Molecular dynamics simulation of relationship between local structure and dynamics during glass transition of Mg_7Zn_3 alloy

The rapid solidification process of Mg7Zn3 alloy was simulated by the molecular dynamics method. The relationship between the local structure and the dynamics during the liquid-glass transition was deeply investigated. It was found that the Mg-centered FK polyhedron and the Zn-centered icosahedron play a critical role in the formation of Mg7Zn3 metallic glass. The self-diffusion coefficients of Mg and Zn atoms deviate from the Arrhenius law near the melting temperature and then satisfy the power law. According to the time correlation functions of mean-square displacement, incoherent intermediate scattering function and non-Gaussian parameter, it was found that the β-relaxation in Mg7Zn3 supercooled liquid becomes more and more evident with decreasing temperature, and the α-relaxation time rapidly increases in the VFT law. Moreover, the smaller Zn atom has a faster relaxation behavior than the Mg atom. Some local atomic structures with short-range order have lower mobility, and they play a critical role in the appearance of cage effect in theβ-relaxation regime. The dynamics deviates from the Arrhenius law just at the temperature as the number of local atomic structures begins to rapidly increase. The dynamic glass transition temperature （Tc） is close to the glass transition point in structure （TgStr）.

Effects of C60 on the Glass Transition Temperature of Carbazole-based Photorefractive Polyphosphazenes

The bi-functional carbazole-based photorefractive polyphosphazenes with different content of C_（60）-doped were fabricated. The glass transition temperature（T_g） of these polymer composite materials was determined using a differential scanning calorimetric（DSC） method. According to the DSC measurement results with different heating rates, the variation of T_g and the active energy of glass transition（E_g） were analyzed in detail. The analysis results indicate that the transition region shifts to higher temperatures with increasing heating rate, and C_（60） content（below 1.0 wt%） can influence the T_g of photorefractive polyphosphazenes. The T_g first increases and then decreases with the C_（60） content（below 1.0 wt%）. The probable causes of the influence of C_（60） on T_g was proposed.

QSPR Study on the Glass Transition Temperature of Polyacrylates

Structural parameters of 22 polyacrylic compounds were computed at two levels using Hartree-Fock and DFT methods. Based on the experimental data of glass transition temperature （Tg）, four-parameter （energy of the lowest unoccupied molecular orbital （ELoMO）, the highest positive charge （Qmax^＋）, dipole moments（μ） and the next highest occupied molecular orbital （ENLOMO）） dependent equations were developed using structural parameters as theoretical descriptors. Especially, Tg dependent equation calculated at the HF/6-31G（d） level is more advantageous than others in view of their correlation and predictive abilities. This dependent equation was validated by variance inflation factors （VIF） and t-test methods.

Kinetics of Glass Transition and Crystallization in Carbon Nanotube Reinforced Mg-Cu-Gd Bulk Metallic Glass

Mg65Cu25Gd10 bulk metallic glass and its carbon nanotube reinforced composite were prepared. Differential scanning calorimeter （DSC） was used to investigate the kinetics of glass transition and crystallization processes. The influence of CNTs addition to the glass matrix on the glass transition and crystallization kinetics was studied. It is shown that the kinetic effect on glass transition and crystallization are preserved for both the monothetic glass and its glass composite. Adding CNTs in to the glass matrix reduces the influence of the heating rate on the crystallization process. In addition, the CNTs increase the energetic barrier for the glass transition. This results in the decrease of GFA. The mechanism of the GFA decrease was also discussed.

Solving the initial condition of the string relaxation equation of the string model for glass transition:part-Ⅱ

The string model for the glass transition can quantitatively describe the universal a-relaxation in glassformers. The string relaxation equation （SRE） of the model simplifies the well-known Debye and Rouse-Zimm relaxation equations at high and low enough temperatures, respectively. However, its initial condition, necessary to the further model predictions of glassy dynamics, has not been solved. In this paper, the general initial condition of the SRE for stochastically spatially configurative strings is solved exactly based on the obtained special initial condition of the SRE for straight strings in a previous paper （J. L. Zhang et al. 2010 Chin. Phys. B 19, 056403）.

