Machine learning(ML)has emerged as a powerful tool for predicting polymer properties,including glass transition temperature(Tg),which is a critical factor influencing polymer applications.In this study,a dataset of po...Machine learning(ML)has emerged as a powerful tool for predicting polymer properties,including glass transition temperature(Tg),which is a critical factor influencing polymer applications.In this study,a dataset of polymer structures and their Tg values were created and represented as adjacency matrices based on molecular graph theory.Four key structural descriptors,flexibility,side chain occupancy length,polarity,and hydrogen bonding capacity,were extracted and used as inputs for ML models:Extra Trees(ET),Random Forest(RF),Gaussian Process Regression(GPR),and Gradient Boosting(GB).Among these,ET and GPR achieved the highest predictive performance,with R2 values of 0.97,and mean absolute errors(MAE)of approximately 7–7.5 K.The use of these extracted features significantly improved the prediction accuracy compared to previous studies.Feature importance analysis revealed that flexibility had the strongest influence on Tg,followed by side-chain occupancy length,hydrogen bonding,and polarity.This work demonstrates the potential of data-driven approaches in polymer science,providing a fast and reliable method for Tg prediction that does not require experimental inputs.展开更多
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...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）.展开更多
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 ...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.展开更多
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 l...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.展开更多
In this paper, we report a strain rate related glass transition in model SrCaYbMg（Li）Zn（Cu） metallic glasses at room temperature. A critical strain rate, equivalent to glass transition temperature, is found for th...In this paper, we report a strain rate related glass transition in model SrCaYbMg（Li）Zn（Cu） metallic glasses at room temperature. A critical strain rate, equivalent to glass transition temperature, is found for the strain rate induced glassy state to liquid-like viscoplastic state translation. The results show that the observation time, equivalent to temperature and stress, is a key parameter for the transition between the glass and supercooled liquid states. A three-dimension glass transition diagram involved in time, temperature and stress in metallic glasses is established.展开更多
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 proce...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.展开更多
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 rela...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）.展开更多
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 relaxa...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.展开更多
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 B...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.展开更多
In this study, the glass transition and uniaxial tensile properties of a commercially available epoxy adhesive were investigated using experimental measurements and molecular dynamics （MD） simulation. Differential s...In this study, the glass transition and uniaxial tensile properties of a commercially available epoxy adhesive were investigated using experimental measurements and molecular dynamics （MD） simulation. Differential scanning calorimetry （DSC） was used to study the change of glass transition temperature （Tg） with cross-link density （CLD）. Uniaxial tensile test was performed to measure the Young＇s modulus （E）, Poisson＇s ratio （v） and yielding strength （tyv）. In MD simulation, the complicated epoxy system was simplified as the mixture of two kinds of simple molecules, with the key information well preserved and the less important details omitted. The molecular model of the cross-linked epoxy network was constructed and its mechanical properties were calculated using MD simulation. Overall, the MD simulation results agreed with experimental ones, which proved the validity of the molecular model and justified the simplification method of the industry- level epoxy system.展开更多
Exploring the phase transition of high entropy alloys(HEAs)with multiple major elements is of great importance for understanding the underlying physical mechanisms.Macroscopic martensitic phase tran-sition has been fr...Exploring the phase transition of high entropy alloys(HEAs)with multiple major elements is of great importance for understanding the underlying physical mechanisms.Macroscopic martensitic phase tran-sition has been frequently reported in HEAs,however,nanoscale microstructural phase evolution has not been investigated to the same extent.Herein,we have prepared the Ti_(33)Nb_(15)Zr_(25)Hf_(25)O_(2)HEA and investi-gated the strain glass transition and its associated properties using dynamic mechanical analysis and mi-crostructure characterization.We have found that the elastic modulus in Ti_(33)Nb_(15)Zr_(25)Hf_(25)O_(2)HEA deviates from Wachtman’s equation and observed the Elinvar effect in the form of temperature-independent mod-ulus in the temperature range from 150 K to 450 K and frequency-dependence modulus around 220 K.The strain glass transition has been evidenced in Ti_(33)Nb_(15)Zr_(25)Hf_(25)O_(2)HEA by the formation and growth of nano-sized domains during in-situ transmission electron microscopy(TEM)cooling,and substantiated by the broken ergodicity during zero-field-cooling/field-cooling.The strain glass transition is believed to account for the Elinvar effect,where the modulus hardening of nano-sized domains compensates dynam-ically with the modulus softening of the transformable matrix.展开更多
