the crystalline phases that can form as a function of time and temperature for a given waste type or more specifically, the borosilicate glass waste form. In order to assess durability, the Product Consistency Test (PCT) was used and the durability results compared to the Environmental Assessment (EA) glass. The measurement of glass transition temperature and the development of TTT diagrams have already been performed for the seven Defense Waste Processing Facility (DWPF) projected compositions as defined in the Waste Form Compliance Plan (WCP). These measurements were performed before DWPF start-up and the results were incorporated in Volume 7 of the Waste Form Qualification Report (WQR). Additional information exists for other projected compositions, but overall these compositions did not consider some of the processing scenarios now envisioned for DWPF to accelerate throughput. Changes in DWPF processing strategy have required this WAPS specification to be revisited to ensure that the resulting phases have been bounded. Frit 418 was primarily used to process HLW Sludge Batch 3 (SB3) at 38% waste loading (WL) through the DWPF. The Savannah River National Laboratory (SRNL) fabricated a cache of glass from reagent grade oxides to simulate the SB3-Frit 418 system at a 38 wt % WL for glass

The structural origin of the hard-sphere glass transition in granular packing.

Science.gov (United States)

Xia, Chengjie; Li, Jindong; Cao, Yixin; Kou, Binquan; Xiao, Xianghui; Fezzaa, Kamel; Xiao, Tiqiao; Wang, Yujie

2015-09-28

Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a 'hidden' polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Additionally, as the packing fraction increases, its growth follows an entropy-driven nucleation process, similar to that of the random first-order transition theory. Our study essentially identifies a long-sought-after structural glass order in hard-sphere glasses.

Connection between slow and fast dynamics of molecular liquids around the glass transition

International Nuclear Information System (INIS)

Niss, Kristine; Dalle-Ferrier, Cecile; Frick, Bernhard; Russo, Daniela; Dyre, Jeppe; Alba-Simionesco, Christiane

2010-01-01

The mean-square displacement (MSD) was measured by neutron scattering at various temperatures and pressures for a number of molecular glass-forming liquids. The MSD is invariant along the glass-transition line at the pressure studied, thus establishing an 'intrinsic' Lindemann criterion for any given liquid. A one-to-one connection between the MSD's temperature dependence and the liquid's fragility is found when the MSD is evaluated on a time scale of ∼4 ns, but does not hold when the MSD is evaluated at shorter times. The findings are discussed in terms of the elastic model and the role of relaxations, and the correlations between slow and fast dynamics are addressed.

Evaluation of glass transition temperature and dynamic mechanical properties of autopolymerized hard direct denture reline resins.

Science.gov (United States)

Takase, Kazuma; Watanabe, Ikuya; Kurogi, Tadafumi; Murata, Hiroshi

2015-01-01

This study assessed methods for evaluation of glass transition temperature (Tg) of autopolymerized hard direct denture reline resins using dynamic mechanical analysis and differential scanning calorimetry in addition to the dynamic mechanical properties. The Tg values of 3 different reline resins were determined using a dynamic viscoelastometer and differential scanning calorimeter, and rheological parameters were also determined. Although all materials exhibited higher storage modulus and loss modulus values, and a lower loss tangent at 37˚C with a higher frequency, the frequency dependence was not large. Tg values obtained by dynamic mechanical analysis were higher than those by differential scanning calorimetry and higher frequency led to higher Tg, while more stable Tg values were also obtained by that method. These results suggest that dynamic mechanical analysis is more advantageous for characterization of autopolymerized hard direct denture reline resins than differential scanning calorimetry.

Evaluation of a Novel Temperature Sensing Probe for Monitoring and Controlling Glass Temperature in a Joule-Heated Glass Melter

International Nuclear Information System (INIS)

Watkins, A. D.; Musick, C. A.; Cannon, C.; Carlson, N. M.; Mullenix, P.D.; Tillotson, R. D.

1999-01-01

A self-verifying temperature sensor that employs advanced contact thermocouple probe technology was tested in a laboratory-scale, joule-heated, refractory-lined glass melter used for radioactive waste vitrification. The novel temperature probe monitors melt temperature at any given level of the melt chamber. The data acquisition system provides the real-time temperature for molten glass. Test results indicate that the self-verifying sensor is more accurate and reliable than classic platinum/rhodium thermocouple and sheath assemblies. The results of this test are reported as well as enhancements being made to the temperature probe. To obtain more reliable temperature measurements of the molten glass for improving production efficiency and ensuring consistent glass properties, optical sensing was reviewed for application in a high temperature environment

Thermodynamic evidence for cluster ordering in Cu46Zr42Al7Y5 ribbons during glass transition

DEFF Research Database (Denmark)

Zheng, H.J.; Lv, Y.M.; Sun, Q.J.

2016-01-01

This work investigated the response of Cu46Zr42Al7Y5 glass ribbons to both dynamic and static heating using differential scanning calorimeter (DSC). The DSC curve manifests three exothermic responses to dynamic heating, among which the first and the third one are the signatures of the normal sub......-Tg (Tg, glass transition temperature) relaxation and the crystallization process, respectively. The second one is attributed to a partial overlap between the endothermic response to the glass transition and the exothermic response to the formation of ordered clusters. The cluster ordering, which begins...... at the final stage of glass transition, has been verified by the differences in the activation energy of the sub-Tg relaxation, the cluster ordering and primary crystallization for both the as-spun and annealed ribbons. The cluster ordering could be driven by the large difference between the Zr–Y mixing...

Preparation and Dynamic Mechanical Properties at Elevated Temperatures of a Tungsten/Glass Composite

Science.gov (United States)

Gao, Chong; Wang, Yingchun; Ma, Xueya; Liu, Keyi; Wang, Yubing; Li, Shukui; Cheng, Xingwang

2018-03-01

Experiments were conducted to prepare a borosilicate glass matrix composite containing 50 vol.% tungsten and examine its dynamic compressive behavior at elevated temperatures in the range of 450-775 °C. The results show that the homogenous microstructure of the tungsten/glass composite with relative density of 97% can be obtained by hot-pressing sintering at 800 °C for 1 h under pressure of 30 MPa. Dynamic compressive testing was carried out by a separate Hopkinson pressure bar system with a synchronous device. The results show that the peak stress decreases and the composite transforms from brittle to ductile in nature with testing temperature increasing from 450 to 750 °C. The brittle-ductile transition temperature is about 500 °C. Over 775 °C, the composite loses load-bearing capacity totally because of the excessive softening of the glass phase. In addition, the deformation and failure mechanism were analyzed.

Glass transition in soft-sphere dispersions

International Nuclear Information System (INIS)

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

2009-01-01

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

Synthesis of POSS-based ionic conductors with low glass transition temperatures for efficient solid-state dye-sensitized solar cells.

Science.gov (United States)

Zhang, Wei; Wang, Zhong-Sheng

2014-07-09

Replacing liquid-state electrolytes with solid-state electrolytes has been proven to be an effective way to improve the durability of dye-sensitized solar cells (DSSCs). We report herein the synthesis of amorphous ionic conductors based on polyhedral oligomeric silsesquioxane (POSS) with low glass transition temperatures for solid-state DSSCs. As the ionic conductor is amorphous and in the elastomeric state at the operating temperature of DSSCs, good pore filling in the TiO2 film and good interfacial contact between the solid-state electrolyte and the TiO2 film can be guaranteed. When the POSS-based ionic conductor containing an allyl group is doped with only iodine as the solid-state electrolyte without any other additives, power conversion efficiency of 6.29% has been achieved with good long-term stability under one-sun soaking for 1000 h.

Discontinuous nature of the repulsive-to-attractive colloidal glass transition.

Science.gov (United States)

van de Laar, T; Higler, R; Schroën, K; Sprakel, J

2016-03-04

In purely repulsive colloidal systems a glass transition can be reached by increasing the particle volume fraction beyond a certain threshold. The resulting glassy state is governed by configurational cages which confine particles and restrict their motion. A colloidal glass may also be formed by inducing attractive interactions between the particles. When attraction is turned on in a repulsive colloidal glass a re-entrant solidification ensues. Initially, the repulsive glass melts as free volume in the system increases. As the attraction strength is increased further, this weakened configurational glass gives way to an attractive glass in which motion is hindered by the formation of physical bonds between neighboring particles. In this paper, we study the transition from repulsive-to-attractive glasses using three-dimensional imaging at the single-particle level. We show how the onset of cage weakening and bond formation is signalled by subtle changes in local structure. We then demonstrate the discontinuous nature of the solid-solid transition, which is marked by a critical onset at a threshold bonding energy. Finally, we highlight how the interplay between bonding and caging leads to complex and heterogeneous dynamics at the microscale.

Glass transition, crystallization kinetics and pressure effect on crystallization of ZrNbCuNiBe bulk metallic glass

DEFF Research Database (Denmark)

Xing, P.F.; Zhuang, Yanxin; Wang, W.H.

2002-01-01

The glass transition behavior and crystallization kinetics of Zr48Nb8Cu14Ni12Be18 bulk metallic glass have been investigated by differential scanning calorimetry and x-ray powder diffraction (XRD). The activation energies of both glass transition and crystallization events have been obtained using...... the Kissinger method. Results indicate that this glass crystallizes by a three-stage reaction: (1) phase separation and primary crystallization of glass, (2) formation of intermetallic compounds, and (3) decomposition of intermetallic compounds and crystallization of residual amorphous phase. The pressure...

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

Science.gov (United States)

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

2012-07-01

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

Local structural mechanism for frozen-in dynamics in metallic glasses

Science.gov (United States)

Liu, X. J.; Wang, S. D.; Wang, H.; Wu, Y.; Liu, C. T.; Li, M.; Lu, Z. P.

2018-04-01

The nature of the glass transition is a fundamental and long-standing intriguing issue in the condensed-matter physics and materials science community. In particular, the structural response by which a liquid is arrested dynamically to form a glass or amorphous solid upon approaching its freezing temperature [the glass transition temperature (Tg)] remains unclear. Various structural scenarios in terms of the percolation theory have been proposed recently to understand such a phenomenon; however, there is still no consensus on what the general percolation entity is and how the entity responds to the sudden slowdown dynamics during the glass transition. In this paper, we demonstrate that one-dimensional local linear ordering (LLO) is a universal structural motif associated with the glass transition for various metallic glasses. The quantitative evolution of LLO with temperature indicates that a percolating LLO network forms to serve as the backbone of the rigid glass solid when the temperature approaches the freezing point, resulting in the frozen-in dynamics accompanying the glass transition. The percolation transition occurs by pinning different LLO networks together, which only needs the introduction of a small number of "joint" atoms between them, and therefore the energy expenditure is very low.

