Study on nanometric cutting of germanium by molecular dynamics simulation

Three-dimensional molecular dynamics simulations are conducted to study the nanometric cutting of germanium. The phenomena of extrusion, ploughing, and stagnation region are observed from the material flow. The uncut thickness which is defined as the depth from bottom of the tool to the stagnation region is in proportion to the undeformed chip thickness on the scale of our simulation and is almost independent of the machined crystal plane. The cutting resistance on (111) face is greater than that on (010) face due to anisotropy of germanium. During nanometric cutting, both phase transformation from diamond cubic structure to β-Sn phase and direct amorphization of germanium occur. The machined surface presents amorphous structure.     

Composition-structure-properties relationship of lithium-calcium borosilicate glasses studied by molecular dynamics simulation

The composition-structure-properties relationship of the lithium-calcium borosilicate (LCBS) glasses, which have a composition of 0.4[(1-x)Li₂O-xCaO]-0.6[(1-y)B₂O₃-ySiO₂] with x in the range of 0–1 and y in the range of 0.33–0.83, is investigated by the molecular dynamics (MD) simulation with the Buckingham potential. The structure of the silicon-oxygen tetrahedron is relatively independent of the glass compositions; however, the structure of the boron-oxygen polyhedron and the local environment around the modifier cations change significantly with increasing [SiO₂]/[B₂O₃] ratio (K) and CaO content. The relationships between glass composition and simulated linear thermal expansion coefficient (α_L), glass transition temperature (T_g), self-diffusivity (D), activation energy of electrical conductivity (Ea^σ) and fragility (m) are strongly affected by the change of glass network structure, and consistent with those of experimental results.     

A molecular dynamics simulation study on the crystallization of 22,8-polyurethane

By means of the molecular dynamics (MD) simulation, the crystallization mechanism of 22,8-polyurethane which contains hydrogen-bond units is investigated and the results show that the crystallization process at a fixed temperature can be characterized by three stages: (1) The extended chain collapses to a globular random coil; (2) The random coil reorganizes into an ordered lamellar structure; (3) Accompanied with the segments clustering due to the hydrogen-bond formation, the lamellar develops with local defects. Two kinds of hydrogen-bond, which are formed between NH group and CO group (N-H?OC), and between NH group and urethane alkoxy oxygen (N-H?O), respectively, are found to play an important role in the crystallization process of 22,8-polyurethane. Furthermore, the effect of temperature on the crystallization is also studied by selecting three temperatures 200, 300 and 400 K. The lower the crystal temperature is, the slower the crystallization rate is and the stronger the hydrogen-bonding interactions are presented. This is in harmony with the experimental results.     

Compatibility of polyvinyl alcohol and poly(methyl vinyl ether-co-maleic acid) blends estimated by molecular dynamics

The CSIR has developed a novel oxygen barrier technology for plastics packaging based on interpolymer complex formation between PVOH (polyvinyl alcohol) and PMVE-MA (poly(methyl vinyl ether-co-maleic acid)). As interpolymer complexation interactions are strongly dependent on stoichiometric ratios, the estimation of the optimum blend ratio is an important component of blend design.This study used molecular dynamics modelling to predict the ratio of optimum interaction for PVOH:PMVE-MA blends. Amorphous cells were constructed containing blends of short-chain repeat units of PVOH and PMVE-MA. The oligomers were equilibrated using both NVT and NPT dynamics and the cohesive energy densities (CED's) of the models were computed. From the CED's, energies of mixing and Flory-Huggins Chi Parameter (χ) values were estimated.The χ-values were negative for all blends, indicating favorable interaction between the two polymers. The minimum χ-values were found around 0.6-0.7 mass fraction of PMVE-MA, which agrees well with experimental viscosity results (this work), which indicated optimum interaction around 0.7 mass fraction PMVE-MA. These results confirm that molecular dynamics can be used as a tool for investigating interpolymer complexation phenomena.     