Solving the initial condition of the string relaxation equation of the string model for glass transition:part-I

The string model for the glass transition can quantitatively describe the universal a-relaxation in glassformers, including the average relaxation time, the distribution function of the relaxation time, and the relaxation strength as functions of temperature. The string relaxation equation （SRE） of the model, at high enough temperatures, simplifies to the well-known single particle mean-field Debye relaxation equation, and at low enough temperatures to the well-known Rouse-Zimm relaxation equation that describes the relaxation dynamics of linear macromolecules. However, its initial condition, necessary to the further model predictions of glassy dynamics, has not been solved. In this paper, the special initial condition （SIC） of the SRE, i.e. for straight strings and the dielectric spectrum technique that is one of the most common methods to measure the glassy dynamics, was solved exactly. It should be expected that the obtained SIC would benefit the solution of the general initial condition of the SRE of the string model, i.e. for stochastically spatially eonfigurating strings, as will be described in separate publications.

Dynamic mechanical behavior of a Zr-based bulk metallic glass during glass transition and crystallization

The dynamic mechanical behaviors of the Zr41Ti14Cu12.5Ni8Be22.5Fe2 bulk metallic glass （BMG） during continuous heating at a constant rate were investigated. The glass transition and crystallization of the Zr-based BMG were thus characterized by the measurements of storage modulus E′ and internal friction Q^-1. It was found that the variations of these dynamic mechanical quantities with temperature were interre-lated and were well in agreement with the DSC trace obtained at the same heating rate. The origin of the first peak in the internal friction curve was closely related to the dynamic glass transition and subsequent primary crystallization. Moreover, it can be well described by a physical model, which can characterize atomic mobility and mechanical response of disordered condense materials. In comparison with the DSC trace, the relative position of the first internal friction peak of the BMG was found to be dependent on its thermal stability against crys-tallization.

Calorimetric Studies on Enthalpy Relaxation in Maltitol Glass Transition Based on Phenomenological Models

To investigate the enthalpy relaxation behavior of maltitol glass system,differential scanning calorimetry（DSC） was used to obtain the specific heat capacity[C p（T）] near the glass transition temperature（T g） at different cooling rates ranged between 1 and 20 K/min.Three phenomenological models of enthalpy relaxation,ToolNarayanaswamy-Moynihan（TNM） model,Adam-Gibbs-Vogel（AGV） model and Gómez Ribelles（GR） model,were used to simulate the experimental data.The models＇ parameters were obtained via a curve-fitting method.The results indicate that TNM and AGV models gave the almost identical prediction powers and can reproduce the curves of experimental C p（T） very well.However,the prediction power of GR model evolved from configurational entropy approach is not so good as those of TNM and AGV models.In particular,the metastable limit state parameter（δ） introduced by Gómez Ribelles has insignificant effect on the enthalpy relaxation of the small molecular hydrogen-bonding glass system.

Glass transition kinetics of La_(55)Al_(25)Ni_(10)Cu_(10) bulk metallic glass by electrical resistivity measurement

The glass transition behavior of La55A125-Ni10CU10 bulk metallic glass was investigated using elec-trical resistivity and differential-scanning calorimetry measurements. There are good agreements of the onset temperature （Tg-onset） and the end temperature （Tg-end） of the glass transition between the DSC curve and tempera-ture dependent electrical resistivity （TER） curve in the same heating rate. Kinetics of the glass transition is studied with the electrical resistivity data. The apparent activation energy of the glass transition （△Eg） is found to be 306.4 kJ.mol^-1. Fragility parameter D^＊ and VFT temper-ature To are 9.8 and 324.9 K, respectively.

FOURIER TRANSFORM INFRARED STUDIES OF POLY (ETHYLENE TEREPHTHALATE) FILM IN THE GLASS TRANSITION REGION

Three specimens from a solution-cast poly (ethylene terephthalate) (PET) film, one being liquid-N_2 quenched from 92℃(Q), one being slowly cooled from 92℃(SC) and one being quenched and sub-T_g annealed at 67℃(AN), have been studied by specimen difference spectra Q-SC and AN-Q and temperature difference spectra T-70 and T_2-T_1 for every 2℃ steps on heating to 90℃ at 2℃ /min. SC and AN showed more gauche conformers than Q. That means that the PET chain has more trans conformers at higher temperatures and some of these are frozen during quenching through T_g. A band at 1340 cm^(-1) has been found to be complex containing overlapping bands reflecting trans in crystalline regions and trans in amorphous regions. The temperature difference spectra on heating through T_g showed that the spectral changes in Q are gradual while a rather abrupt change occurs in AN at 80—82℃ for the bands at 1340, 1042 and 1020 cm^(-1). No new conformational structure or new vibrational mode is involved. A kind of locking mechanism is suggested which hinders the molecular vibrational changes in AN below T_g until a sudden release occurs at T_g. These locking sites can be nothing else than sites of tighter local packing of chain segments. Consequently it is believed that inter-chain van der Waals attraction energy plays a dominating role in the volume relaxation and sub-T_g annealing of quenched amorphous polymers.