Simple solvable energy-landscape model that shows a thermodynamic phase transition and a glass transition.

Science.gov (United States)

Naumis, Gerardo G

2012-06-01

When a liquid melt is cooled, a glass or phase transition can be obtained depending on the cooling rate. Yet, this behavior has not been clearly captured in energy-landscape models. Here, a model is provided in which two key ingredients are considered in the landscape, metastable states and their multiplicity. Metastable states are considered as in two level system models. However, their multiplicity and topology allows a phase transition in the thermodynamic limit for slow cooling, while a transition to the glass is obtained for fast cooling. By solving the corresponding master equation, the minimal speed of cooling required to produce the glass is obtained as a function of the distribution of metastable states.

Lifetime Prediction of Nano-Silica based Glass Fibre/Epoxy composite by Time Temperature Superposition Principle

Science.gov (United States)

Anand, Abhijeet; Banerjee, Poulami; Prusty, Rajesh Kumar; Ray, Bankin Chandra

2018-03-01

The incorporation of nano fillers in Fibre reinforced polymer (FRP) composites has been a source of experimentation for researchers. Addition of nano fillers has been found to improve mechanical, thermal as well as electrical properties of Glass fibre reinforced polymer (GFRP) composites. The in-plane mechanical properties of GFRP composite are mainly controlled by fibers and therefore exhibit good values. However, composite exhibits poor through-thickness properties, in which the matrix and interface are the dominant factors. Therefore, it is conducive to modify the matrix through dispersion of nano fillers. Creep is defined as the plastic deformation experienced by a material for a temperature at constant stress over a prolonged period of time. Determination of Master Curve using time-temperature superposition principle is conducive for predicting the lifetime of materials involved in naval and structural applications. This is because such materials remain in service for a prolonged time period before failure which is difficult to be kept marked. However, the failure analysis can be extrapolated from its behaviour in a shorter time at an elevated temperature as is done in master creep analysis. The present research work dealt with time-temperature analysis of 0.1% SiO2-based GFRP composites fabricated through hand-layup method. Composition of 0.1% for SiO2nano fillers with respect to the weight of the fibers was observed to provide optimized flexural properties. Time and temperature dependence of flexural properties of GFRP composites with and without nano SiO2 was determined by conducting 3-point bend flexural creep tests over a range of temperature. Stepwise isothermal creep tests from room temperature (30°C) to the glass transition temperature Tg (120°C) were performed with an alternative creep/relaxation period of 1 hour at each temperature. A constant stress of 40MPa was applied during the creep tests. The time-temperature superposition principle was

Quantum spin-glass transition in the two-dimensional electron gas

Indian Academy of Sciences (India)

Home; Journals; Pramana – Journal of Physics; Volume 58; Issue 2 ... Spin glasses; quantum phase transition; ferromagnetism; electron gas. ... We argue that a quantum transition involving the destruction of the spin-glass order in an applied in-plane magnetic field offers a natural explanation of some features of recent ...

Glass transitions in lubricants - Its relation to elastohydrodynamic lubrication /EHD/

Science.gov (United States)

Alsaad, M.; Bair, S.; Sanborn, D. M.; Winer, W. O.

1977-01-01

A preliminary investigation into the possible role of glass transition and glassy state behavior of lubricants in EHD contacts is reported. Measurements of the glass transition of lubricants as a function of pressure by two methods are presented along with a discussion indicating possible implications of the results to EHD lubrication.

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

Science.gov (United States)

Kreck, Cara A; Mancera, Ricardo L

2014-02-20

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

Optical transitions of Tm3+ in oxyfluoride glasses and compositional and thermal effect on upconversion luminescence of Tm3+/Yb3+-codoped oxyfluoride glasses.

Science.gov (United States)

Feng, Li; Wu, Yinsu; Liu, Zhuo; Guo, Tao

2014-01-24

Optical properties of Tm(3+)-doped SiO2-BaF2-ZnF2 glasses have been investigated on the basis of the Judd-Ofelt theory. Judd-Ofelt intensity parameters, radiative transition probabilities, fluorescence branching ratios and radiative lifetimes have been calculated for different glass compositions. Upconversion emissions were observed in Tm(3+)/Yb(3+)-codoped SiO2-BaF2-ZnF2 glasses under 980 nm excitation. The effects of composition, concentration of the doping ions, temperature, and excitation pump power on the upconversion emissions were also systematically studied. Copyright © 2013 Elsevier B.V. All rights reserved.

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

Science.gov (United States)

Ogawa, Shigesaburo; Asakura, Kouichi; Osanai, Shuichi

2010-11-22

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

Study of rigidity of semiconducting vanadate glasses and its ...

Indian Academy of Sciences (India)

These parameters along with the coordination number of the glasses affect the glass transition temperature. The correlation between the elastic moduli and thermal properties of these samples showed that 0.25MoO3–0.25PbO–0.5V2O5 glass is the most rigid and has an applicable glass transition temperature for coating.

Glass transition behavior and crystallization kinetics of Cu0.3(SSe20)0.7 chalcogenide glass

International Nuclear Information System (INIS)

Soliman, A.A.

2005-01-01

The glass transition behavior and crystallization kinetics of Cu 0.3 (SSe 20 ) 0.7 chalcogenide glass were investigated using differential scanning calorimetry (DSC), X-ray diffraction (XRD). Two crystalline phases (SSe 20 and Cu 2 Se) were identified after annealing the glass at 773 K for 24 h. The activation energy of the glass transition (E g ), the activation energy of crystallization (E c ), the Avrami exponent (n) and the dimensionality of growth (m) were determined. Results indicate that this glass crystallizes by a two-stage bulk crystallization process upon heating. The first transformation, in which SSe 20 precipitates from the amorphous matrix with a three-dimensional crystal growth. The second transformation, in which the residual amorphous phase transforms into Cu 2 Se compound with a two-dimensional crystal growth

Asymptotic solutions of glass temperature profiles during steady optical fibre drawing

KAUST Repository

Taroni, M.

2013-03-12

In this paper we derive realistic simplified models for the high-speed drawing of glass optical fibres via the downdraw method that capture the fluid dynamics and heat transport in the fibre via conduction, convection and radiative heating. We exploit the small aspect ratio of the fibre and the relative orders of magnitude of the dimensionless parameters that characterize the heat transfer to reduce the problem to one- or two-dimensional systems via asymptotic analysis. The resulting equations may be readily solved numerically and in many cases admit exact analytic solutions. The systematic asymptotic breakdown presented is used to elucidate the relative importance of furnace temperature profile, convection, surface radiation and conduction in each portion of the furnace and the role of each in controlling the glass temperature. The models derived predict many of the qualitative features observed in real industrial processes, such as the glass temperature profile within the furnace and the sharp transition in fibre thickness. The models thus offer a desirable route to quick scenario testing, providing valuable practical information about the dependencies of the solution on the parameters and the dominant heat-transport mechanism. © 2013 Springer Science+Business Media Dordrecht.

Hydrothermal metallurgy for recycling of slag and glass

International Nuclear Information System (INIS)

Tanaka, Toshihiro; Yoshikawa, Takeshi; Hirai, Nobumitsu; Katsuyama, Shigeru

2009-01-01

The authors have applied hydrothermal reactions to develop recycling processing of slag or glass. As an example, under hydrothermal conditions such as 200 300 deg. C and 30 40MPa with H 2 O, powders made of glass can be sintered to become solidified glass materials containing about 10mass% H 2 O. When the glass containing H 2 O is heated again under normal pressure, the glass expands releasing H 2 O to make porous microstructure. H 2 O starts to emit just above the glass transition temperature. Therefore, when we have a glass with low glass transition temperature, we can make low temperature foaming glass. The SiO 2 -Na 2 O-B 2 O 3 glass is a candidate to be such a foaming glass. In this paper, we describe our recent trial on the fabrication of the low temperature foaming glass by using hydrothermal reaction.

Are the dynamics of silicate glasses and glass-forming liquids embedded in their elastic properties?

DEFF Research Database (Denmark)

Smedskjær, Morten Mattrup; Mauro, John C.

According to the elastic theory of the glass transition, the dynamics of glasses and glass-forming liquids are controlled by the evolution of shear modulus. In particular, the elastic shoving model expresses dynamics in terms of an activation energy required to shove aside the surrounding atoms......, which is determined by the shear modulus. First, we here present an in situ high-temperature Brillouin spectroscopy test of the shoving model near the glass transition of eight aluminosilicate glass-forming systems. We find that the measured viscosity data agree qualitatively with the measured...... temperature dependence of shear moduli, as predicted by the shoving model. However, the model systematically underpredicts the values of fragility. Second, we also present a thorough test of the shoving model for predicting the low temperature dynamics of an aluminosilicate glass system. This is done...

Studying the Adhesion Force and Glass Transition of Thin Polystyrene Films by Atomic Force Microscopy

DEFF Research Database (Denmark)

Kang, Hua; Qian, Xiaoqin; Guan, Li

2018-01-01

microscopy (AFM)-based forcedistance curve to study the relaxation dynamics and the film thickness dependence of glass transition temperature (T-g) for normal thin polystyrene (PS) films supported on silicon substrate. The adhesion force (F-ad) between AFM tip and normal thin PS film surfaces...

