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）.

Molecular Dynamics Simulation of Glass Transition Behavior of Polyimide Ensemble

The effect of chromophores to the glass transition temperature of polyimide ensemble has been investigated by means of molecular dynamics simulation in conjunction with barrier analysis. Simulated Tg results indicated a good agreement with experimental value. This study showed the MD simulation could estimate the effect of chromophores to the Tg of polyimide ensemble conveniently and an estimation approach method had a surprising deviation of Tg from experiment. At the same time, a polyimide structure with higher barrier energy was designed and validated by MD simulation.

Multi-scale Studies of Glass Transition and Uniaxial Tensile Properties of a Commercially Available Epoxy Adhesive Using Experimental Measurements and Molecular Dynamics Simulation

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.

Molecular Dynamics Simulation of the Glass Transition Temperature of Fullerene Filled Cis-1,4-polybutadiene Nanocomposites

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.

Molecular Dynamic Simulation Study on Glass Transition Temperature of DGEBA-THPA/SWCNTs Composites

Molecular dynamic (MD) simulations were carried out to predict the thermo-mechanical properties of the cured epoxy network composed of diglycidyl ether bisphenol A (DGEBA) epoxy resin and tetrahydrophthalic anhydride (THPA) curing agent and their single-walled carbon nanotubes (SWCNT) reinforced the epoxy matrix composites. Different characters such as the density of the materials and mean square displacements (MSDs) were calculated to estimate the glass transition temperatures (Tgs) of of the materials. 365 K and 423 K of the Tgs were obtained respectively, whereas the latter is much higher than the former. The simulation results indicated that the incorporation of SWCNTs in the epoxy matrix can significantly improve the Tg of the cured epoxy. The approach presented in this study is ready to be applied more widely to a large group of candidate polymers and nanofillers.

Molecular dynamics of amorphous pharmaceutical fenofibrate studied by broadband dielectric spectroscopy

Fenofibrate is mainly used to reduce cholesterol level in patients at risk of cardiovascular disease. Thermal transition study with the help of differential scanning calorimetry （DSC） shows that the aforesaid active pharmaceutical ingredient （API） is a good glass former. Based on our DSC study, the molecular dynamics of this API has been carried out by broadband dielectric spectroscopy （BDS） covering wide temperature and frequency ranges. Dielectric measurements of amorphous fenofibrate were per- formed after its vitrification by fast cooling from a few degrees above the melting point （Tm=354.11 K） to deep glassy state. The sample does not show any crystallization tendency during cooling and reaches the glassy state. The temperature dependence of the structural relaxation has been fitted by single Vogel- Fulcher-Tamman （VFT） equation. From VFT fit, glass transition temperature （Tg） was estimated as 250.56 K and fragility （m） was determined as 94.02. This drug is classified as a fragile glass former. Deviations of experimental data from Kohlrausch-Williams-Watts （KWW） fits on high-frequency flank of α-peak indicate the presence of an excess wing in fenofibrate. Based on Ngai＇s coupling model, we identified the excess wing as true Johari-Goldstein （JG） process. Below the glass transition temperature one can clearly see a secondary relaxation （γ） with an activation energy of 32.67 kJ/mol.

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.

Molecular dynamics simulations on specific heat capacity and glass transition temperature of liquid silver

The embedded-atom method is adopted to simulate the specific heat capacity of liquid silver. The relationship between the specific heat capacity and the temperature above and below melting point is derived. The results show that there exists an anormaly of the specific heat capacity of liquid silver near 950 K. Simulated pair distribution functions show that the liquid-to-glass transition takes place at this temperature.

Thermodynamic and structural properties of polystyrene/C60 composites: A molecular dynamics study

To tailor properties of polymer composites are very important for their applications.Very small concentrations of nanoparticles can significantly alter their physical characteristics.In this work,molecular dynamics simulations are performed to study the thermodynamic and structural properties of polystyrene/C60(PS/C60)composites.The calculated densities,glass transition temperatures,and coefficient of thermal expansion of the bulk PS are in agreement with the experimental data available,implying that our calculations are reasonable.We find that the glass transition temperature Tg increases accordingly with an added concentration of C60 for PS/C60 composites.However,the self-diffusion coefficient D decreases with increase of addition of C60.For the volumetric coefficients of thermal expansion(CTE)of bulk PS and PS/C60 composites,it can be seen that the CTE increases with increasing content of C60 above Tg(rubbery region).However,the CTE decreases with increasing content of C60 below Tg(glassy region).

Predicting Glass Transition Temperature of Polyethylene/Graphene Nanocomposites by Molecular Dynamic Simulation

The glass transition temperature of polyethylene/graphene nanocomposites was investigated by molecular dynamic simulation. The specific volumes of three systems（polycthylene, polyethylene with a small graphene sheet and two small graphene sheets） were examined as a function of temperature. We found that the glass transition temperature decreases with increasing graphene. Then the van der Waals energy changes obviously with increasing graphene and the torsion energy also plays an important role in the glass transition of polymer. The radial distribution functions of the inter-molecular carbon atoms suggest the interaction between PE and graphene weakens with increasing graphene. These indicate that graphene can prompt the motion of chain segments of polymer and decrease the glass transition temperature （Tg） of polymer.