Material properties of the cross-linked epoxy resin compound predicted by molecular dynamics simulation

Molecular dynamics (MD) simulations were conducted to estimate the material properties of the cross-linked epoxy resin compound. A periodic amorphous structure of the cross-linked epoxy resin compound was constructed and it was simulated by continuous accumulation of structure configurations at various temperatures. Based on the simulation results, glass transition temperature (T_g), linear thermal expansion coefficients and Young's modulus of the cross-linked epoxy resin compound were predicted. The predicted values of these material properties are in good agreement with the experimental values in the literature.     

A molecular dynamics simulation study of the influence of free surfaces on the morphology of self-associating polymers

Molecular dynamics simulations of thin films and bulk melts of model self-associating polymers have been performed in order to gain understanding of the influence of free surfaces on the morphology of these polymers. The self-associating polymers were represented by a simple bead-necklace model with attractive groups (stickers) at the chain ends (end-functionalized polymer) and in the chain interior (interior-functionalized polymer). The functionalized groups were found to form clusters in the melt whose size is representative of that found experimentally in many ionomer melts. While the size distribution and shape of the clusters in the thin films were found to be relatively unperturbed compared to their corresponding bulk melts, the morphology of the self-associating melts was found to be significantly perturbed by the free surfaces. Specifically, a strong depletion of stickers near the interface and the emergence of clearly defined layers of stickers parallel to the surface was observed. Increased bridging of clusters by the functionalized polymers was also observed near the free surface. We conclude that these effects can be associated with a high free energy for stickers in the low-density interfacial regime: stickers prefer to be in the higher-density interior of the film where relatively unperturbed sticker clusters can form.     

A study of solvation of o-/m-hydroxybenzoic acid in supercritical CO2-methanol co-solvent system based on intermolecular interaction by molecular dynamics simulation

Solvation behavior of o-hydroxybenzoic acid (o-HBA) and m-hydroxybenzoic acid (m-HBA) in CO₂ and methanol mixtures was investigated by molecular dynamics simulation. The results indicated that the distribution of methanol around o-, m-HBA molecules was different, and it was ascribed to the different hydrogen bonding numbers formed between methanol and HBA molecules. Moreover, the interaction or hydrogen bonds between m-HBA and methanol was much stronger than that between o-HBA and methanol, and with the increasing of CO₂ pressure, it did not change for the former, but decreased for the latter. In addition, the local mole fraction enhancement was also studied. It was demonstrated that the methanol molecules become less aggregate with increasing CO₂ pressure.     

Diffusivity of n-hexane in poly(ethylene-stat-octene)s assessed by molecular dynamics simulation

Molecular dynamics simulations have been used to study diffusion of n-hexane in wholly amorphous poly(ethylene-stat-octene)s with comonomer contents ranging from 0 to 11.5 mol%. The branches in the polymer increased the specific volume by affecting the packing of the chains in the rubbery state in accordance with experimental data. The diffusion of n-hexane at penetrant concentrations between 0.5 and 9.1 wt% was simulated within time-scales between 0.1 and 0.2 μs. The penetrant diffusivity unexpectedly decreased with increasing comonomer content. The penetrant molecule motion statistics showed that systems with high comonomer content showed a greater tendency for short distance motion (over a sampling period of 3 ps) whereas the systems with lower comonomer content showed penetrant motion over longer distances. It seems that the branches retarded local chain mobility of the polymer thereby trapping the penetrant molecules. All systems studied showed a minimum in penetrant diffusivity at ca. 1 wt% n-hexane and a marked increase in diffusivity at higher penetrant concentrations. The volumetric data for the different polymer-penetrant systems were consonant with additional volumes of the different components. Comparison between simulated diffusivities (for a wholly amorphous polymer) and experimentally obtained diffusivity data for semicrystalline polymers showed that constraining effect of the crystals were substantial for the highly crystalline systems and that it gradually decreased with decreasing crystallinity.     