Glass transition behaviour of the quaternary ammonium type ionic liquid, {[DEME][I] + H2O} mixtures

International Nuclear Information System (INIS)

Imai, Yusuke; Abe, Hiroshi; Matsumoto, Hitoshi; Shimada, Osamu; Hanasaki, Tomonori; Yoshimura, Yukihiro

2011-01-01

By a simple DTA system, the glass transition temperatures of the quaternary ammonium type ionic liquid, {N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium iodide, [DEME][I] + H 2 O} mixtures after quick pre-cooling were measured as a function of water concentration (x mol% H 2 O). Results were compared with the previous results of {[DEME][BF 4 ] + H 2 O} mixtures in which double glass transitions were observed in the water concentration region of (16.5 to 30.0) mol% H 2 O. Remarkably, we observed the double glass transition phenomenon in {[DEME][I] + H 2 O} mixtures too, but the two-T g s regions lie towards the water-rich side of (77.5 to 85.0) mol% H 2 O. These clearly reflect the difference in the anionic effect between BF 4 - and I - on the water structure. The end of the glass-formation region of {[DEME][I] + H 2 O} mixtures is around x = 95.0 mol% H 2 O, and this is comparable to that of {[DEME][BF 4 ] + H 2 O} mixtures (x = 96.0 mol% H 2 O).

Mechanical relaxation in glasses

International Nuclear Information System (INIS)

Hiki, Y.

2004-01-01

The basic properties of glasses and the characteristics of mechanical relaxation in glasses were briefly reviewed, and then our studies concerned were presented. Experimental methods adopted were viscosity, internal friction, ultrasonic attenuation, and Brillouin scattering measurements. The specimens used were several kinds of inorganic, organic, and metallic glasses. The measurements were mainly carried out from the room temperature up to the glass transition temperature, and the relaxation time was determined as a function of temperature. The 'double relaxation' composed of two Arrhenius-type relaxations was observed in many materials. In both relaxations, the 'compensation effect' showing a correlation of the pre-exponential factor and the activation energy was observed. These results were explained by considering the 'complex relaxation' due to cooperative motions of atoms or group of atoms. Values of activation energy near the glass transition determined by the various experimental methods were compared with each other

Structure, glass transition temperature and spectroscopic properties of 10Li2O-xP2O5-(89-x)TeO2-1CuO (5≤x≤25 mol%) glass system.

Science.gov (United States)

Upender, G; Babu, J Chinna; Mouli, V Chandra

2012-04-01

X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), energy dispersive X-ray spectrometry (EDS), differential scanning calorimetry (DSC), infrared (IR), Raman, electron paramagnetic resonance (EPR) and optical absorption studies on 10Li2O-xP2O5-(89-x)TeO2-1CuO glasses (where x=5, 10, 15, 20 and 25 mol%) have been carried out. The amorphous nature of the glasses was confirmed using XRD and FESEM measurements. The glass transition temperature (Tg) of glass samples have been estimated from DSC traces and found that the Tg increases with increasing P2O5 content. Both the IR and Raman studies have been showed that the present glass system consists of [TeO3], [TeO4], [PO3] and [PO4] units. The spin-Hamiltonian parameters such as g∥, g⊥, and A∥ have been determined from EPR spectra and it was found that the Cu2+ ion is present in tetragonal distorted octahedral site with [Formula: see text] as the ground state. Bonding parameters and bonding symmetry of Cu2+ ions have been calculated by correlating EPR and optical data and were found to be composition dependent. Copyright © 2012 Elsevier B.V. All rights reserved.

Exploring the dynamics about the glass transition by muon spin relaxation and muon spin rotation

International Nuclear Information System (INIS)

Bermejo, F J; Bustinduy, I; Cox, S F J; Lord, J S; Cabrillo, C; Gonzalez, M A

2006-01-01

The capability of muon spin rotation and muon spin relaxation to explore dynamics in the vicinity of the glass transition is illustrated by results pertaining to three materials exhibiting two different glass-forming abilities. Measurements under transverse magnetic fields enable us to monitor the dynamics of muonium-labelled closed-shell molecules within the microsecond range. The results display the onset of stochastic molecular motions taking place upon crossing from below the glass-transition temperature. In turn, the molecular dynamics of radicals formed by addition of atomic muonium to unsaturated organic molecules can also be explored up to far shorter times by means of relaxation measurements under longitudinal fields. The technique is then shown to be capable of singling out stochastic reorientational motions from others, which usually are strongly coupled to them and usually dominate the material response when measured using higher-frequency probes such as neutron and light scattering

Effect of mixed transition metal ions on DC conductivity in lithium bismuth borate glasses

Energy Technology Data Exchange (ETDEWEB)

Khasa, S.; Yadav, Arti, E-mail: artidabhur@gmail.com; Dahiya, M. S.; Seema,; Ashima [Physics Department, Deenbandhu Chhotu Ram University of Science & Technology, Murthal-131039 (India); Agarwal, A. [Physics Department, G.J. University of science and technology, Hisar-125001 (India)

2015-06-24

The DC conductivities of glasses having composition x(2NiO·V{sub 2}O{sub 5})·(30-x)Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} (with x=0, 2, 5, 7 and 10, i.e. NVLBB glasses) and glass samples having composition 7NiO·23 Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} and 7V{sub 2}O{sub 5}·23Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} (NLBB and VLBB respectively) are investigated as a function of temperature. Conductivity for glasses containing higher percentage of lithium ions is predominantly ionic and in glasses containing higher percentage of transition metal (TM) ions is predominantly electronic. The observed increase in conductivity with x and peak-like behavior at x=7 in NVLBB glasses due to competitive transport of small polaron contributing to a significant structural change in NVLBB glasses. Variation of molar volume and density was also observed with x. In NVLBB glasses, as x increases density increases except a slight decrease at x=7. Also density increases in NLBB whereas in case of VLBB it decreases in comparison to NVLBB1 glass composition. Mott’s small polaron hopping (SPH) model has been applied to analyze the high temperature conductivity data and activation energy.

On the Frequency Correction in Temperature-Modulated Differential Scanning Calorimetry of Glass Transition

DEFF Research Database (Denmark)

Guo, Xiaoju; Mauro, J.C.; Allan, D.C.

2012-01-01

Temperature-modulated differential scanning calorimetry (TMDSC) is based on conventional DSC but with a sinusoidally modulated temperature path. Simulations of TMDSC signals were performed for Corning EAGLE XG® glass over a wide range of modulation frequencies. Our results reveal that the frequency...... correction commonly used in the interpretation of TMDSC signals leads to a master nonreversing heat flow curve independent of modulation frequency, provided that sufficiently high frequencies are employed in the TMDSC measurement. A master reversing heat flow curve can also be generated through the frequency...

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

Science.gov (United States)

Shor, Stanislav; Yahel, Eyal; Makov, Guy

2018-04-01

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

Long-wavelength fluctuations and the glass transition in two dimensions and three dimensions.

Science.gov (United States)

Vivek, Skanda; Kelleher, Colm P; Chaikin, Paul M; Weeks, Eric R

2017-02-21

Phase transitions significantly differ between 2D and 3D systems, but the influence of dimensionality on the glass transition is unresolved. We use microscopy to study colloidal systems as they approach their glass transitions at high concentrations and find differences between two dimensions and three dimensions. We find that, in two dimensions, particles can undergo large displacements without changing their position relative to their neighbors, in contrast with three dimensions. This is related to Mermin-Wagner long-wavelength fluctuations that influence phase transitions in two dimensions. However, when measuring particle motion only relative to their neighbors, two dimensions and three dimensions have similar behavior as the glass transition is approached, showing that the long-wavelength fluctuations do not cause a fundamental distinction between 2D and 3D glass transitions.

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

Science.gov (United States)

Halalay, Ion C.

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

Dynamic and thermodynamic characteristics associated with the glass transition of amorphous trehalose-water mixtures.

Science.gov (United States)

Weng, Lindong; Elliott, Gloria D

2014-06-21

The glass transition temperature Tg of biopreservative formulations is important for predicting the long-term storage of biological specimens. As a complementary tool to thermal analysis techniques, which are the mainstay for determining Tg, molecular dynamics simulations have been successfully applied to predict the Tg of several protectants and their mixtures with water. These molecular analyses, however, rarely focused on the glass transition behavior of aqueous trehalose solutions, a subject that has attracted wide scientific attention via experimental approaches. Important behavior, such as hydrogen-bonding dynamics and self-aggregation has yet to be explored in detail, particularly below, or in the vicinity of, Tg. Using molecular dynamics simulations of several dynamic and thermodynamic properties, this study reproduced the supplemented phase diagram of trehalose-water mixtures (i.e., Tg as a function of the solution composition) based on experimental data. The structure and dynamics of the hydrogen-bonding network in the trehalose-water systems were also analyzed. The hydrogen-bonding lifetime was determined to be an order of magnitude higher in the glassy state than in the liquid state, while the constitution of the hydrogen-bonding network exhibited no noticeable change through the glass transition. It was also found that trehalose molecules preferred to form small, scattered clusters above Tg, but self-aggregation was substantially increased below Tg. The average cluster size in the glassy state was observed to be dependent on the trehalose concentration. Our findings provided insights into the glass transition characteristics of aqueous trehalose solutions as they relate to biopreservation.

Molecular Orientation in Two Component Vapor-Deposited Glasses: Effect of Substrate Temperature and Molecular Shape

Science.gov (United States)

Powell, Charles; Jiang, Jing; Walters, Diane; Ediger, Mark

Vapor-deposited glasses are widely investigated for use in organic electronics including the emitting layers of OLED devices. These materials, while macroscopically homogenous, have anisotropic packing and molecular orientation. By controlling this orientation, outcoupling efficiency can be increased by aligning the transition dipole moment of the light-emitting molecules parallel to the substrate. Light-emitting molecules are typically dispersed in a host matrix, as such, it is imperative to understand molecular orientation in two-component systems. In this study we examine two-component vapor-deposited films and the orientations of the constituent molecules using spectroscopic ellipsometry, UV-vis and IR spectroscopy. The role of temperature, composition and molecular shape as it effects molecular orientation is examined for mixtures of DSA-Ph in Alq3 and in TPD. Deposition temperature relative to the glass transition temperature of the two-component mixture is the primary controlling factor for molecular orientation. In mixtures of DSA-Ph in Alq3, the linear DSA-Ph has a horizontal orientation at low temperatures and slight vertical orientation maximized at 0.96Tg,mixture, analogous to one-component films.

Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition

Science.gov (United States)

Wong DeRieux, Wing-Sy; Li, Ying; Lin, Peng; Laskin, Julia; Laskin, Alexander; Bertram, Allan K.; Nizkorodov, Sergey A.; Shiraiwa, Manabu

2018-05-01

Secondary organic aerosol (SOA) accounts for a large fraction of submicron particles in the atmosphere. SOA can occur in amorphous solid or semi-solid phase states depending on chemical composition, relative humidity (RH), and temperature. The phase transition between amorphous solid and semi-solid states occurs at the glass transition temperature (Tg). We have recently developed a method to estimate Tg of pure compounds containing carbon, hydrogen, and oxygen atoms (CHO compounds) with molar mass less than 450 g mol-1 based on their molar mass and atomic O : C ratio. In this study, we refine and extend this method for CH and CHO compounds with molar mass up to ˜ 1100 g mol-1 using the number of carbon, hydrogen, and oxygen atoms. We predict viscosity from the Tg-scaled Arrhenius plot of fragility (viscosity vs. Tg/T) as a function of the fragility parameter D. We compiled D values of organic compounds from the literature and found that D approaches a lower limit of ˜ 10 (±1.7) as the molar mass increases. We estimated the viscosity of α-pinene and isoprene SOA as a function of RH by accounting for the hygroscopic growth of SOA and applying the Gordon-Taylor mixing rule, reproducing previously published experimental measurements very well. Sensitivity studies were conducted to evaluate impacts of Tg, D, the hygroscopicity parameter (κ), and the Gordon-Taylor constant on viscosity predictions. The viscosity of toluene SOA was predicted using the elemental composition obtained by high-resolution mass spectrometry (HRMS), resulting in a good agreement with the measured viscosity. We also estimated the viscosity of biomass burning particles using the chemical composition measured by HRMS with two different ionization techniques: electrospray ionization (ESI) and atmospheric pressure photoionization (APPI). Due to differences in detected organic compounds and signal intensity, predicted viscosities at low RH based on ESI and APPI measurements differ by 2-5 orders

Free volume model: High-temperature deformation of a Zr-based bulk metallic glass

International Nuclear Information System (INIS)

Bletry, M.; Guyot, P.; Blandin, J.J.; Soubeyroux, J.L.

2006-01-01

The homogeneous deformation of a zirconium-based bulk metallic glass is investigated in the glass transition region. Compression tests at different temperatures and strain rates have been conducted. The mechanical behavior is analyzed in the framework of the free volume model, taking into account the dependence of the flow defect concentration on deformation. The activation volume is evaluated and allows one to gather the viscosity data (for the different strain rates and temperatures) on a unique master curve. It is also shown that, due to the relation between flow defect concentration and free volume, it is not possible to deduce the equilibrium flow defect concentration directly from mechanical measurements. However, if this parameter is arbitrarily chosen, mechanical measurements give access to the other parameters of the model, these parameters for the alloy under investigation being of the same order of magnitude as those for other metallic glasses

Optical properties of 3d transition metal ion-doped sodium borosilicate glass

International Nuclear Information System (INIS)

Wen, Hongli; Tanner, Peter A.

2015-01-01

Graphical abstract: Photographs of undoped (SiO 2 ) 50 (Na 2 O) 25 (B 2 O 3 ) 25 (SiNaB) glass and transition metal ion-doped (TM) 0.5 (SiO 2 ) 49.5 (Na 2 O) 25 (B 2 O 3 ) 25 glass samples. - Highlights: • 3d transition metal ion (from Ti to Zn) doped SiO 2 -Na 2 O-B 2 O 3 glasses. • Optical properties of doped glasses investigated. • V(IV,V); Cr(III, VI); Mn(II,III); Fe(II,III); Co(II); Ni(II); Cu(II) by XANES, DRS. • Strong visible absorption but only vanadium ion gives strong emission in glass. - Abstract: SiO 2 -Na 2 O-B 2 O 3 glasses doped with 3d-transition metal species from Ti to Zn were prepared by the melting-quenching technique and their optical properties were investigated. The X-ray absorption near edge spectra of V, Cr, and Mn-doped glasses indicate that the oxidation states of V(IV, V), Cr(III, VI) and Mn(II, III) exist in the studied glasses. The oxidation states revealed from the diffuse reflectance spectra of the glasses are V(IV, V), Cr(III, VI), Mn(III), Fe(II, III), Co(II), Ni(II), and Cu(II). Most of the 3d transition element ions exhibit strong absorption in the visible spectral region in the glass. Under ultraviolet excitation, the undoped sodium borosilicate glass produces weak and broad emission, while doping of vanadium introduces strong and broad emission due to the V(V) charge transfer transition. Only weak emission is observed from Ti(IV), Mn(II), Fe(III) and Cu(II), partly resulting from the strong electron–phonon coupling of the 3d-electrons and the relatively high phonon energy of the studied glass host, with the former leading to dominant nonradiative relaxation based on multiphonon processes for most of the 3d excited states

Stereodynamic insight into the thermal history effects on poly(vinyl chloride) calorimetric sub-glass and glass transitions as a fragile glass model.

Science.gov (United States)

Pin, Jean-Mathieu; Behazin, Ehsan; Misra, Manjusri; Mohanty, Amar

2018-05-02

The dynamic thermal history impact of poly(vinyl chloride) (PVC) has been explored for a wide range of pre-cooling rates, from 1 to 30 °C min-1. A first macroscopic insight into the dynamic thermal history influence has been highlighted through a decrease in the apparent activation energy (Eapp) in the first stage of the glass transition. The overall glass transition Eapp surface was successfully modeled in a polynomial fashion regarding the pre-cooling range. Raman scattering was used to associate the Eapp variations along the glass transition conversion with the stereochemistry evolution during the polymeric relaxation. Herein, the selection of atactic PVC as the polymer model permits us to monitor the glassy polymer segment stereodynamics during the heating ramp through the C-Cl stretching. The intermolecular H-Cl dipole interactions, as well as intramolecular conformational reorganizations among syndiotactic, isotactic and heterotactic polymer sequences, have been associated with non-cooperative and cooperative motions, i.e. the β- and α-process, respectively. The fruitful comparison of the two extreme values of the pre-cooling rates permits us to propose a thermokinetic scenario that explains the occurrence, intensity, and inter-dependence of β- and α-processes in the glassy state and during the glass transition. This scenario could potentially be generalized to all the other polymeric glass-formers.

Effects of temperature changes and stress loading on the mechanical and shape memory properties of thermoplastic materials with different glass transition behaviours and crystal structures.

Science.gov (United States)

Iijima, Masahiro; Kohda, Naohisa; Kawaguchi, Kyotaro; Muguruma, Takeshi; Ohta, Mitsuru; Naganishi, Atsuko; Murakami, Takashi; Mizoguchi, Itaru

2015-12-01

To investigate the effects of temperature changes and stress loading on the mechanical and shape memory properties of thermoplastic materials with different glass transition behaviours and crystal structures. Five thermoplastic materials, polyethylene terephthalate glycol (Duran®, Scheu Dental), polypropylene (Hardcast®, Scheu Dental), and polyurethane (SMP MM®, SMP Technologies) with three different glass transition temperatures (T g) were selected. The T g and crystal structure were assessed using differential scanning calorimetry and X-ray diffraction. The deterioration of mechanical properties by thermal cycling and the orthodontic forces during stepwise temperature changes were investigated using nanoindentation testing and custom-made force-measuring system. The mechanical properties were also evaluated by three-point bending tests; shape recovery with heating was then investigated. The mechanical properties for each material were decreased significantly by 2500 cycles and great decrease was observed for Hardcast (crystal plastic) with higher T g (155.5°C) and PU 1 (crystalline or semi-crystalline plastic) with lower T g (29.6°C). The Duran, PU 2, and PU 3 with intermediate T g (75.3°C for Duran, 56.5°C for PU 2, and 80.7°C for PU 3) showed relatively stable mechanical properties with thermal cycling. The polyurethane polymers showed perfect shape memory effect within the range of intraoral temperature changes. The orthodontic force produced by thermoplastic appliances decreased with the stepwise temperature change for all materials. Orthodontic forces delivered by thermoplastic appliances may influence by the T g of the materials, but not the crystal structure. Polyurethane is attractive thermoplastic materials due to their unique shape memory phenomenon, but stress relaxation with temperature changes is expected. © The Author 2015. Published by Oxford University Press on behalf of the European Orthodontic Society. All rights reserved. For

Effects of configurational changes on electrical resistivity during glass-liquid transition of two bulk metal-alloy glasses

Energy Technology Data Exchange (ETDEWEB)

Aji, D. P. B.; Johari, G. P., E-mail: joharig@mcmaster.ca [Department of Materials Science and Engineering, McMaster University, Hamilton, Ontario L8S 4L7 (Canada)

2014-12-14

Consequences of increase in structural fluctuations on heating Pd{sub 40}Ni{sub 10}Cu{sub 30}P{sub 20} and Zr{sub 46.75}Ti{sub 8.25}Cu{sub 7.5}Ni{sub 10}Be{sub 27.5} through their glass to liquid transition range were investigated by measuring the electrical resistivity, ρ, an electron scattering property. The temperature coefficient of resistivity (TCR = (1/ρ) dρ/dT) of the liquid and glassy states is negative. The plots of their ρ against T in the T{sub g} (glass to liquid transition) range show a gradual change in the slope similar to the change observed generally for the plots of the density, elastic modulus, and refractive index. As fluctuations in the melt structure involve fewer configurations on cooling, ρ increases. In the energy landscape description, the melt's structure explores fewer minima with decrease in T, vibrational frequencies increase, and electron scattering and ρ increase. Plots of (−dρ/dT) against T resemble the plot of the specific heat of other glasses and show a sub-T{sub g} feature and a rapid rise at T near T{sub g}. Analysis shows that the magnitude of negative TCR is dominated by change in the phonon characteristics, and configurational fluctuations make it more negative. The TCR of the liquid and glassy states seems qualitatively consistent with the variation in the structure factor in Ziman's model for pure liquid metals as extended by Nagel to metal alloys and used to explain the negative TCR of a two-component metal glass.

