Dynamics of conformations,hydrogen bonds and translational diffusion of poly(methacrylic acid) in aqueous solution and the concentration transition in MD simulations

The dynamic behaviour of chain conformations, hydrogen bonds and translational diffusion of aqueous poly(methacrylic acid) (PMA) solution as a function of polymer volume fraction Φ_p across dilute to concentrated regimes inclusive of the pure polymer amorphous state was studied by molecular dynamics simulations. The behaviour of the relaxation time (τ) of the backbone dihedral angle auto-correlation function (ACF) reveals slower relaxation at higher level of polymer concentration and the existence of a concentration-driven relaxation transition for the aqueous polymer solution which occurs in the polymer volume fraction range, specifically 54% < Φ_p < 82% for this system. The relaxation constant τ for backbone dihedral angle exhibits a linear variation with Φ_p, indicating a first-order kinetic transition. The intermittent ACF for decay of the H-bond correlation shows that H-bonds among water molecules relax faster than those of the PMA–PMA and PMA–water type. The relaxation rate of PMA–water H-bonds shows a decrease up to Φ_p = 72% and becomes faster at Φ_p = 82% due to the confining influence of neighbouring PMA chains. PMA–water and water–water H-bond dynamics show transitions around Φ_p = 72% PMA. With increase in Φ_p PMA diffusion coefficient decreases exponentially and water diffusion coefficient decreases linearly, in agreement with experimental observations using fluorescence and nuclear magnetic resonance (NMR) spectroscopic studies.     

Effect of water–methanol content on the structure of Nafion in the sandwich model and solvent dynamics in nano-channels; a molecular dynamics study

Continuing an ongoing study, molecular dynamics (MD) simulations were performed to investigate the effects of methanol concentration on Nafion morphology, such as the size of solvent cluster, solvent location, and polymer structure via the sandwich model. Our survey shows that high methanol concentrations resulted in increment of solvent cluster size in Nafion membrane. The sulfonic acid clusters also befall much in order as subsequent layers of such ionic clusters are formed. The number of neighbouring hydronium ions around a sulfur atom is independent of methanol concentration, but the first shell of hydronium and water around sulfonic acid clusters is broader. Although methanol would prefer to interact with water molecules rather than sulfonic acid groups, gathering of methanol molecules via hydrophobic self-aggregation is preferred. Methanol is located closer to the hydrophobic part of the polymer than water, while water is located closer to the hydrophilic part of the polymer. It was found that methanol distributes specifically more than water in nano-channels. Investigation of solvent dynamics in nano-channels shows that diffusion coefficients (D) of water, methanol, and hydronium decrease with increasing methanol concentration and they may be ordered as follows: D _Water?>?D _Methanol?>?D _Hydronium (D _Water?≈?1.6–2.0D _Methanol and D _Methanol?≈?2.1–3.0D _Hydronium).     

Postexposure evolution of a photoinduced grating in a polymer material with phenanthrenequinone

The specific features of the postexposure evolution of photoinduced (holographic) gratings in a model medium that consists of poly(methyl methacrylate) with distributed phenanthrenequinone and is characterized by a diffusion enhancement are investigated using the holographic relaxation technique. It is established that the evolution process occurs in four stages controlled by different mechanisms: (i) initial nonmonotonic changes governed by the diffusion of an intermediate radical photoreaction product and its transformation into a stable product due to attachment to the macromolecules, (ii) hologram enhancement through the diffusion of phenanthrenequinone molecules, (iii) rapid partial degradation associated with the spatially confined motion of polymer chain segments, and (iv) slow degradation as a result of macromolecular diffusion. In the course of polymer relaxation after a temperature jump, the processes associated with the mobility of molecules are retarded and the depth of rapid degradation decreases. The effective diffusion coefficient characterizing the destruction of reflection gratings is smaller than that for transmission gratings. This can be explained by the spatial inhomogeneity of the polymer.     