A two-stage transition upon crossing the glass transition of polystyrene with increasing temperature was precisely determined and interpreted by using solid-state nuclear magnetic resonance （SSNMR）, 1H-XH dipolar co...A two-stage transition upon crossing the glass transition of polystyrene with increasing temperature was precisely determined and interpreted by using solid-state nuclear magnetic resonance （SSNMR）, 1H-XH dipolar couplings based double quantum-filtered （DQF） and dipolar filter （DF） experiments and 13C chemical shift anisotropy （CSA） based centerband-only detection of exchange （CODEX） experiment are used to fully characterize the time scale of molecular motions during the glass transition. While differential scanning calorimetry （DSC） and CODEX experiment predicted the first stage of glass transiton, DQF and DF experiments provided the evidence for the second stage transition during which the time scale of molecular motions changed from very slow （t 〉 ms） to very fast （t 〈 Its）. The first stage of glass transition begins with the occurrence of remarkable slow re-orientation motions of the polymer backbone segments and ends when the degree of slow motion reaches maximum. The onset and endpoint of the conventional calorimetric glass transition of polystyrene can be quantitatively determined at the molecular level by SSNMR. In the second stage, a subsequent dramatic transition associated with the melting of the glassy components was observed. In this stage liquid-like NMR signals appeared and rapidly increased in intensity after a characteristic temperature Tf （-1.1Tg）. The signals associated with the glassy components completely disappeared at another characteristic temperature Tc （-1.2Tg）.展开更多
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...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.展开更多
We defined the plastic deformability under constrained loading conditions as malleability for bulk metallic glass （BMG） materials. Quaternary Zr-Ti-Cu-Al alloys in the Zr-rich composition range are selected to inves...We defined the plastic deformability under constrained loading conditions as malleability for bulk metallic glass （BMG） materials. Quaternary Zr-Ti-Cu-Al alloys in the Zr-rich composition range are selected to investigate the compositional dependence of malleability assessed by bending testing and glass transition temperature （Tg ）. As indicated, increasing the Al or Cu concentration in the alloys leads to the rise of T g . The Zr（61）Ti2Cu（25）Al（12） （ZT1） and Zr（61.6）Ti（4.4）Cu（24）Al（10） （ZT3） alloys exhibit an optimal combination of lower T g and higher glass-forming ability. The malleable BMGs such as ZT1 manifests two characters during deformation, the stable propagation of a single shear band indicated by large shear offsets and easy proliferation of shear bands. With increasing the T g of BMG, the yield strength σy,Young＇s modulus and shear modulus simultaneously increase as well, while the Poisson s ratio decreases. The σy of ZT1 BMG is about 1680 MPa in compression and 1600 MPa in tension. In tensile loading, no any visible plasticity appears even when the strain rate increases up to the order of magnitude of 10（-1）s（-1）. In consistent with the T g , malleability of Zr-Ti-Cu-Al BMGs manifests significant compositional dependence. The malleable BMG is associated with lower Tg , as well as lower shear modulus or higher Poisson s ratio, which can be understood on the basis of the correlation of Tg with shear energy barrier in metallic glass. Thus, the calorimetric Tg can be used as an indicator to screen malleable BMG-forming composition, with advantage of experimental accessibility.展开更多
Glass transition behavior of hydrogen bonded polymer blends of poly（vinyl phenol） （PVPh） and poly（ethylene oxide） （PEO） is systematically investigated using normal differential scanning calorimetry （DSC） and...Glass transition behavior of hydrogen bonded polymer blends of poly（vinyl phenol） （PVPh） and poly（ethylene oxide） （PEO） is systematically investigated using normal differential scanning calorimetry （DSC） and recently developed multifrequency temperature-modulated DSC （TOPEM）, in combination with Fourier transform infrared spectroscopy （FTIR） and nuclear magnetic resonance （NMR） techniques, focusing on the effect of the PEO molecular weight on the spatial and dynamic heterogeneity. It is found, for the first time, that both the glass transition temperature （Tg） and activity energy （Ea） of the blends strongly depend on PEO molecular weight, and a common turning point, which separates the rapid and slow increasing regions, can be found. The interchain hydrogen bonding interactions, both determined by FTIR measurements and obtained from the Kwei equation, decrease with increasing PEO molecular weight, indicating a decrease of the componential miscibility. A series of parameters related to the microscopic spatial and dynamic heterogeneity, such as the activity energy, fragility, nonexponential factor and the size of cooperatively rearranging regions, are calculated from frequency dependency complex heat capacity measured using TOPEM. It is found that each of these parameters monotonically changes with increasing the PEO molecular weight during the glass transition process, demonstrating that hydrogen bonding interaction is the key factor in controlling the spatial and dynamic heterogeneity, thus the glass transition. NMR relaxation results reveal the existence of obvious phase separation large than 5 nm, implying that the cooperatively rearranging regions should be closely related to the interphase region between the two components. The above obtained origin and evolution of spatial and dynamic heterogeneity provide a new insight into the glass transition behavior of polymer blends.展开更多