Characterization of structural relaxation in inorganic glasses using length dilatometry

Science.gov (United States)

Koontz, Erick

The processes that govern how a glass relaxes towards its thermodynamic quasi-equilibrium state are major factors in understanding glass behavior near the glass transition region, as characterized by the glass transition temperature (Tg). Intrinsic glass properties such as specific volume, enthalpy, entropy, density, etc. are used to map the behavior of the glass network below in and near the transition region. The question of whether a true thermodynamic second order phase transition takes place in the glass transition region is another pending question. Linking viscosity behavior to entropy, or viewing the glass configuration as an energy landscape are just a couple of the most prevalent methods used for attempting to understand the glass transition. The structural relaxation behavior of inorganic glasses is important for more than scientific reasons, many commercial glass processing operations including glass melting and certain forms of optical fabrication include significant time spent in the glass transition region. For this reason knowledge of structural relaxation processes can, at a minimum, provide information for annealing duration of melt-quenched glasses. The development of a predictive model for annealing time prescription has the potential to save glass manufacturers significant time and money as well as increasing volume throughput. In optical hot forming processes such as precision glass molding, molded optical components can significantly change in shape upon cooling through the glass transition. This change in shape is not scientifically predictable as of yet though manufacturers typically use empirical rules developed in house. The classification of glass behavior in the glass transition region would allow molds to be accurately designed and save money for the producers. The work discussed in this dissertation is comprised of the development of a dilatometric measurement and characterization method of structural relaxation. The measurement and

Ellipsometry measurements of glass transition breadth in bulk films of random, block, and gradient copolymers.

Science.gov (United States)

Mok, M M; Kim, J; Marrou, S R; Torkelson, J M

2010-03-01

Bulk films of random, block and gradient copolymer systems were studied using ellipsometry to demonstrate the applicability of the numerical differentiation technique pioneered by Kawana and Jones for studying the glass transition temperature (T (g)) behavior and thermal expansivities of copolymers possessing different architectures and different levels of nanoheterogeneity. In a series of styrene/n -butyl methacrylate (S/nBMA) random copolymers, T (g) breadths were observed to increase from approximately 17( degrees ) C in styrene-rich cases to almost 30( degrees ) C in nBMA-rich cases, reflecting previous observations of significant nanoheterogeneity in PnBMA homopolymers. The derivative technique also revealed for the first time a substantial increase in glassy-state expansivity with increasing nBMA content in S/nBMA random copolymers, from 1.4x10(-4) K-1 in PS to 3.5x10(-4) K-1 in PnBMA. The first characterization of block copolymer T (g) 's and T (g) breadths by ellipsometry is given, examining the impact of nanophase-segregated copolymer structure on ellipsometric measurements of glass transition. The results show that, while the technique is effective in detecting the two T (g) 's expected in certain block copolymer systems, the details of the glass transition can become suppressed in ellipsometry measurements of a rubbery minor phase under conditions where the matrix is glassy; meanwhile, both transitions are easily discernible by differential scanning calorimetry. Finally, broad glass transition regions were measured in gradient copolymers, yielding in some cases extraordinary T (g) breadths of 69- 71( degrees ) C , factors of 4-5 larger than the T (g) breadths of related homopolymers and random copolymers. Surprisingly, one gradient copolymer demonstrated a slightly narrower T (g) breadth than the S/nBMA random copolymers with the highest nBMA content. This highlights the fact that nanoheterogeneity relevant to the glass transition response in selected

Sealed glass coating of high temperature ceramic superconductors

Science.gov (United States)

Wu, Weite; Chu, Cha Y.; Goretta, Kenneth C.; Routbort, Jules L.

1995-01-01

A method and article of manufacture of a lead oxide based glass coating on a high temperature superconductor. The method includes preparing a dispersion of glass powders in a solution, applying the dispersion to the superconductor, drying the dispersion before applying another coating and heating the glass powder dispersion at temperatures below oxygen diffusion onset and above the glass melting point to form a continuous glass coating on the superconductor to establish compressive stresses which enhance the fracture strength of the superconductor.

Quantification of Protein Hydration, Glass Transitions, and Structural Relaxations of Aqueous Protein and Carbohydrate-Protein Systems.

Science.gov (United States)

Roos, Yrjö H; Potes, Naritchaya

2015-06-11

Water distribution and miscibility of carbohydrate and protein components in biological materials and their structural contributions in concentrated solids are poorly understood. In the present study, structural relaxations and a glass transition of protein hydration water and antiplasticization of the hydration water at low temperatures were measured using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) for bovine whey protein (BWP), aqueous glucose-fructose (GF), and their mixture. Thermal transitions of α-lactalbumin and β-lactoglobulin components of BWP included water-content-dependent endothermic but reversible dehydration and denaturation, and exothermic and irreversible aggregation. An α-relaxation assigned to hydration water in BWP appeared at water-content-dependent temperatures and increased to over the range of 150-200 K at decreasing water content and in the presence of GF. Two separate glass transitions and individual fractions of unfrozen water of ternary GF-BWP-water systems contributed to uncoupled α-relaxations, suggesting different roles of protein hydration water and carbohydrate vitrification in concentrated solids during freezing and dehydration. Hydration water in the BWP fraction of GF-BWP systems was derived from equilibrium water sorption and glass transition data of the GF fraction, which gave a significant universal method to quantify (i) protein hydration water and (ii) the unfrozen water in protein-carbohydrate systems for such applications as cryopreservation, freezing, lyophilization, and dehydration of biological materials. A ternary supplemented phase diagram (state diagram) established for the GF-BWP-water system can be used for the analysis of the water distribution across carbohydrate and protein components in such applications.

Mechanical Properties of Stable Glasses Using Nanoindentation

Science.gov (United States)

Wolf, Sarah; Liu, Tianyi; Jiang, Yijie; Ablajan, Keyume; Zhang, Yue; Walsh, Patrick; Turner, Kevin; Fakhraai, Zahra

Glasses with enhanced stability over ordinary, liquid quenched glasses have been formed via the process of Physical Vapor Deposition (PVD) by using a sufficiently slow deposition rate and a substrate temperature slightly below the glass transition temperature. These stable glasses have been shown to exhibit higher density, lower enthalpy, and better kinetic stability over ordinary glass, and are typically optically birefringent, due to packing and orientational anisotropy. Given these exceptional properties, it is of interest to further investigate how the properties of stable glasses compare to those of ordinary glass. In particular, the mechanical properties of stable glasses remain relatively under-investigated. While the speed of sound and elastic moduli have been shown to increase with increased stability, little is known about their hardness and fracture toughness compared to ordinary glasses. In this study, glasses of 9-(3,5-di(naphthalen-1-yl)phenyl)anthracene were deposited at varying temperatures relative to their glass transition temperature, and their mechanical properties measured by nanoindentation. Hardness and elastic modulus of the glasses were compared across substrate temperatures. After indentation, the topography of these films were studied using Atomic Force Microscopy (AFM) in order to further compare the relationship between thermodynamic and kinetic stability and mechanical failure. Z.F. and P.W. acknowledge funding from NSF(DMREF-1628407).

Optical temperature sensor based on the Nd{sup 3+} infrared thermalized emissions in a fluorotellurite glass

Energy Technology Data Exchange (ETDEWEB)

Lalla, E.A. [Departamento de Física, Universidad de la Laguna, San Cristóbal de la Laguna, 38200 Santa Cruz de Tenerife (Spain); León-Luis, S.F., E-mail: sleonlui@ull.es [Departamento de Física, Universidad de la Laguna, San Cristóbal de la Laguna, 38200 Santa Cruz de Tenerife (Spain); Malta Consolider Team, Universidad de la Laguna, San Cristóbal de la Laguna, 38200 Santa Cruz de Tenerife (Spain); Monteseguro, V. [Departamento de Física, Universidad de la Laguna, San Cristóbal de la Laguna, 38200 Santa Cruz de Tenerife (Spain); Malta Consolider Team, Universidad de la Laguna, San Cristóbal de la Laguna, 38200 Santa Cruz de Tenerife (Spain); Pérez-Rodríguez, C. [Departamento de Física, Universidad de la Laguna, San Cristóbal de la Laguna, 38200 Santa Cruz de Tenerife (Spain); Cáceres, J.M. [Departamento de Ingeniería Industrial, Universidad de la Laguna, San Cristóbal de la Laguna, 38200 Santa Cruz de Tenerife (Spain); and others

2015-10-15

The temperature dependence of the infrared luminescence of a fluorotellurite glass doped with 0.01 and 2.5 mol% of Nd{sup 3+} ions was studied in order to use it as a high temperature sensing probe. For this purpose, the emission intensities of the ({sup 4}S{sub 3/2}, {sup 4}F{sub 7/2}), ({sup 2}H{sub 9/2}, {sup 4}F{sub 5/2}),{sup 4}F{sub 3/2}→{sup 4}I{sub 9/2} transitions were measured in a wide range of temperatures from 300 upto 650 K. The changes in the emission profiles were calibrated by means of the fluorescence intensity ratio technique. The calibrations showed a strong dependence on the Nd{sup 3+} ions concentration, having the low-doped concentrated sample the best response to changes of temperature. The maximum value obtained for the thermal sensibility is 17×10{sup −4} K{sup −1} at 640 K, being one of the highest values found in the literature for Nd{sup 3+} optical temperature sensors. Finally, the experimental calibrations were compared with the theoretical temperature luminescence response calculated from the Judd–Ofelt theory. - Highlights: • Nd{sup 3+}-doped fluorotellurite glasses were prepared. • The intensities of the ({sup 4}S{sub 3/2},{sup 4}F{sub 7/2}),({sup 2}H{sub 9/2},{sup 4}F{sub 5/2}), {sup 4}F{sub 3/2}→{sup 4}I{sub 9/2} transitions. • The highest thermal sensitivity has been obtained for the glass with the lowest concentration of Nd{sup 3+} ions. • The Nd{sup 3+}-doped fluorotellurite glass fits the requirement for a good temperature sensor.

Using Combined Computational Techniques to Predict the Glass Transition Temperatures of Aromatic Polybenzoxazines

Science.gov (United States)

Mhlanga, Phumzile; Wan Hassan, Wan Aminah; Hamerton, Ian; Howlin, Brendan J.