Temperature effects on the diffusion of water and monovalent counterions in the hydrated montmorillonite

We investigate here the effect of temperature on the diffusion of water and cations in the Wyoming-type montmorillonite clay. The considered cations are monovalent compensating ions, such as Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ in one-, two- and three-hydration states. For this purpose, molecular dynamics simulations have been performed to obtain the dynamic behaviour regarding the interlayer ions and water molecules under a temperature range between 260 and 400 K. The diffusion coefficient of water and cations in different hydrated clays increases with temperature. The influence of temperature on the diffusion of water is much greater than that of cations in one-, two- or three-hydrated clay. The degree of hydration plays an important role on the diffusion behaviour of water and counterions. We found that the effect of temperature is negligible in weakly hydrated clay, whereas it became significant in highly hydrated one. Besides, the size and mass of cations’ hydrate also affect the diffusion behaviour of water and cations in the interlayer space of hydrated clay.     

Theory of transport of long polymer molecules through carbon nanotube channels

A theory of transport of long chain polymer molecules through carbon nanotube (CNT) channels is developed using the Fokker-Planck equation and direct molecular dynamics simulations. The mean transport or translocation time tau is found to depend on the chemical potential energy, the entropy, and the diffusion coefficient. A power law dependence tau approximately N2 is found, where N is the number of monomers in a molecule. For 10(5)-unit long polyethylene molecules, tau is estimated to be approximately 1 micros. The diffusion coefficient of long polymer molecules inside CNTs, like that of short ones, is found to be a few orders of magnitude larger than in ordinary silicate based zeolite systems.     

氢气在多层球壳中扩散过程的模拟计算

 从Fick第二定律出发,推导了氢气在多层球壳中,扩散过程的浓度分布表达式,即氢气浓度与扩散时间和扩散距离的关系。每层中,在一定的扩散时间内,一定量的氢气的扩散浓度与扩散深度之间近似为抛物线关系,说明渗透物沿着聚合物链段膨胀的方向进行扩散。在同一位置,一定量氢气的浓度,随着时间的延长而增加,说明渗透物使聚合物链段发生膨胀,自由体积增大,扩散路径增多,扩散系数随着浓度的增加而增大。     

A study on the electrochemical behaviour of polypyrrole films in concentrated aqueous alkali halide electrolytes

The electrochemical behaviour of polypyrrole films doped with dodecyl benzene sulfonate (PPy/DBS) in LiCl aqueous electrolytes has been investigated in order to find the electrolyte concentration suitable for the operation of PPy/DBS-based soft actuators. For this investigation, PPy/DBS films deposited on gold-coated quartz crystals by electropolymerization and simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance techniques were used. During the first redox cycle, while large water movement is observed along with the counter ions in dilute electrolytes, such water transport in concentrated electrolytes is found to be very low. In dilute electrolytes, water molecules accompany counter ions as solvated molecules and due to osmotic effect. In concentrated electrolytes, water movement is less due to limited availability of free water as well as a smaller osmotic pressure difference. In highly concentrated aqueous electrolytes, the mass of the PPy/DBS film at the end of each redox cycle is found to drift, which can be controlled by changing the concentration of the electrolyte. The PPy/DBS films were also cycled at different scan rates in various alkali halide aqueous electrolytes of concentrations 0.1 and 1 M to determine the effective diffusion coefficients of alkali ions in the films. The effective diffusion coefficients were found to increase with the concentration of the electrolytes and decrease with the increase in size of cations.     

Sodium diffusion in cryolite at elevated temperatures studied by quasielastic neutron scattering

Quasielastic neutron scattering (QENS) has been applied to study the sodium mobility on nanosecond time scales in the perovskite fluoride cryolite, Na₃AlF₆, at high temperatures. Up to T = 1153 K the diffusion of Na ions is well described by a diffusion process of jumps between six and eight-fold coordinated sites. Above this temperature, where a step-like increase in the electrical conductivity occurs, the jump length increases, which indicates additional jumps over larger distances. The electrical conductivity derived from the self-diffusion coefficient via the Nernst–Einstein relation and the corresponding activation energy are in excellent agreement with the previous conductivity measurements. We conclude that the jump diffusion of sodium ions is the dominant mechanism for the electrical conductivity in cryolite at high temperatures up to T = 1153 K.     