Effect of chain composition on the mechanical response of structural gel: A molecular dynamics simulation

Polymer gels, defined either from the structural point of view (structural gel) or by their mechanical properties (mechanical gel), are ubiquitous in our daily life. In our previous work (J. Phys. Chem. B, 2011, 115, 11345), we reported that, the mechanical gel formed by strong solvophobic ABA block copolymers with fixed chain compositions shows a strong mechanical response, which meant the formed gel had a high modulus. In this work, we focus on the effect of chain composition on the relationship between structural gel and mechanical gel, where the chain length of block copolymer is lower than its entanglement chain length for simplicity. Our results show that the chain composition has a great effect on the mechanical response of the ABA copolymer solutions with a strong solvophobicity. On the other hand, for the structural gel formed by weak solvophobic block polymers, we do not find any strong mechanical responses even we change the chain composition in a wide range. Moreover, we find three typical gelation processes, companied with three kinds of different mechanical responses. These results may provide us an effective method to control the mechanical property of a polymer gel as expected.     

Effect of molecular architecture on the morphology diversity of the multicompartment micelles: A dissipative particle dynamics simulation study

Dissipative particle dynamics simulation is performed to study the sensitive influence of the molecular architecture and/or segment sequence on the morphology diversity of the multicompartment micelles. The multicompartment micelle morphologies formed by ABC triblock copolymers with various molecular architectures, such as the linear, the pentalinear, the cyclic, the star-like, the tetra-arm, and the π-shape are investigated, and different morphologies of the multicompartment micelles, for example, worm-like, “hamburger”, sheet-like with pores, “sweet potato” with alternating layers, sheet-like with cylinder-inclusion, and three-dimensional network are observed in this work. The density profiles and the radial distribution functions are calculated to characterize the structures of the multicompartment micelles. The preparation of complex multicompartment micelles can be fulfilled by simply changing the segment sequence and molecular architecture such as adding new bonds and grafting points.     

Effect of ligand chain length on hydrophobic charge induction chromatography revealed by molecular dynamics simulations

Hydrophobic charge induction chromatography (HCIC) is a mixed-mode chromatography which is advantageous for high adsorption capacity and facile elution. The effect of the ligand chain length on protein behavior in HCIC was studied. A coarse-grain adsorbent pore model established in an earlier work was modified to construct adsorbents with different chain lengths, including one with shorter ligands (CL2) and one with longer ligands (CL4). The adsorption, desorption, and conformational transition of the proteins with CL2 and CL4 were examined using molecular dynamics simulations. The ligand chain length has a significant effect on both the probability and the irreversibility of the adsorption/desorption. Longer ligands reduced the energy barrier of adsorption, leading to stronger and more irreversible adsorption, as well as a little more unfolding of the protein. The simulation results elucidated the effect of the ligand chain length, which is beneficial for the rational design of adsorbents and parameter optimization for high-performance HCIC.     

Investigation of the polyurethane chain length influence on the molecular dynamics in networks crosslinked by hyperbranched polyester

Several non-conventional polyurethane (PU) networks crosslinked with hyperbranched polyester (Boltorn^®H40) were synthesised with an aim to determine an influence of the PU chain length on molecular relaxations in such systems. The PU chain length was regulated by changing the macrodiol length or by changing the number of the repeating macrodiol/diisocyanate units n. Molecular dynamics were investigated by broadband dielectric spectroscopy and by dynamic mechanical analysis. It was found that the macrodiol length has a strong influence on the glass transition and the α-relaxation, and also on the crystallization. By contrast, the changes of n practically do not affect the molecular relaxations. This effect was explained by the formation of a physical network by hydrogen bonds between urethane groups, controlling the molecular mobility. The rheological measurements have shown, that at temperatures above 150 °C, when hydrogen bonds were thermally destroyed, not only macrodiol length but also n had strong influence on the flowing point.     