2013-01-01

The Molecular Operating Environment software (MOE) is used to construct a series of benzoxazine monomers for which a variety of parameters relating to the structures (e.g. water accessible surface area, negative van der Waals surface area, hydrophobic volume and the sum of atomic polarizabilities, etc.) are obtained and quantitative structure property relationships (QSPR) models are formulated. Three QSPR models (formulated using up to 5 descriptors) are first used to make predictions for the initiator data set (n = 9) and compared to published thermal data; in all of the QSPR models there is a high level of agreement between the actual data and the predicted data (within 0.63–1.86 K of the entire dataset). The water accessible surface area is found to be the most important descriptor in the prediction of Tg. Molecular modelling simulations of the benzoxazine polymer (minus initiator) carried out at the same time using the Materials Studio software suite provide an independent prediction of Tg. Predicted Tg values from molecular modelling fall in the middle of the range of the experimentally determined Tg values, indicating that the structure of the network is influenced by the nature of the initiator used. Hence both techniques can provide predictions of glass transition temperatures and provide complementary data for polymer design. PMID:23326419

Using combined computational techniques to predict the glass transition temperatures of aromatic polybenzoxazines.

Directory of Open Access Journals (Sweden)

Phumzile Mhlanga

Full Text Available The Molecular Operating Environment software (MOE is used to construct a series of benzoxazine monomers for which a variety of parameters relating to the structures (e.g. water accessible surface area, negative van der Waals surface area, hydrophobic volume and the sum of atomic polarizabilities, etc. are obtained and quantitative structure property relationships (QSPR models are formulated. Three QSPR models (formulated using up to 5 descriptors are first used to make predictions for the initiator data set (n = 9 and compared to published thermal data; in all of the QSPR models there is a high level of agreement between the actual data and the predicted data (within 0.63-1.86 K of the entire dataset. The water accessible surface area is found to be the most important descriptor in the prediction of T(g. Molecular modelling simulations of the benzoxazine polymer (minus initiator carried out at the same time using the Materials Studio software suite provide an independent prediction of T(g. Predicted T(g values from molecular modelling fall in the middle of the range of the experimentally determined T(g values, indicating that the structure of the network is influenced by the nature of the initiator used. Hence both techniques can provide predictions of glass transition temperatures and provide complementary data for polymer design.

Structure of cesium loaded iron phosphate glasses: An infrared and Raman spectroscopy study

International Nuclear Information System (INIS)

Joseph, Kitheri; Premila, M.; Amarendra, G.; Govindan Kutty, K.V.; Sundar, C.S.; Vasudeva Rao, P.R.

2012-01-01

The structure of cesium loaded iron phosphate glasses (IPG) was investigated using infrared and Raman spectroscopy. The spectra of the cesium doped samples revealed a structural modification of the parent glass owing to the incorporation of cesium. The structural changes could be correlated with the variation observed in the glass transition temperature of these glasses. Increased Cs-mediated cationic cross linking appears to be the reason for the initial rise in glass transition temperature up to 21 mol% Cs 2 O in IPG; while, breakdown of the phosphate network with increasing cesium content, brings down the glass transition temperature.

Nuclear waste immobilization in iron phosphate glasses

International Nuclear Information System (INIS)

Garcia, D.A.; Rodriguez, Diego A.; Menghini, Jorge E.; Bevilacqua, Arturo

2007-01-01

Iron-phosphate glasses have become important in the nuclear waste immobilization area because they have some advantages over silicate-based glasses, such as a lower processing temperature and a higher nuclear waste load without losing chemical and mechanical properties. Structure and chemical properties of iron-phosphate glasses are determined in terms of the main components, in this case, phosphate oxide along with the other oxides that are added to improve some of the characteristics of the glasses. For example, Iron oxide improves chemical durability, lead oxide lowers fusion temperature and sodium oxide reduces viscosity at high temperature. In this work a study based on the composition-property relations was made. We used different techniques to characterize a series of iron-lead-phosphate glasses with uranium and aluminium oxide as simulated nuclear waste. We used the Arquimedes method to determine the bulk density, differential temperature analysis (DTA) to determine both glass transition temperature and crystallization temperature, dilatometric analysis to calculate the linear thermal expansion coefficient, chemical durability (MCC-1 test) and X-ray diffraction (XRD). We also applied some theoretic models to calculate activation energies associated with the glass transition temperature and crystallization processes. (author)

Glass precursor approach to high-temperature superconductors

Science.gov (United States)

Bansal, Narottam P.

1992-01-01

The available studies on the synthesis of high T sub c superconductors (HTS) via the glass precursor approach were reviewed. Melts of the Bi-Sr-Ca-Cu-O system as well as those doped with oxides of some other elements (Pb, Al, V, Te, Nb, etc.) could be quenched into glasses which, on further heat treatments under appropriate conditions, crystallized into the superconducting phase(s). The nature of the HTS phase(s) formed depends on the annealing temperature, time, atmosphere, and the cooling rate and also on the glass composition. Long term annealing was needed to obtain a large fraction of the 110 K phase. The high T sub c phase did not crystallize out directly from the glass matrix, but was preceded by the precipitation of other phases. The 110 K HTS was produced at high temperatures by reaction between the phases formed at lower temperatures resulting in multiphase material. The presence of a glass former such as B2O3 was necessary for the Y-Ba-Cu-O melt to form a glass on fast cooling. A discontinuous YBa2Cu3O(7-delta) HTS phase crystallized out on heat treatment of this glass. Attempts to prepare Tl-Ba-Ca-Cu-O system in the glassy state were not successful.

The electronic and optical properties of germanium tellurite glasses containing various transition metal oxides

International Nuclear Information System (INIS)

Khan, M.N.

1988-01-01

Various transition metal oxides, such as TiO 2 , V 2 O 5 , NiO, CuO, and ZnO are added to germanium-tellurite glass and measurements are reported of the electrical conductivity, density, optical absorption, infra-red absorption spectra, and electron spin resonance. It is found that the d.c. conductivity of glasses containing the same amount of V 2 O 5 is higher than that of germanium tellurite glasses containing a similar amount of other transition metal oxides, and is due to hopping between localized states. The optical absorption measurements show that the fundamental absorption edge is a function of glass composition and the optical absorption is due to forbidden indirect transitions. From the infra-red absorption spectra, it is found that the addition of transition metal oxides does not introduce any new absorption band in the infra-red spectrum of germanium tellurite glasses. A small shift of existing absorptions toward higher wave number is observed. The ESR measurements revealed that some transition metal ions are diamagnetic while others are paramagnetic in the glass network. (author)

A FeNiMnC alloy with strain glass transition

Directory of Open Access Journals (Sweden)

Hui Ma

2018-02-01

Full Text Available Recent experimental and theoretical investigations suggested that doping sufficient point defects into a normal ferroelastic/martensitic alloy systems could lead to a frozen disordered state of local lattice strains (nanomartensite domains, thereby suppressing the long-range strain-ordering martensitic transition. In this study, we attempt to explore the possibility of developing novel ferrous Elinvar alloys by replacing nickel with carbon and manganese as dopant species. A nominal Fe89Ni5Mn4.6C1.4 alloy was prepared by argon arc melting, and XRD, DSC, DMA and TEM techniques were employed to characterize the strain glass transition signatures, such as invariance in average structure, frequency dispersion in dynamic mechanical properties (storage modulus and internal friction and the formation of nanosized strain domains. It is indicated that doping of Ni, Mn and C suppresses γ→α long-range strain-ordering martensitic transformation in Fe89Ni5Mn4.6C1.4 alloy, generating randomly distributed nanosized domains by strain glass transition. Keywords: Strain glass transition, Elinvar alloys, Point defects, Nanosized domains

Numerical detection of the Gardner transition in a mean-field glass former.

Science.gov (United States)

Charbonneau, Patrick; Jin, Yuliang; Parisi, Giorgio; Rainone, Corrado; Seoane, Beatriz; Zamponi, Francesco

2015-07-01

Recent theoretical advances predict the existence, deep into the glass phase, of a novel phase transition, the so-called Gardner transition. This transition is associated with the emergence of a complex free energy landscape composed of many marginally stable sub-basins within a glass metabasin. In this study, we explore several methods to detect numerically the Gardner transition in a simple structural glass former, the infinite-range Mari-Kurchan model. The transition point is robustly located from three independent approaches: (i) the divergence of the characteristic relaxation time, (ii) the divergence of the caging susceptibility, and (iii) the abnormal tail in the probability distribution function of cage order parameters. We show that the numerical results are fully consistent with the theoretical expectation. The methods we propose may also be generalized to more realistic numerical models as well as to experimental systems.

Glass transition of poly (methyl methacrylate) filled with nanosilica and core-shell structured silica

DEFF Research Database (Denmark)

Song, Yihu; Bu, Jing; Zuo, Min

2017-01-01

transition and segmental dynamics of PMMA in the nanocomposites prepared via solution casting was compared. The remarkable depression (≥10 °C) of glass transition temperature (Tg) induced by the incorporation of SiO2 and CS was both observed at low loadings. Here, different mechanisms were responsible...... for the effect of SiO2 and CS on the segmental acceleration of PMMA matrix. The formation of rigid amorphous fraction (RAF) layer around SiO2 with the thickness of 16.4 nm led to the adjacent molecular packing frustration, while the “lubrication” effect of nonwetting interface between the grafted crosslinked......Core-shell (CS) nanocomposite particles with 53.4 wt% cross-linked poly (methyl methacrylate) (PMMA) shell of 11.6 nm in thickness were fabricated via miniemulsion polymerization of methyl methacrylate in the presence of modified nanosilica. The influence of nanosilica and CS nanoparticles on glass...