Effect of melt cooling rate on glass transition kinetics and structural relaxation of Vit1 metallic glass

The thin ribbons and the bulk cylindrical rods with diameters of 2 mm and 10 mm of the Vit1 metallic glass(MG)were prepared by the single roller melt spinning method and the copper mold injection casting method,respectively.The cooling rates of the samples during melt solidification were evaluated.The glass transition behaviors of three groups of MG samples with different solidification cooling rates were studied by differential scanning calorimetry(DSC)at different heating rates.The effects of melt cooling rate on the glass transition kinetic parameters such as apparent activation energy(E)and fragility parameter(m)of the Vit1 MG were studied using the Kissinger and the Vogel-Fulcher-Tammann(VFT)equations.Additionally,the structural relaxation enthalpy(ΔHrel)of three groups of MG samples was quantitatively analyzed by DSC through multi-step temperature rise and fall measurements.Results show that the melt cooling rate(R)has a significant effect on the glass transition kinetics and the structural relaxation of the Vit1 MG.As R decreases in the order of magnitude,the glass transition temperature(Tg),E,m,andΔHrel of the Vit1 MG gradually decreases.Furthermore,in the range of the experimental cooling rates,E,m,andΔHrel all have an approximately linear relationship with lgR.

Mode-Coupling Theory for Glass Transition of Active-Passive Binary Mixture

Collective behaviours of active particle systems have gained great research attentions in re- cent years. Here we present a mode-coupling theory （MCT） framework to study the glass transition of a mixture system of active and passive Brownian particles. The starting point is an eff）ctive Smoluchowski equation, which governs the dynamics of the probability dis- tribution function in the position phase space. With the assumption of the existence of a nonequilibrium steady state, we are able to obtain dynamic equations for the intermediate scattering functions （ISFs）, wherein an irreducible memory function is introduced which in turn can be written as functions of the ISFs based on standard mode-coupling approximations. The effect of particle activity is included through an effective difIusion coefficient which can be obtained via short time simulations. By calculating the long-time limit of the ISF, the Debye-Waller （DW） factor, one can determine the critical packing fraction ηc of glass transition. We find that for active-passive （AP） mixtures with the same particle sizes, ηc increases as the partial fraction of active particle xA increases, which is in agreement with previous simulation works. For system with different active/passive particle sizes, we find an interesting reentrance behaviour of glass transition, i.e., ηc shows a non-monotonic dependence on xa. In addition, such a reentrance behaviour would disappear if the particle activity is large enough. Our results thus provide a useful theoretical scheme to study glass transition behaviour of active-passive mixture systems in a promising way.

Electrical Resistance Measurement of Glass Transition and Crystallization Characteristics of Zr-Al-Cu-Ni Metallic Glasses

In this paper, glass transition and thermal stability of the Zr-AI-Cu-Ni metallic glasses were investigated by using electrical resistance measurement (ERM), DSC and X-ray diffraction techniques. The experimental results show that the ERM is capable of detecting the glass transition of the amorphous alloys and can help to distinguish the crystallization products of the Zr-AI-Cu-Ni metallic glasses owing to the difference of the electrical resistivity between the precipitation phases.

GLASS TRANSITION IN AMORPHOUS Se

The glass transition in amorphous semi-conducting Se has been studied by DSC thermal ana- lysis,infrared absorption spectra and positron annihilation measurements.The results show that the glas transition seems to be reasonably explained from the viewpoints of MDS model and valence alternation pair theory proposed by Mott,Kaster et al.,respectively.

Anion type-dependent confinement effect on glass transitions of solutions of LiTFSI and LiFSI

We present findings on the effect of nanometer-sized silica-based pores on the glass transition of aqueous solutions of lithium bis(trifluoromethane)sulfonimide(LiTFSI)and lithium difluorosulfimide(LiFSI),respectively.Our experimental results demonstrate a clear dependence of the confinement effect on the anion type,particularly for water-rich solutions,in which the precipitation of crystalized ice under cooling process induces the formation of freeze-concentrated phase confined between pore wall and core ice.As this liquid layer becomes thinner,the freeze-concentrated phase experiences glass transition at increasingly higher temperatures in solutions of LiTFSI.However,differently,for solutions of LiFSI and LiCl,this secondary confinement has a negligible effect on the glass transition of solutions confined wherein.These different behaviors emphasize the obvious difference in the dynamic properties’response of LiTFSI and LiFSI solutions to spatial confinement and particularly to the presence of the hydrophilic pore wall.