Study of the molecular weight dependence of glass transition temperature for amorphous poly(l-lactide) by molecular dynamics simulation

Molecular dynamics simulation has been used to investigate the molecular weight dependence of glass transition temperature for amorphous poly(l-lactide). Amorphous PLLA systems were created using molecular modeling and NPT ensemble MD simulations were carried out using the modified OPLS-AA force field. The fractal dimension of the PLA systems was 1.62. The molecular weight dependence of glass transition temperature, self-diffusion coefficient and shear viscosity were studied and the good agreement between the simulation results and experiments was obtained.     

Adsorption and diffusion of light alkanes on nanoporous faujasite catalysts investigated by molecular dynamics simulations

Molecular dynamics simulations were performed for ethane, propane, and n-butane in siliceous faujasite for different numbers of molecules per unit cell (loadings) at 300 K. Both the adsorbed molecules and the zeolite framework were modeled as flexible entities. A new semiempirical analytical potential function for the systems was constructed. From the mean-square displacement of the molecules, self-diffusion coefficients of 18.7 × 10⁻⁵, 13.3 × 10⁻⁵, and 4.3 × 10⁻⁵ cm²/s were calculated for ethane, propane, and n-butane, respectively at a loading of 8 molecules/unit cell. They compare well with experimental values from pulsed-field gradient NMR measurements (10 × 10⁻⁵, 9 × 10⁻⁵, and 6 × 10⁻⁵ cm²/s, respectively). Besides depending on the size of the hydrocarbon, the heats of adsorption and self-diffusion coefficients also strongly depend on the loading of adsorbate molecules. The results suggest that the new intermolecular force field can reasonably describe the adsorption and diffusion behavior of ethane, propane, and n-butane in faujasite zeolite.     

基于分子动力学模拟的轮胎橡胶催化热解制氢机理

采用分子动力学模拟方法,选取Ni、ZSM-5以及Ni/ZSM-5催化剂,对轮胎橡胶热解制氢的机理进行探究,并同时与前人做过的实验研究进行对比验证模拟计算。文中利用Material Studio建立轮胎橡胶模型,DMol3模块对生成氢气路径进行过渡态搜索,CULP模块对其加入Ni催化剂的热解过程进行模拟。模拟结果表明,制氢催化效果顺序为Ni>Ni/ZSM-5>ZSM-5。催化热解大致分为两个阶段：①低温阶段长链裂解成单体化合物,单体主要是异戊二烯、苯乙烯以及1,3-丁二烯;②高温阶段自由基攻击单体生成小分子物质。加入Ni催化剂后降低了热解终止温度。催化剂的加入在低温阶段主要表现在加快热解进程,增加低温阶段时单体数量。在高温阶段主要表现在改变了气体产物分布,Ni的加入降低了轮胎热解温度,并且使氢比例增加。     

Molecular dynamics simulation on ionic conduction process of oxygen in Ce1−xMxO2−x/2

Molecular dynamics simulation of CeO₂ doped with M³⁺ (a trivalent cation) with ionic radii ranging from 1.019 Å (Y³⁺) to 1.160 Å (La³⁺) were performed to examine the effects of the dopant cation size on ionic conductivity. Interatomic potential parameters were empirically fitted with equilibrium properties and energy barriers from ab initio calculations. Vacancy trapping and edge blocking mechanisms were studied. Analysis on vacancy trapping showed that the effect was more pronounced in La- and Y-doped ceria than those doped with Gd and Sm. Analysis of the edge blocking effect showed that larger-sized dopants would limit the available pathways for vacancy hopping. The combined effects satisfactorily explained the influence of the dopant cation size on the ionic conductivity of heavily doped ceria.     