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

National Research Council Canada - National Science Library

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

2006-01-01

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

A phenomenological molecular model for yielding and brittle-ductile transition of polymer glasses

Science.gov (United States)

Wang, Shi-Qing; Cheng, Shiwang; Lin, Panpan; Li, Xiaoxiao

2014-09-01

This work formulates, at a molecular level, a phenomenological theoretical description of the brittle-ductile transition (BDT) in tensile extension, exhibited by all polymeric glasses of high molecular weight (MW). The starting point is our perception of a polymer glass (under large deformation) as a structural hybrid, consisting of a primary structure due to the van der Waals bonding and a chain network whose junctions are made of pairs of hairpins and function like chemical crosslinks due to the intermolecular uncrossability. During extension, load-bearing strands (LBSs) emerge between the junctions in the affinely strained chain network. Above the BDT, i.e., at "warmer" temperatures where the glass is less vitreous, the influence of the chain network reaches out everywhere by activating all segments populated transversely between LBSs, starting from those adjacent to LBSs. It is the chain network that drives the primary structure to undergo yielding and plastic flow. Below the BDT, the glassy state is too vitreous to yield before the chain network suffers a structural breakdown. Thus, brittle failure becomes inevitable. For any given polymer glass of high MW, there is one temperature TBD or a very narrow range of temperature where the yielding of the glass barely takes place as the chain network also reaches the point of a structural failure. This is the point of the BDT. A theoretical analysis of the available experimental data reveals that (a) chain pullout occurs at the BDT when the chain tension builds up to reach a critical value fcp during tensile extension; (b) the limiting value of fcp, extrapolated to far below the glass transition temperature Tg, is of a universal magnitude around 0.2-0.3 nN, for all eight polymers examined in this work; (c) pressurization, which is known [K. Matsushige, S. V. Radcliffe, and E. Baer, J. Appl. Polym. Sci. 20, 1853 (1976)] to make brittle polystyrene (PS) and poly(methyl methacrylate) (PMMA) ductile at room temperature

A phenomenological molecular model for yielding and brittle-ductile transition of polymer glasses.

Science.gov (United States)

Wang, Shi-Qing; Cheng, Shiwang; Lin, Panpan; Li, Xiaoxiao

2014-09-07

This work formulates, at a molecular level, a phenomenological theoretical description of the brittle-ductile transition (BDT) in tensile extension, exhibited by all polymeric glasses of high molecular weight (MW). The starting point is our perception of a polymer glass (under large deformation) as a structural hybrid, consisting of a primary structure due to the van der Waals bonding and a chain network whose junctions are made of pairs of hairpins and function like chemical crosslinks due to the intermolecular uncrossability. During extension, load-bearing strands (LBSs) emerge between the junctions in the affinely strained chain network. Above the BDT, i.e., at "warmer" temperatures where the glass is less vitreous, the influence of the chain network reaches out everywhere by activating all segments populated transversely between LBSs, starting from those adjacent to LBSs. It is the chain network that drives the primary structure to undergo yielding and plastic flow. Below the BDT, the glassy state is too vitreous to yield before the chain network suffers a structural breakdown. Thus, brittle failure becomes inevitable. For any given polymer glass of high MW, there is one temperature TBD or a very narrow range of temperature where the yielding of the glass barely takes place as the chain network also reaches the point of a structural failure. This is the point of the BDT. A theoretical analysis of the available experimental data reveals that (a) chain pullout occurs at the BDT when the chain tension builds up to reach a critical value f(cp) during tensile extension; (b) the limiting value of f(cp), extrapolated to far below the glass transition temperature T(g), is of a universal magnitude around 0.2-0.3 nN, for all eight polymers examined in this work; (c) pressurization, which is known [K. Matsushige, S. V. Radcliffe, and E. Baer, J. Appl. Polym. Sci. 20, 1853 (1976)] to make brittle polystyrene (PS) and poly(methyl methacrylate) (PMMA) ductile at room

Aluminosilicate melts and glasses at 1 to 3 GPa: Temperature and pressure effects on recovered structural and density changes

Science.gov (United States)

Bista, S; Stebbins, Jonathan; Hankins, William B.; Sisson, Thomas W.

2015-01-01

In the pressure range in the Earth’s mantle where many basaltic magmas are generated (1 to 3 GPa) (Stolper et al. 1981), increases in the coordination numbers of the network-forming cations in aluminosilicate melts have generally been considered to be minor, although effects on silicon and particularly on aluminum coordination in non-bridging oxygen-rich glasses from the higher, 5 to 12 GPa range, are now well known. Most high-precision measurements of network cation coordination in such samples have been made by spectroscopy (notably 27Al and 29Si NMR) on glasses quenched from high-temperature, high-pressure melts synthesized in solid-media apparatuses and decompressed to room temperature and 1 bar pressure. There are several effects that could lead to the underestimation of the extent of actual structural (and density) changes in high-pressure/temperature melts from such data. For non-bridging oxygen-rich sodium and calcium aluminosilicate compositions in the 1 to 3 GPa range, we show here that glasses annealed near to their glass transition temperatures systematically record higher recovered increases in aluminum coordination and in density than samples quenched from high-temperature melts. In the piston-cylinder apparatus used, rates of cooling through the glass transition are measured as very similar for both higher and lower initial temperatures, indicating that fictive temperature effects are not the likely explanation of these differences. Instead, transient decreases in melt pressure during thermal quenching, which may be especially large for high initial run temperatures, of as much as 0.5 to 1 GPa, may be responsible. As a result, the equilibrium proportion of high-coordinated Al in this pressure range may be 50 to 90% greater than previously estimated, reaching mean coordination numbers (e.g., 4.5) that are probably high enough to significantly affect melt properties. New data on jadeite (NaAlSi2O6) glass confirm that aluminum coordination increase

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

Science.gov (United States)

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

2014-01-01

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

Temperature-dependent luminescence and temperature-stimulated NIR-to-VIS up-conversion in Nd3+-doped La2O3-Na2O-ZnO-TeO2 glasses

Science.gov (United States)

Sobczyk, Marcin

2013-04-01

Telluride glasses of the composition xNd2O3-(7-x)La2O3-3Na2O-25ZnO-65TeO2, where (0≤x≤7) were prepared by the melt quench technique. Some physical and optical properties of the glasses were evaluated. The thermal behavior i.e. glass transition and crystallization temperatures were studied by using TGA-DTA technique. Optical properties of Nd3+-doped telluride glasses were investigated between 298 and 700 K. Basing on the obtained values of J-O parameter values (×10-20 cm2: Ω2=4.49±0.84, Ω4=5.03±0.61, Ω6=4.31±0.73), the radiative transition probabilities (AT), radiative lifetimes (τR), fluorescence branching ratios (β) and emission cross-sections (σem) were calculated for the 4F3/2→4IJ/2 (where J=9, 11 and 13) transitions of Nd3+ ions. The τR value of the 4F3/2 level amount to 164 μs and is slightly higher than the measured decay time of 162 μs. With the increasing of Nd2O3 concentration from 0.5 to 7.0 mol% the experimental lifetime of the fluorescent level decreases from 162 to 5.6 μs. The estimated quantum efficiency amount to 100%, based on a comparison of τR and the experimental decay time of a slightly doped Nd3+ telluride glass. An analysis of the non-radiative decay was based on the cross-relaxation mechanisms. The 4F3/2→4I9/2 and 4F5/2→4I9/2 transitions were analyzed with respect to the fluorescence intensity ratio (FIR) and were found to be temperature dependent. Infrared-to-visible up-conversion emissions with a maximum at 603.0 and 635.3 nm were observed at high temperatures using the 804 nm excitation and are due to the 4G5/2→4I9/2 and 4G5/2→4I11/2 transitions of Nd3+ ions, respectively. The near quadratic dependence of fluorescence on excitation laser power confirms that two photons contribute to up-conversion of the orange emissions. The temperature-stimulated up-conversion excitation processes have been analyzed in detail. The optical results indicate that the investigated glasses are potentially applicable as a 1063 nm

Copper oxide content dependence of crystallization behavior, glass forming ability, glass stability and fragility of lithium borate glasses

International Nuclear Information System (INIS)

Soliman, A.A.; Kashif, I.

2010-01-01

Differential thermal analysis (DTA) and X-ray diffraction (XRD) have been employed to investigate the copper oxide content dependence of the glass transition temperatures data, activation energy for the glass transition E t , glass stability GS, fragility index Fi, the glass-forming ability (GFA) and crystallization behavior of {(100-x) mol% Li 2 B 4 O 7 -x mol% CuO} glass samples, where x=0-40 mol% CuO. From the dependence of the glass transition temperature T g on the heating rate β, the fragility, F i , and the activation energy, E t , have been calculated. It is seen that F i and E t are attained their minimum values at 0 x -T g , SCL region and the GS. The GFA has been investigated on the basis of Hruby parameter K H , which is a strong indicator of GFA, and the relaxation time. Results of GFA are in good agreement with the fragility index, F i , calculations indicating that {90Li 2 B 4 O 7 .10CuO} is the best glass former. The stronger glass forming ability has decreasing the fragility index. XRD result indicates that no fully amorphous samples but a mixture of crystalline and amorphous phases are formed in the samples containing x>25 mol% CuO and below it composed of glassy phase. Increasing the CuO content above 25 mol% helps the crystallization process, and thus promotes a distinct SCL region. XRD suggests the presence of micro-crystallites of remaining residual amorphous matrix by increasing the CuO content.

Structural relaxation in annealed hyperquenched basaltic glasses

DEFF Research Database (Denmark)

Guo, Xiaoju; Mauro, John C.; Potuzak, M.

2012-01-01

The enthalpy relaxation behavior of hyperquenched (HQ) and annealed hyperquenched (AHQ) basaltic glass is investigated through calorimetric measurements. The results reveal a common onset temperature of the glass transition for all the HQ and AHQ glasses under study, indicating that the primary...... relaxation is activated at the same temperature regardless of the initial departure from equilibrium. The analysis of secondary relaxation at different annealing temperatures provides insights into the enthalpy recovery of HQ glasses....

Glass temperatures in free-standing canisters

International Nuclear Information System (INIS)

Hardy, B.J.; Hensel, S.J.

1993-01-01

The waste-forms produced by the Defense Waste Processing Facility (DWPF) are subject to the requirements of the Waste Acceptance Product Specifications (WAPS). The WAPS sets the maximum post cooldown temperature of the waste-form glass at 400 degrees C. This criterion must be satisfied for the ambient conditions and heat generation rates expected for the waste-forms. As part of the work described in task plan, WSRC-RP-93-1177, Rev. 0, a computer model was used to calculate the maximum glass temperatures in free standing wasteforms for a variety of ambient temperatures and heat generation rates

Brittle to ductile transition in densified silica glass.