绝缘油在水和酸共同作用下的分子动力学模拟

为探讨水分和温度对变压器油中酸扩散行为的影响,在分子模拟软件内建立了水分子、矿物油分子、甲酸分子的复合模型,水的体积分数分别为1%,3%,5%,甲酸的质量分数为3%.通过分子动力学方法模拟计算了甲酸分子在不同含水量油模型中的扩散系数、径向分布函数以及复合模型的总动能;此外,选取了水体积分数为1%的复合模型为研究对象,以温度为变量进行动力学模拟.结果表明:随着水含量的增多,甲酸的扩散系数并没有逐渐增大,甲酸分子与水分子之间的氢键数目呈逐渐减少的趋势.而随着温度的升高,油模型具有的动能越大,酸分子的扩散逐渐增强.油模型中,含水量越多,水和酸在热运动下碰撞油分子的能量越大;温度越高,相互之间的碰撞越激烈.模拟结果说明水分增加或温度增高,均对油分子的结构稳定性造成一定程度的破坏.     

模耦合理论计算纳米粒子在聚合物熔体中的含时扩散系数与常规扩散常数 (cited: 2)

分析和计算了纳米粒子在聚合物熔体中的含时扩散系数与常规扩散常数. 采用广义朗之万方程描述扩散动力学,并通过模耦合理论计算摩擦记忆内核.为简单起见,只考虑了来自两体碰撞和溶剂密度涨落耦合作用两类微观因素对摩擦记忆内核的贡献. 采用聚合物参考作用点模型以及Percus-Yevick闭合条件计算了聚合物-纳米粒子复合溶液的平衡态结构信息函数;详尽分析了纳米粒子的尺寸与聚合物链的尺寸对扩散动力学的影响. 揭示了结构函数、摩擦记忆内核以及扩散系数等随着纳米粒子半径和聚合物链长的变化关系. 结果表明,对于小尺寸的纳米粒子或者短链的聚合物,短时间的非马尔可夫扩散 动力学特征比较显著,含时扩散系数需要更长的时间弛豫到常规扩散常数. 微观因素对扩散常数的贡献随着纳米粒子尺寸的增加而减小,却随着聚合物链长的增加而增大. 此外,模耦合理论得到的扩散常数与Stokes-Einstein关系的预测值进行比较,发现对于小尺寸的纳米粒子或者长链的聚合物,微观因素对扩散常数的的贡献占主导地位. 相反,当纳米粒子较大或者聚合物链长较短时,流体力学的贡献会发挥重要作用.     

Simulation of small molecule diffusion using continuous space disordered networks

Disordered networks were created and kinetic Monte Carlo simulations were conducted in order to assess the effects of jump network connectivity on the diffusion coefficient. Off-lattice jump networks were created using reverse Monte Carlo, with an objective function defined by agreement to specified inter-site connectivity, inter-site (jump path) distance and consecutive jump angle distributions. Both Gaussian and Poisson distributions of connectivity were applied, with average connectivities spanning a range appropriate for small molecules within a variety of polymers. Distance and angle distributions were taken from earlier work on jump networks in polypropylene. At short times, anomalous diffusion with a range of exponents n ≥ 0.4 was found over the domain of average connectivities. At longer times, diffusion was normal for connectivities above the percolation threshold, while particles were trapped for lower connectivities. The percolation threshold was slightly higher for Gaussian distributions of connectivity than for Poisson distributions. The diffusion coefficient increased linearly for connectivities well above the threshold, with slightly faster diffusion occurring for Gaussian distributions of connectivity.     

Operator product expansion on a fractal: The short chain expansion for polymer networks

We prove to all orders of renormalized perturbative polymer field theory the existence of a short chain expansion applying to polymer solutions of long and short chains. For a general polymer network with long and short chains we show factorization of its partition sum by a short chain factor and a long chain factor in the short chain limit. This corresponds to an expansion for short distance along the fractal perimeter of the polymer chains connecting the network vertices and is related to a large mass expansion of field theory.

The scaling of the second virial coefficient for bimodal solutions is explained. Our method also applies to the correlations of the multifractal measure of harmonic diffusion onto an absorbing polymer. We give a result for expanding these correlations for short distance along the fractal carrier of the measure.     