Computer simulation studies of the influence of side alkyl chain on glass transition behavior of carbazole trimer

In this work,all-atom molecular dynamics simulations were employed to study the influence of the side alkyl chain on glass transition behavior of several carbazole trimers(CT) in a temperature range from 423 to 183 K.The glass transition temperatures were obtained from the break in the slope of the volume-temperature curves and found to agree with the experimental values.The short time dynamics of four CT molecules were probed by usingvelocity autocorrelation functions and mean-square displacements.The current studies showed that the dynamics of CT systems can be easily interpreted through the cage effect.Furthermore,the investigation of the torsional autocorrelation function and P_(2-state)/P_(3-state) functions showed that the rotational barriers of side chains can slow down the conformational relaxation and lead to stronger temperature dependence of conformational relaxation.The relaxation time,characteristic time of P_(2-state)(t) and P_(3-state)(t) functions were all found to have Arrhenius-type temperature dependence.

Study on the gas permeabilities in styrene-butadiene rubber by molecular dynamics simulation

In this research,molecular dynamics(MD)simulations were used to study the transport properties of small gas molecules in the butadiene-styrene copolymer(SBR).The condensed-phase optimized molecular potentials for atomistic simulation studies(COMPASS)force field was applied.The diffusion coefficients were obtained from MD(NVT ensemble)and the relationship between gas permeability;the chemical structure and free volume of butadiene-styrene copolymer were investigated.The results indicated that the diffusion coefficient of oxygen declined with increasing styrene content.The fraction of free volume(FFV)in butadiene-styrene copolymer was calculated.It was concluded that diffusion coefficient increased as the FFV increases,which is in accordance with the analysis of the small molecular hop through the free volume in polymer matrix.Subsequently,the glass transition temperatures of these copolymers were calculated by MD.The result showed that the glass transition temperature increased with increasing styrene content in polymer.

Effect of Branching Architecture on Glass Transition Behavior of Hyperbranched Copolystyrenes:the Experiment and Simulation Studies

By controlling the feed ratio of CMS/styrene and the polymerization time, a series of hyperbranched copolystyrenes（HBCPS） were synthesized with comparable weight-averaged molecular weights（Mw） but different degree of branching（DB） through atom transfer radical self-condensing vinyl copolymerization（ATR-SCVCP） with Cu Br/2,2？-bipyridyl as the catalyst. The resulting HBCPS samples were used to investigate the effect of branching architecture on their glass transition behavior. With the DB increased, the glass transition temperatures（Tg） of HBCPS samples measured by DMA and DSC both decreased. Their spin-lattice relaxation times（1H T1r） of protons displayed the same downtrend with increasing DB. Besides, a correlation between the Tgs and the DB was well established by all-atom molecular dynamics（MD） simulations. The values of MD-determined Tgs are little higher than the corresponding experimental ones. However, the dependence of Tgs on DB is in good agreement with the experimental results, i.e., Tg decreases both in experiments and simulations with increasing DB.

Structural relaxation and glass transition behavior of binary hard-ellipse mixtures

Structural relaxation and glass transition in binary hard-spherical particle mixtures have been reported to exhibit unusual features depending on the size disparity and composition. However, the mechanism by which the mixing effects lead to these features and whether these features are universal for particles with anisotropic geometries remains unclear. Here, we employ event-driven molecular dynamics simulation to investigate the dynamical and structural properties of binary two-dimensional hard-ellipse mixtures. We find that the relaxation dynamics for translational degrees of freedom exhibit equivalent trends as those observed in binary hard-spherical mixtures. However, the glass transition densities for translational and rotational degrees of freedom present different dependencies on size disparity and composition. Furthermore,we propose a mechanism based on structural properties that explain the observed mixing effects and decoupling behavior between translational and rotational motions in binary hard-ellipse systems.

Analysis of Activation Energies &Experimental Evidence for Energetic Phase Separation in Ge_xSe_1-xGlassy System

Glass science reveals peculiar properties due to the lack of long range order and presence of heterogeneity in Chalcogenide glasses. In thermal studies, structural relaxation at the glass transition region is governed by the activation energy of the cooperative unit (zU). In the cooperative molecular dynamics, we are considering the analysis of three activation energies, namely activation energy per BMS (U), activation energy of the cooperative unit (zU) and the apparent activation energy (z2U). From the energetic dynamics of activation energy analysis across the GexSe1-x glass series, data represent three-phase segregation. From our data, we also observed that the value of UCRR/RTg across the GexSe1-x glass series is nominally changed from 34.343 to 36.19.