Science.gov (United States)

Yuan, Fenglin; Huang, Liping

2014-05-22

Current understanding of the brittleness of glass is limited by our poor understanding and control over the microscopic structure. In this study, we used a pressure quenching route to tune the structure of silica glass in a controllable manner, and observed a systematic increase in ductility in samples quenched under increasingly higher pressure. The brittle to ductile transition in densified silica glass can be attributed to the critical role of 5-fold Si coordination defects (bonded to 5 O neighbors) in facilitating shear deformation and in dissipating energy by converting back to the 4-fold coordination state during deformation. As an archetypal glass former and one of the most abundant minerals in the Earth's crest, a fundamental understanding of the microscopic structure underpinning the ductility of silica glass will not only pave the way toward rational design of strong glasses, but also advance our knowledge of the geological processes in the Earth's interior.

Crystallization study of Te–Bi–Se glasses

Indian Academy of Sciences (India)

Unknown

Thermal stability; chalcogenide glasses; glass forming ability; glass transition temperature. 1. Introduction ... as well as their wide technological applications including threshold and ... are other important aspects such as ON-state current,.

Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition

Directory of Open Access Journals (Sweden)

W.-S. W. DeRieux

2018-05-01

Full Text Available Secondary organic aerosol (SOA accounts for a large fraction of submicron particles in the atmosphere. SOA can occur in amorphous solid or semi-solid phase states depending on chemical composition, relative humidity (RH, and temperature. The phase transition between amorphous solid and semi-solid states occurs at the glass transition temperature (Tg. We have recently developed a method to estimate Tg of pure compounds containing carbon, hydrogen, and oxygen atoms (CHO compounds with molar mass less than 450 g mol−1 based on their molar mass and atomic O : C ratio. In this study, we refine and extend this method for CH and CHO compounds with molar mass up to ∼ 1100 g mol−1 using the number of carbon, hydrogen, and oxygen atoms. We predict viscosity from the Tg-scaled Arrhenius plot of fragility (viscosity vs. Tg∕T as a function of the fragility parameter D. We compiled D values of organic compounds from the literature and found that D approaches a lower limit of ∼ 10 (±1.7 as the molar mass increases. We estimated the viscosity of α-pinene and isoprene SOA as a function of RH by accounting for the hygroscopic growth of SOA and applying the Gordon–Taylor mixing rule, reproducing previously published experimental measurements very well. Sensitivity studies were conducted to evaluate impacts of Tg, D, the hygroscopicity parameter (κ, and the Gordon–Taylor constant on viscosity predictions. The viscosity of toluene SOA was predicted using the elemental composition obtained by high-resolution mass spectrometry (HRMS, resulting in a good agreement with the measured viscosity. We also estimated the viscosity of biomass burning particles using the chemical composition measured by HRMS with two different ionization techniques: electrospray ionization (ESI and atmospheric pressure photoionization (APPI. Due to differences in detected organic compounds and signal intensity, predicted viscosities at low RH based on ESI and

Temperature-induced structural changes in fluorozirconate glasses and liquids

International Nuclear Information System (INIS)

Sen, S.; Youngman, R.E.

2002-01-01

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

Introduction to the crystallization phenomenon in nuclear glass

International Nuclear Information System (INIS)

Jacquet Francillon, N.

1997-01-01

Crystallization is a subject for concern because of its potentially detrimental effects on the technological feasibility of high-temperature melting, and on the chemical durability of the material at intermediate and low temperatures during interim storage or after disposal. The tendency of glass to crystallize depends to a large extent on the composition of the frit and/or of the waste to be solidified. It depends too of the thermal history of the glass generally, the knowledge is mainly upon determination of the time-temperature-transition (TTT) curves, crystal identification and quantification techniques, and their effects on the durability of the glass matrix. French experience is presented. Only a few authors addressed the long-term development of crystalline phases, notably at temperatures below the vitreous transition temperature Tg. Some recommendations for glass crystallization studies are made but glass crystallization after disposal is acceptable provided some conditions are met. (author)

Dimensional study of the caging order parameter at the glass transition.

Science.gov (United States)

Charbonneau, Patrick; Ikeda, Atsushi; Parisi, Giorgio; Zamponi, Francesco

2012-08-28

The glass problem is notoriously hard and controversial. Even at the mean-field level, little is agreed upon regarding why a fluid becomes sluggish while exhibiting but unremarkable structural changes. It is clear, however, that the process involves self-caging, which provides an order parameter for the transition. It is also broadly assumed that this cage should have a gaussian shape in the mean-field limit. Here we show that this ansatz does not hold. By performing simulations as a function of spatial dimension d, we find the cage to keep a nontrivial form. Quantitative mean-field descriptions of the glass transition, such as mode-coupling theory, density functional theory, and replica theory, all miss this crucial element. Although the mean-field random first-order transition scenario of the glass transition is qualitatively supported here and non-mean-field corrections are found to remain small on decreasing d, reconsideration of its implementation is needed for it to result in a coherent description of experimental observations.

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.

Superconducting Metallic Glass Transition-Edge-Sensors

Science.gov (United States)

Hays, Charles C. (Inventor)

2013-01-01

A superconducting metallic glass transition-edge sensor (MGTES) and a method for fabricating the MGTES are provided. A single-layer superconducting amorphous metal alloy is deposited on a substrate. The single-layer superconducting amorphous metal alloy is an absorber for the MGTES and is electrically connected to a circuit configured for readout and biasing to sense electromagnetic radiation.

Modification of the glass surface induced by redox reactions and internal diffusion processes

DEFF Research Database (Denmark)

Smedskjær, Morten Mattrup; Deubener, Joachim; Yue, Yuanzheng

In this paper we report a novel way to modify the glass surface in favor of some physical performances. The main step is to perform iso-thermal treatments on the selected silicate glasses containing transition metal at temperatures near the glass transition temperature for various durations under...

Electrical Conductivity, Relaxation and the Glass Transition: A New Look at a Familiar Phenomenon

Science.gov (United States)

Angel, Paul W.; Cooper, Alfred R.; DeGuire, Mark R.

1996-01-01

Annealed samples from a single melt of a 10 mol% K2O-90SiO2 glass were reheated to temperatures ranging from 450 to 800 C, held isothermally for 20 min, and then quenched in either air or a silicon oil bath. The complex impedance of both the annealed and quenched samples was measured as a function of temperature from 120 to 250 C using ac impedance spectroscopy from 1 Hz to 1 MHz. The dc conductivity, sigma(sub dc), was measured from the low frequency intercept of depressed semicircle fits to the complex impedance data. When the sigma(sub dc) at 150 C was plotted against soak temperature, the results fell into three separate regions that are explained in terms of the glass structural relaxation time, tau(sub S). This sigma(sub dc) plot provides a new way to look the glass transition range, Delta T(sub r). In addition, sigma(sub dc) was measured for different soak times at 550 C, from which an average relaxation time of 7.3 min was calculated. It was found that the size and position of the Delta T(sub r) is controlled by both the soak time and cooling rate.

The electronic conduction of glass and glass ceramics containing various transition metal oxides

International Nuclear Information System (INIS)

Yoshida, T.; Matsuno, Y.

1980-01-01

Nb 2 O 5 -V 2 O 5 -P 2 O 5 glasses containing only Group Va oxides have been investigated to elucidate their electronic conduction and structure, as compared with other glasses obtained by the addition of various transition metal oxides to vanadium phosphate. The P 2 O 5 introduction for Nb 2 O 5 in this glass with the same amount of V 2 O 5 increased the conductivity about two times. Glass ceramics having high conductivity increased by two orders of magnitude and the activation energy for conduction decreased from about 0.5 to 0.2 eV. The crystals were confirmed to be (V,Nb) 2 O 5 and Nb phosphate, one of which was highly conductive and developed a pillar-like shape with a length of more than 20 μm. (orig.)

Phase-glass scaling near the coherence transition in granular HoBa{sub 2}Cu{sub 3}O{sub 7-{delta}} superconducting thin films

Energy Technology Data Exchange (ETDEWEB)

Roa-Rojas, J.; Landinez Tellez, D.A. [Grupo de Fisica de Nuevos Materiales, Departamento de Fisica, Universidad Nacional de Colombia, A. A. 14490, Bogota DC (Colombia); Prieto, P. [Grupo de Peliculas Delgadas, Departamento de Fisica, Universidad del Valle, A. A. 25360, Cali (Colombia)

2005-07-01

Systematic measurements of electrical magnetoconductivity near the coherence transition of granular HoBa{sub 2}Cu{sub 3}O{sub 7-{delta}} thin films are reported. Experiments performed in magnetic fields ranging from 0 to 2500 Oe reveal that close to the coherence transition temperature T{sub c0}(H), the correlation length scales as a power law of temperature with a thermal-dependent critical exponent, {nu}. In low external fields the corresponding value of {nu} is consistent with the two-dimensional phase-glass model, which is in the same dynamical universality class of the so-called vortex-glass model. At applied fields H > 1000 Oe, the vortex dynamics becomes stronger and the coherence transition is not observed. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Effect of temperature on surface error and laser damage threshold for self-healing BK7 glass.

Science.gov (United States)

Wang, Chu; Wang, Hongxiang; Shen, Lu; Hou, Jing; Xu, Qiao; Wang, Jian; Chen, Xianhua; Liu, Zhichao

2018-03-20

Cracks caused during the lapping and polishing process can decrease the laser-induced damage threshold (LIDT) of the BK7 glass optical elements, which would shorten the lifetime and limit the output power of the high-energy laser system. When BK7 glass is heated under appropriate conditions, the surface cracks can exhibit a self-healing phenomenon. In this paper, based on thermodynamics and viscous fluid mechanics theory, the mechanisms of crack self-healing are explained. The heat-healing experiment was carried out, and the effect of water was analyzed. The multi-spatial-frequency analysis was used to investigate the effect of temperature on surface error for self-healing BK7 glass, and the lapped BK7 glass specimens before and after heat healing were detected by an interferometer and atomic force microscopy. The low-spatial-frequency error was analyzed by peak to valley and root mean square, the mid-spatial-frequency error was analyzed by power spectral density, and the high-spatial-frequency error was analyzed by surface roughness. The results showed that the optimal heating temperature for BK7 was 450°C, and when the heating temperature was higher than the glass transition temperature (555°C), the surface quality decreased a lot. The laser damage test was performed, and the specimen heated at 450°C showed an improvement in LIDT.