Water molecules migration at oil–paper interface under the coupling fields of electric and temperature: a molecular dynamics study

Moisture is an important factor affecting the insulation properties of transformers. Due to the limitations of macroscopic experimental methods, the diffusion of water at oil–paper interface cannot be accurately measured. Therefore, molecular dynamics method was used in this work to establish oil–paper layer model of 10⁵ atoms. Through jointly analysing the aggregation degree, diffusion coefficient, free volume as well as radial distribution function of water molecules, the diffusion mechanism of water molecules at oil–paper interface was studied. The results show that when the initial water content in paper was high, water molecules would accumulate at oil–paper interface to form the local high-water region during heating. The polarisation of the electric field strengthened the hydrogen bonding interaction between water molecules and increased the probability of occurrence of the high-water region. Meanwhile, electric field reduced the free volume and diffusion coefficient of water molecules and rendered its diffusion coefficient anisotropic. What’s more, when the electric field was combined with the temperature field, the electric field played a leading role in the diffusion of water molecules while the temperature field was less affected. Diffusion coefficients of water molecules at different temperatures from molecular dynamics simulations were well consistent with experimental results, which verified the rationality of the model.     

Unusual behaviour of poly(ethylene-oxide) in aqueous mixtures

The model system of poly(ethylene-oxide) or PEO, where the changing hydrogen-bond connectivity of the water has large effect on the conformation of the polymer chain, in mixtures of water and acetonitrile, is experimentally studied. The results show the existence of a threshold water content in the system at which the 3d connectivity of the water network begins. Unusual expansion of the polymer chain, an effect larger than that observed in either of the pure solvents, is seen. Upon addition of small amounts of a monovalent salt, binding of ion to polymer takes place in pure acetonitrile solutions. Salt ions begin to co-ordinate with water molecules at the same solvent ratio as the threshold for water network formation. Ions now no longer complex to PEO; instead, hydrogen bonding of water to the polymer strongly dictates conformation in this regime.Received: 10 September 2004, Published online: 3 November 2004PACS: 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 61.12.Ex Neutron scattering techniques (including small-angle scattering) - 36.20.Ey Conformation (statistics and dynamics)     

Effective temperature scaled dynamics of a flexible polymer in an active bath

Langevin dynamics simulations are employed to study the dynamical properties of a flexible polymer in an active bath. The diffusion of the centre of mass and end-to-end distance fluctuation are particularly analysed. We modulate both active force and active particle size to probe the activity-induced facilitation of polymer dynamics. Results indicate diffusivity and chain relaxation time can be well scaled by the effective temperature of the active bath. In addition, diffusion dynamics demonstrates an anomalous superdiffusive behaviour in short time scales, which becomes more prominent with increasing active particle size. Lastly, we extract the effective viscosity experienced by the probed chain, showing a sharp decrease with increment of effective temperature. The attenuation of effective viscosity due to activity might be responsible for the facilitated polymer dynamics.     

Temperature effect in a montmorillonite clay at low hydration—microscopic simulation

The effect of temperature in the range 0–150°C was studied for homo-ionic montmorillonite clays with Na⁺ and Cs⁺ compensating ions in low hydration states. Monte Carlo and molecular dynamics simulations were employed to provide both static and dynamic information concerning the interlayer ions and water molecules, and emphasis was laid on the temperature activation of the diffusion coefficients. Principal structural changes were limited to the interlayer water phase. In the monohydrated systems, neither of the cations was seen to enter into the hexagonal cavities of the clay. Cs⁺ exhibited clear site-to-site diffusion between sites allowing coordination to six oxygen atoms of the clay sheets, this behaviour persisting to high temperatures. Preferential sites for the Na⁺ counterion were much less well-defined, even at low temperatures. The behaviour of the water phase in the monohydrated states was similar for the two ions. A rapid approach to bulk dynamics was seen in the transition from monohydrated to bihydrated Na-montmorillonite. A detailed quantitative comparison of the temperature activation of diffusion for a two-dimensional water phase and three-dimensional bulk water is presented for the first time.     