Simulations of the flipping images and microparameters of molecular orientations in liquids according to the molecule string model

The relaxation dynamics of liquids is one of the fundamental problems in liquid physics, and it is also one of the key issues to understand the glass transition mechanism. It will undoubtedly provide enlightenment on understanding and calculating the relaxation dynamics if the molecular orientation flipping images and relevant microparameters of liquids are studied. In this paper, we first give five microparameters to describe the individual molecular string （MS） relaxation based on the dynamical Hamiltonian of the MS model, and then simulate the images of individual MS ensemble, and at the same time calculate the parameters of the equilibrium state. The results show that the main molecular orientation flipping image in liquids （including supercooled liquid） is similar to the random walk. In addition, two pairs of the parameters are equal, and one can be ignored compared with the other. This conclusion will effectively reduce the difficulties in calculating the individual MS relaxation based on the single-molecule orientation flipping rate of the general Glauber type, and the computer simulation time of interaction MS relaxation. Moreover, the conclusion is of reference significance for solving and simulating the multi-state MS model.

Preparation of Chitosan Copper Complexes: Molecular Dynamic Studies of Chitosan and Chitosan Copper Complexes

This work studied the effect of copper ions concentration chelated by functional groups in chitosan on its molecular dynamic. Chitosan Copper complexes prepared having different copper concentrations by the electrochemical oxidation technique in aqueous-acetic acid medium. It was carried out at constant voltage (2 volt.) at room temperature at different electro-oxidation time. The result of partial elemental analysis and XRD studies of chitosan copper complexes compared with chitosan confirmed that the percentage composition of the complexes were found to be depend on the time of electrolysis which is in good agreement with our previous work. Interpretation of the effect of copper ions concentration on molecular motion of chitosan studied using dielectric spectroscopy, the results showed that dielectric constant of chitosan is higher than that of chitosan copper complexes. This may be attributed to the relatively fast segmental motion of chitosan chain slowed down by complexation with copper ions of all complex samples. Calculated activation energy from Arrhenius variation showed increase in value with increasing the copper concentration and all in the range that required for ionic conduction. Temperature dependence part of dielectric parameters gives very useful representation in the glass transition temperature determination.

Novel Soft Magnetic Co-Based Ternary Co-Er-B Bulk Metallic Glasses

In this work,a series of Co-based ternary Co-Er-B bulk metallic glasses(BMGs)with excellent soft magnetic properties and high strength were developed,and the local atomic structure of a typical Co_(71.5)Er_(3.5)B_(25) metallic glass was studied through in situ high-energy synchrotron X-ray diffraction and ab initio molecular dynamics simulations.The results reveal that the BMG samples can be obtained in a composition region of Co_(68.5-71.5)Er_(3.5-4)B_(25-27.5) by a conventional copper-mold casting method.The Co-Er-B metallic glasses possess stronger atomic bond strengths and denser local atomic packing structure composed of a higher fraction of icosahedral-like clusters but fewer deformed body-centered cubic and crystal-like polyhedrons,and they exhibit slower atomic diffusion behaviors during solidification,as compared to Co-Y-B counterparts.The enhancement in structural stability and the retardation of atomic-ordered diffusion lead to the better glass-forming ability of the Co-Er-B alloys.The smaller magnetic anisotropy energy in the Co-Er-B metallic glasses results in a lower coercivity of less than 1.3 A/m.The Co-Er-B BMGs exhibit high-yield strength of 3560-3969 MPa along with distinct plasticity of around 0.50%.

基于分子动力学模拟预测环氧树脂形状记忆性能研究

形状记忆环氧树脂是制备可展开空间结构的重要材料之一,通过分子动力学模拟预测环氧树脂的形状记忆性能是设计与制备形状记忆环氧树脂的有效指导手段。在pcff力场下,通过分子动力学模拟方法,构建了交联度分别为36%、48%、59%、72%和84%的三乙烯四胺固化的双酚A环氧树脂聚合物模型,并模拟计算了其玻璃化转变温度、力学性能及形状记忆性能。结果表明,不同交联度的环氧树脂聚合物模型均表现出较好的形状固定率,为80%~86%;分析聚合物模型的x、y、z三轴回复性可知,36%交联度的环氧树脂不具有形状记忆性能,48%交联度的环氧树脂形状记忆性能较差,而59%、72%、84%交联度的环氧树脂的形状回复率均能达到80%以上,具有良好的形状记忆性能,且交联度越高形状回复速度越慢。

HTPB推进剂固化体系结构和性质的分子动力学模拟

为了研究端羟基聚丁二烯(Hydroxyl-Terminated Polybutadiene,HTPB)固体推进剂内HTPB、甲苯二异氰酸酯(Toluene Diisocyanate,TDI)和氧化膦(Tris-1-(2-methylaziridinyl)phosphine oxide,MAPO)的不同组分含量对固化体系结构和性质的影响,理论推导了固化体系的模型参数,采用分子动力学方法建立了3种不同固化参数组成的固化体系分子模型,计算了固化体系的结合能、力学性质、径向分布函数、玻璃化转变温度和溶度参数等特征参数,分析了组分含量与这些特征参数的关系。结果表明:TDI和MAPO含量的变化会对固化体系的性质产生较大影响,二者含量增加时可有效提高固化体系的结合能和玻璃化转变温度;二者含量减少时可使得溶度参数、剪切模量G和杨氏模量随之减小,而体积模量B、Cauchy压力和B/G增大;随着温度的升高,3种固化体系的溶度参数均呈现明显的下降趋势。