Modulated-temperature differential scanning calorimetric and dynamic mechanical analyses and dielectric spectroscopy were used to investigate the glass transition of hydrated wheat gliadin powders with moisture absorp...Modulated-temperature differential scanning calorimetric and dynamic mechanical analyses and dielectric spectroscopy were used to investigate the glass transition of hydrated wheat gliadin powders with moisture absorption ranged from 2.30 db% to 18.21 db%. Glass transition temperature （Tg） of dry wheat gliadin was estimated according to the Gordon- Taylor equation. Structural heterogeneity at high degrees of hydration was revealed in dielectric temperature and frequency spectra. The activation energies （Ea） of the two relaxations were calculated from Arrhenius equation.展开更多
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 temperat...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.展开更多
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),...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.展开更多
We device a relaxed lattice model （RLM） to study the mechanism of glass transition, which unifies the cage- effects from particle-particle interaction and entropy. By analyzing entropy in RLM with considering the in...We device a relaxed lattice model （RLM） to study the mechanism of glass transition, which unifies the cage- effects from particle-particle interaction and entropy. By analyzing entropy in RLM with considering the influence of interactions on equilibrium, we demonstrate that glass transition is a second-order phase transition. For a perfect one- dimensional linked particle system like linear polymer under normal pressure, the free volume at glass transition is rigorously deduced out to be 2.6%, which provides a theoretical basis for the iso-free volume of 2.5% given by Willian, Landel and Ferry （WLF） equation. Extending to system with dead particles linked with higher dimensions like branched or cross-linked chains under positive or negative pressure, free volume at glass transition is varied, based on which we construct a phase diagram of glass transition in the space of free volume-dead particle-pressure. This demonstrates that free volume is not the single parameter determining glass transition, while either dead particles like cross-linked points or external force fields like pressure can vary free volume at the glass transition.展开更多
In this work, the effect of the fullerene（C_（60）） weight fraction and PB-C_（60） interaction on the glass transition temperature（T_g） of polymer chains has been systemically investigated by adopting the united ...In this work, the effect of the fullerene（C_（60）） weight fraction and PB-C_（60） interaction on the glass transition temperature（T_g） of polymer chains has been systemically investigated by adopting the united atom model of cis-1,4-poly（butadiene）（cis-PB）. Various chain dynamics properties, such as atom translational mobility, bond/segment reorientation dynamics, torsional dynamics, conformational transition rate and dynamic heterogeneity of the cis-PB chains, are analyzed in detail. It is found that T_g could be affected by the C_（60） weight fraction due to its inhibition effect on the mobility of the cis-PB chains. However, T_g is different, which depends on different dynamics scales. Among the chain dynamics properties, T_g is the lowest from atom translational mobility, while it is the highest from the dynamic heterogeneity. In addition, T_g can be more clearly distinguished from the dynamic heterogeneity; however, the conformational transition rate seems to be not very sensitive to the C_（60） weight fraction compared with others. For pure cis-PB chains, T_g and the activation energy in this work can be compared with those of other polymers. In addition, the temperature dependence of the dynamic properties has different Arrhenius behaviors above and below T_g. The activation energy below T_g is lower than that above T_g. This work can help to understand the effect of the C_（60） on the dynamic properties and glass transition temperature of the cis-PB chains from different scales.展开更多
文摘Machine learning(ML)has emerged as a powerful tool for predicting polymer properties,including glass transition temperature(Tg),which is a critical factor influencing polymer applications.In this study,a dataset of polymer structures and their Tg values were created and represented as adjacency matrices based on molecular graph theory.Four key structural descriptors,flexibility,side chain occupancy length,polarity,and hydrogen bonding capacity,were extracted and used as inputs for ML models:Extra Trees(ET),Random Forest(RF),Gaussian Process Regression(GPR),and Gradient Boosting(GB).Among these,ET and GPR achieved the highest predictive performance,with R2 values of 0.97,and mean absolute errors(MAE)of approximately 7–7.5 K.The use of these extracted features significantly improved the prediction accuracy compared to previous studies.Feature importance analysis revealed that flexibility had the strongest influence on Tg,followed by side-chain occupancy length,hydrogen bonding,and polarity.This work demonstrates the potential of data-driven approaches in polymer science,providing a fast and reliable method for Tg prediction that does not require experimental inputs.