The effect of soft bake on adhesion property between SU‐8 photoresist and Ni substrate by molecular dynamics simulation

SU‐8 photoresist is a negative, epoxy‐type, near UV photoresist and is commonly used in micro electro mechanical systems (MEMS) and other thick resist application fields. However, poor adhesion strength between SU‐8 photoresist and metal substrate makes it difficult to bind, even contributes to the lithography failure. This significantly restricts the improvement of image resolution and depth‐to‐width ratio. As soft bake temperature and time are important for the interfacial adhesion property, in this article, molecular dynamics (MD) simulation was performed to investigate the effects of these two parameters on adhesion property between SU‐8 photoresist and Ni substrate. According to the adsorption theory, the simulation results were analyzed and validated by experiments. It is shown that with increasing soft bake temperature the adhesional work firstly increases and then decreases, and with increasing soft bake time the adhesional work decreases. This study provides theory basis for the confirmation of soft bake parameters. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

基于分子动力学模拟的羟基改性调控活性炭对甲苯吸附性能的作用机理研究

本工作通过在六苯并苯分子边缘植入羟基构建不同羟基含量的改性活性炭,采用分子动力学和巨正则蒙特卡罗模拟研究了改性活性炭模型的物理性质、局部电荷和孔径分布,进一步分析了甲苯分子在改性活性炭中的动力学特性和吸附机理。结果表明,引入羟基可加强活性炭对甲苯的吸附能力。在较高相对压强下,羟基含量为39.4%是活性炭改性的最佳浓度,超过此浓度后甲苯的吸附量下降。改性活性炭羟基中强电负性的氧原子与甲苯甲基中的氢原子配合成Lewis酸碱对,形成稳定的吸附结构,进而增强活性炭对甲苯的吸附能力。在较低相对压强下,影响吸附量的主要因素为孔隙率和孔径大小;羟基含量为20.8%和31.4%的改性活性炭内多为微孔且结构较为紧密,使得其吸附甲苯效果较好。羟基改性使得甲苯分子在活性炭内的自扩散系数降低,且在含39.4%羟基的活性炭中扩散系数最低,这是由于甲苯分子与改性活性炭之间的非键相互作用阻碍了甲苯分子的运动。此外通过变温吸附研究发现,由于活性炭吸附甲苯过程具有放热性质,温度升高不利于甲苯的吸附。     

Effects of water and carbon dioxide pressure on the adhesion of Na2SiO3 and K2SiO3 binders on silica sand surface: Comparison of experimental data and molecular dynamics simulation

In this study, the effects of different water amounts, CO₂ blowing pressures, Na₂O:SiO₂ and K₂O:SiO₂ ratios were studied on the bonding strength of Na₂SiO₃ and K₂SiO₃ binders. It was concluded that the increase in water content had an adverse effect on the bonding strength of CO₂-hardened Na₂SiO₃ sand. The blowing pressure did not have a linear relationship with the bonding strength, but it was closely related to the diffusion coefficient of CO₂. Based on scanning electron microscopic results, it was inferred that the low strength was caused by the formation of lamellar crystals after the adhesive was hardened. It was found that the low strength was caused by the formation of lamellar crystals after the adhesive was hardened. Based on molecular dynamics simulations, different pressures and water contents had a great influence on the diffusion coefficient of CO₂ in the silicate binder system. This research provides an important theoretical background to improve the technology of CO₂-hardened Na₂SiO₃- and K₂SiO₃-bonded sands during the casting process.     

用分子动力学模拟研究丁二烯微观结构对丁腈橡胶物理机械性能的影响

采用分子动力学模拟的方法对基于3种不同丁二烯键合结构建立的丁腈橡胶模型(A、B、C模型)进行了模拟计算,以考察丁二烯微观结构对丁腈橡胶物理机械性能的影响.采用恒定应变法计算模型的物理机械性能,然后将模型与铁原子层结合建立摩擦副模型,利用剪切模拟分析丁腈橡胶摩擦过程的磨损机理.结果表明,与A模型和C模型相比,B模型分子链...