POLYMER CHAIN DIFFUSION AT A TEMPERATURE BELOW ITS BULK GLASS TRANSITION TEMPERATURE

In this study, it was examined whether the dynamics of polymer chains at a surface is different from that in thebulk, and if so, to what extent they differ in terms of surface glass transition temperature and diffusion coefficient. Obtainedresults clearly indicate that surface chains can travel for a relatively large distance in comparison with the characteristiclength scale of usual segmental motion even at a temperature below its bulk glass transition temperature, T_g^b. This isconsistent with our previous results that the surface glass transition temperature is much lower than the corresponding T_g^b.Also, it was experimentally revealed that there was a gradient of molecular motion in the surface region.

A MONTE CARLO STUDY OF THE GLASS TRANSITION OF POLYMETHYLENE

By this Monte Carlo simulation we studied the glass transition of polymethylene using the modified bond-fluctuation model combined with considering the rotational-isomeric state model. The configurational properties in the polymethylene (PM) melts, such as the mean length, the mean energy per bond and the mean square radius of gyration were monitored. We found that the chains cannot be in the equilibrium states after a very long time when the temperature of the dense PM chains decreases to 120 K. As the melt vitrifies, these quantities gradually become independent of temperature in a narrow range. The glass transition temperature T-g depends upon the chain length of PM chains, and extrapolation to (CH2)(infinity) gives T-g(infinity) = 212 K. The dynamics in the PM melts was also studied. It was found that the diffusion coefficients can be described by the Vogel-Fulcher law and the Vogel-Fulcher temperature T-0 is 124 K. This method may be used to investigate the glass transition of other real polymer chains.

Liquid-to-glass transition of tetrahydrofuran and 2-methyltetrahydrofuran

Both tetrahydrofuran （THF） and 2-methyltetrahydrofuran （MTHF） are studied systematically at desired temperatures using molecular dynamics simulations. The results show that the calculated densities are well consistent with experiment. Their glass transition temperatures are obtained： 115 K - 130 K for THF and 131 K - 142 K for MTHF. The calculated results from the dipolar orientational time correlation functions indicate that the ＂long time＂ behavior is often associated with a glass transition. From the radial and spatial distributions, we also find that the methyl has a direct impact on the structural symmetry of molecules, which leads to the differences of physical properties between THF and MTHF.

Creep performance of PVC aged at temperature relatively close to glass transition temperature

In order to predict the mechanical performance of the polyvinyl chloride （PVC） at a high operating temperature, a series of short-term tensile creep tests （one- tenth of the physical aging time） of the PVC are carried out at 63 ℃ with a small constant stress by a dynamic mechanical analyzer （DMA）. The Struik-Kohlrausch （SK） formula and Struik shifting methods are used to describe these creep data for various physical aging time. A new phenomenological model based on the multiple relaxation mechanisms of an amorphous polymer is developed to quantitatively characterize the SK parameters （the initial creep compliance, the characteristic retardation time, and the shape factor） determined by the aging time. It is shown that the momentary creep compliance curve of the PVC at 63℃ can be very well fitted by the SK formula for each aging time. However, the SK parameters for the creep curves are not constant during the aging process at the elevated temperatures, and the evolution of these parameters and the creep rate versus aging time curves at the double logarithmic coordinafes have shown a nonlinear phenomenon. Moreover, the creep master curves obtained by the superposition with the Struik shifting methods are unsatisfactory in such a case. Finally, the predicted results calculated from the present model incorporating with the SK formula are in excellent agreement with the creep experimental data for the PVC isothermally aged at the temperature relatively close to the glass transition temperature.

Prediction of Glass Transition Temperatures of Polyarylates Using a Support Vector Machine Model

A three-descriptor quantitative structure-property relationship （QSPR） model, based on the support vector machine （SVM） algorithm, was constructed to predict the glass transition temperatures （Tgs） ofpolyarylates with complex structures. A total of 50 polyarylates were randomly divided into three sets, viz., the training set （30 polymers）, validation set （10 polymers） and prediction set （10 polymers）. By adjusting various parameters by trial and error, the final optimum SVM model based on Austin Model 1 （AM1） calculation is a polynomial kernel with the parameters C of 100, ε of 1.00E-05 and d of 2. The root-mean-square （RMS） errors obtained from the training set, validation set and prediction set are 19.4, 12.8 and 15.5 K, respectively. Research results show that the proposed SVM model has better statistical quality than the previous models. Thus, applying the SVM algorithm to predict Tgs of polymers is feasible.