基金Project (51101022) supported by the National Natural Science Foundation of ChinaProject (CHD2012JC096) supported by the Fundamental Research Funds for the Central Universities,China
文摘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）.
基金the National Science Foundation of China(No.11174258)the Development Foundation of China Academy of Engineering Physics(No.2013A0302016)
文摘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.
基金The project was support by the Natural Science Foundation of University of Anhui Province (No. 2006KJ156B)
文摘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.
基金supported by the National Natural Science Foundation of China (No. 51271195)
文摘In this paper, we report a strain rate related glass transition in model SrCaYbMg（Li）Zn（Cu） metallic glasses at room temperature. A critical strain rate, equivalent to glass transition temperature, is found for the strain rate induced glassy state to liquid-like viscoplastic state translation. The results show that the observation time, equivalent to temperature and stress, is a key parameter for the transition between the glass and supercooled liquid states. A three-dimension glass transition diagram involved in time, temperature and stress in metallic glasses is established.
文摘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.
基金supported by the National Natural Science Foundations of China (Grant Nos. 10774064 and 30860076)the Key Foundation of Xinjiang Education Department (Grant No. XJEDU2007137)the Natural Science Foundations of Xinjiang Science and Technology Department (Grant Nos. 200821104 and 200821184)
文摘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）.
基金Project supported by the National Natural Science Foundations of China (Grant Nos. 10774064 and 30860076)the Key Foundation of Xinjiang Education Department (Grant No. XJEDU2007137)the Natural Science Foundations of Xinjiang Science and Technology Department of China (Grant Nos. 2008211042 and 200821184)
文摘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.
基金supported by the National Natural Science Foundation of China (No. 50571055).
文摘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.
文摘In this study, the glass transition and uniaxial tensile properties of a commercially available epoxy adhesive were investigated using experimental measurements and molecular dynamics （MD） simulation. Differential scanning calorimetry （DSC） was used to study the change of glass transition temperature （Tg） with cross-link density （CLD）. Uniaxial tensile test was performed to measure the Young＇s modulus （E）, Poisson＇s ratio （v） and yielding strength （tyv）. In MD simulation, the complicated epoxy system was simplified as the mixture of two kinds of simple molecules, with the key information well preserved and the less important details omitted. The molecular model of the cross-linked epoxy network was constructed and its mechanical properties were calculated using MD simulation. Overall, the MD simulation results agreed with experimental ones, which proved the validity of the molecular model and justified the simplification method of the industry- level epoxy system.
基金supported by the National Key Research and De-velopment Program of China(No.2022YFB3800052)the National Natural Science Foundation of China(Nos.12002013,51971009,and 51831006)+1 种基金the Zhejiang Natural Science Foundation(No.LZ23E010004).H.L.Hou also acknowledges the support of the Fundamental Research Funds for the Central Universities(No.501LKQB2020105028)the Opening Fund of the State Key Lab-oratory of Nonlinear Mechanics.
文摘Exploring the phase transition of high entropy alloys(HEAs)with multiple major elements is of great importance for understanding the underlying physical mechanisms.Macroscopic martensitic phase tran-sition has been frequently reported in HEAs,however,nanoscale microstructural phase evolution has not been investigated to the same extent.Herein,we have prepared the Ti_(33)Nb_(15)Zr_(25)Hf_(25)O_(2)HEA and investi-gated the strain glass transition and its associated properties using dynamic mechanical analysis and mi-crostructure characterization.We have found that the elastic modulus in Ti_(33)Nb_(15)Zr_(25)Hf_(25)O_(2)HEA deviates from Wachtman’s equation and observed the Elinvar effect in the form of temperature-independent mod-ulus in the temperature range from 150 K to 450 K and frequency-dependence modulus around 220 K.The strain glass transition has been evidenced in Ti_(33)Nb_(15)Zr_(25)Hf_(25)O_(2)HEA by the formation and growth of nano-sized domains during in-situ transmission electron microscopy(TEM)cooling,and substantiated by the broken ergodicity during zero-field-cooling/field-cooling.The strain glass transition is believed to account for the Elinvar effect,where the modulus hardening of nano-sized domains compensates dynam-ically with the modulus softening of the transformable matrix.
基金financially supported by the National Science Fund for Distinguished Young Scholars(No.20825416)the National Natural Science Foundation of China(No.21374051)+2 种基金973 program(No.2012CB821503)PCSIRT(No.IRT1257)CERS-1-61.A.C.S.acknowledges the support of the Natural Science and Engineering Council(NSERC)of Canada
文摘A two-stage transition upon crossing the glass transition of polystyrene with increasing temperature was precisely determined and interpreted by using solid-state nuclear magnetic resonance （SSNMR）, 1H-XH dipolar couplings based double quantum-filtered （DQF） and dipolar filter （DF） experiments and 13C chemical shift anisotropy （CSA） based centerband-only detection of exchange （CODEX） experiment are used to fully characterize the time scale of molecular motions during the glass transition. While differential scanning calorimetry （DSC） and CODEX experiment predicted the first stage of glass transiton, DQF and DF experiments provided the evidence for the second stage transition during which the time scale of molecular motions changed from very slow （t 〉 ms） to very fast （t 〈 Its）. The first stage of glass transition begins with the occurrence of remarkable slow re-orientation motions of the polymer backbone segments and ends when the degree of slow motion reaches maximum. The onset and endpoint of the conventional calorimetric glass transition of polystyrene can be quantitatively determined at the molecular level by SSNMR. In the second stage, a subsequent dramatic transition associated with the melting of the glassy components was observed. In this stage liquid-like NMR signals appeared and rapidly increased in intensity after a characteristic temperature Tf （-1.1Tg）. The signals associated with the glassy components completely disappeared at another characteristic temperature Tc （-1.2Tg）.
基金Supported by the National Natural Science Foundation of China(No.20803016)the Natural Science Foundation of Anhui Province,China(No.070414163)
文摘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.
基金supported by the National Natural Science Foundation of China under Grant No. 51171180
文摘We defined the plastic deformability under constrained loading conditions as malleability for bulk metallic glass （BMG） materials. Quaternary Zr-Ti-Cu-Al alloys in the Zr-rich composition range are selected to investigate the compositional dependence of malleability assessed by bending testing and glass transition temperature （Tg ）. As indicated, increasing the Al or Cu concentration in the alloys leads to the rise of T g . The Zr（61）Ti2Cu（25）Al（12） （ZT1） and Zr（61.6）Ti（4.4）Cu（24）Al（10） （ZT3） alloys exhibit an optimal combination of lower T g and higher glass-forming ability. The malleable BMGs such as ZT1 manifests two characters during deformation, the stable propagation of a single shear band indicated by large shear offsets and easy proliferation of shear bands. With increasing the T g of BMG, the yield strength σy,Young＇s modulus and shear modulus simultaneously increase as well, while the Poisson s ratio decreases. The σy of ZT1 BMG is about 1680 MPa in compression and 1600 MPa in tension. In tensile loading, no any visible plasticity appears even when the strain rate increases up to the order of magnitude of 10（-1）s（-1）. In consistent with the T g , malleability of Zr-Ti-Cu-Al BMGs manifests significant compositional dependence. The malleable BMG is associated with lower Tg , as well as lower shear modulus or higher Poisson s ratio, which can be understood on the basis of the correlation of Tg with shear energy barrier in metallic glass. Thus, the calorimetric Tg can be used as an indicator to screen malleable BMG-forming composition, with advantage of experimental accessibility.
基金supported by the National Natural Science Fund for Distinguished Young Scholars (No.20825416)the National Natural Science Foundation of China(NSFC) through the General Programs(No.20774054)the National Basic Research Program of China(973 Program,2012CB821500)
文摘Glass transition behavior of hydrogen bonded polymer blends of poly（vinyl phenol） （PVPh） and poly（ethylene oxide） （PEO） is systematically investigated using normal differential scanning calorimetry （DSC） and recently developed multifrequency temperature-modulated DSC （TOPEM）, in combination with Fourier transform infrared spectroscopy （FTIR） and nuclear magnetic resonance （NMR） techniques, focusing on the effect of the PEO molecular weight on the spatial and dynamic heterogeneity. It is found, for the first time, that both the glass transition temperature （Tg） and activity energy （Ea） of the blends strongly depend on PEO molecular weight, and a common turning point, which separates the rapid and slow increasing regions, can be found. The interchain hydrogen bonding interactions, both determined by FTIR measurements and obtained from the Kwei equation, decrease with increasing PEO molecular weight, indicating a decrease of the componential miscibility. A series of parameters related to the microscopic spatial and dynamic heterogeneity, such as the activity energy, fragility, nonexponential factor and the size of cooperatively rearranging regions, are calculated from frequency dependency complex heat capacity measured using TOPEM. It is found that each of these parameters monotonically changes with increasing the PEO molecular weight during the glass transition process, demonstrating that hydrogen bonding interaction is the key factor in controlling the spatial and dynamic heterogeneity, thus the glass transition. NMR relaxation results reveal the existence of obvious phase separation large than 5 nm, implying that the cooperatively rearranging regions should be closely related to the interphase region between the two components. The above obtained origin and evolution of spatial and dynamic heterogeneity provide a new insight into the glass transition behavior of polymer blends.
基金supported by the National Natural Science Foundation of China(Nos.50773068 and 50473039)
文摘Modulated-temperature differential scanning calorimetric and dynamic mechanical analyses and dielectric spectroscopy were used to investigate the glass transition of hydrated wheat gliadin powders with moisture absorption ranged from 2.30 db% to 18.21 db%. Glass transition temperature （Tg） of dry wheat gliadin was estimated according to the Gordon- Taylor equation. Structural heterogeneity at high degrees of hydration was revealed in dielectric temperature and frequency spectra. The activation energies （Ea） of the two relaxations were calculated from Arrhenius equation.
基金financially supported by the Fundamental Research Funds for the Central Universities(No.FRFTP-09-026B)the Program for Changjiang Scholars and Innovative Research Team in University,the Specialized Research Fund for the Doctoral Program of Higher Education(No.20100006110013)the National Natural Science Foundation of China(No.51010001)
文摘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.
文摘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.
基金financially supported by the National Natural Science Foundation of China(Nos.51325301 and 51633009)
文摘We device a relaxed lattice model （RLM） to study the mechanism of glass transition, which unifies the cage- effects from particle-particle interaction and entropy. By analyzing entropy in RLM with considering the influence of interactions on equilibrium, we demonstrate that glass transition is a second-order phase transition. For a perfect one- dimensional linked particle system like linear polymer under normal pressure, the free volume at glass transition is rigorously deduced out to be 2.6%, which provides a theoretical basis for the iso-free volume of 2.5% given by Willian, Landel and Ferry （WLF） equation. Extending to system with dead particles linked with higher dimensions like branched or cross-linked chains under positive or negative pressure, free volume at glass transition is varied, based on which we construct a phase diagram of glass transition in the space of free volume-dead particle-pressure. This demonstrates that free volume is not the single parameter determining glass transition, while either dead particles like cross-linked points or external force fields like pressure can vary free volume at the glass transition.
基金financial supports from the start-up funding of Beijing University of Chemical Technology(BUCT)for excellent introduced talentsthe Fundamental Research Funds for the Central Universities(JD1711)
文摘In this work, the effect of the fullerene（C_（60）） weight fraction and PB-C_（60） interaction on the glass transition temperature（T_g） of polymer chains has been systemically investigated by adopting the united atom model of cis-1,4-poly（butadiene）（cis-PB）. Various chain dynamics properties, such as atom translational mobility, bond/segment reorientation dynamics, torsional dynamics, conformational transition rate and dynamic heterogeneity of the cis-PB chains, are analyzed in detail. It is found that T_g could be affected by the C_（60） weight fraction due to its inhibition effect on the mobility of the cis-PB chains. However, T_g is different, which depends on different dynamics scales. Among the chain dynamics properties, T_g is the lowest from atom translational mobility, while it is the highest from the dynamic heterogeneity. In addition, T_g can be more clearly distinguished from the dynamic heterogeneity; however, the conformational transition rate seems to be not very sensitive to the C_（60） weight fraction compared with others. For pure cis-PB chains, T_g and the activation energy in this work can be compared with those of other polymers. In addition, the temperature dependence of the dynamic properties has different Arrhenius behaviors above and below T_g. The activation energy below T_g is lower than that above T_g. This work can help to understand the effect of the C_（60） on the dynamic properties and glass transition temperature of the cis-PB chains from different scales.