Charge Separation at the Evaporation (Condensation) Front of Water and Ice. Charging of Spherical Droplets

Charge separation at evaporation (condensation) front of water and ice is analyzed. Relatively low distribution coefficient of protons and hydroxide ions between vapor and condensed phase that is less than the distribution coefficient of water molecules leads to accumulation of protons and hydroxide ions at the phase front upon evaporation and a decrease in the amount of such species upon condensation. Interphase charge separation is caused by the subsequent diffusion of nonequilibrium protons and hydroxide ions. The charge separation is also affected by the double electric layer generated by orientation defects at the water and ice surfaces. Dependences of electric field at a plane surface of water and ice on the rate of phase transformation are calculated. Electric charges of spherical water droplets are estimated at different field strengths and droplet radii.     

Cooperative Association of p-Alkylbenzene Sulfonates Sodium Salts to Poly-2-(dimethylamino) Ethylmethacrylate-N-alkyl Quaternized at the Water/Chloroform Interface

The association of p-alkyl benzene sulfonate sodium salts with several poly-2-(dimethylamino) ethylmethacrylate-N-alkyl quaternized bromides at the water/chloroform interface was studied. High association percentages were found which increase with both the size of the sulfonate molecule and the length of the polyelectrolyte side chain: octyl, decyl, dodecyl and tetradecyl. The results fit well to the Hill's equation for the association of anionic surfactant to polyelectrolytes. Benzene sulfonate shows an anticooperative behavior for the association, whereas 4-methyl benzene sulfonate and 4-ethylbenzene sulfonate are increasingly cooperative for the association. From the association constants, the standard free energies of transfer from water to the interfacial polyelectrolytes were determined. Their values were a linear function of the number of carbon atoms of the aliphatic residue of the benzene sulfonate molecule ranging from ?15.7 kJ/mol of CH₂ groups for the octyl polyelectrolyte to ?18.9 kJ/mol of CH₂ groups for the tetradecyl derivative. These values are similar to those reported for the association of some of these sulfonates molecules with ammonium type cationic micelles. The results for the incremental free energy of transfer by mol of methylene group from water to micelles are in the same order of magnitude as those reported for p-alkyl phenoxides and p-alkylbenzoates to hexadecyltrimethyl ammonium bromide micelles. The results shows that amphipathic counterions as small as 4-ethylbenzenesulfonate are enough to induce a cooperative effect in their association to cationic polyelectrolytes.     

Properties of aqueous NaCl solutions in external electromagnetic fields

Molecular dynamics simulations are performed to investigate the effects of an external electromagnetic field on aqueous NaCl electrolyte solutions at a temperature of 298 K. The simulations assume that the electromagnetic waves propagate in the x-axis direction with a frequency of 50, 100 or 200 GHz. The intensity of the electromagnetic field is assumed to vary in the range 0.1–0.3 V/Å. The simulations are conducted for two different NaCl solution concentrations, namely 1 m and 5 m (molality). The results indicate that as the intensity of the electromagnetic field is increased, the re-orientation of the water molecules becomes more pronounced and the diffusion coefficient of the aqueous NaCl solution increases. It is also shown that in both the low-concentration and high-concentration solutions, the diffusion coefficients of water molecules and ions increase as the frequency and intensity of the electromagnetic field increase.     

Nano-sized local magnetic field induced by circular motion of ions and molecules in a nanotorus under gigahertz rotating electric fields

Recently, we reported molecular dynamics simulations of stable cyclotron motions of ions and water molecules in a carbon nanotorus, induced by different rotating electric fields (EFs). This study is devoted to the calculation and characterisation of the magnetic field (MF) induced by these cyclotron motions. Results show that carbon nanotorus containing ions or water molecules acts as an EF-to-MF transducer. Components of the instantaneous induced MF show large-scale oscillations superimposed by strong fluctuations arising respectively from overall circular motion and random collisions of moving species. Analysis of the space-dependencies of the induced MF components shows that the induced MF is maximum at the centre of the nanotorus. The MF induced by cyclotron motion of ions follows the orders B(Ca²⁺)?>?B(Na⁺)?≈?B(K⁺) at E?=?1.0?V/nm and B(E?=?1.0?V/nm)?>?B(E?=?0.5?V/nm)?>?B(E?=?0.1?V/nm). The time-averaged induced MF of the cyclotron motion of 81 water molecules is almost 10² times stronger than that of ions. The induced MF strength is decreased with increasing distance from nanotorus and decays effectively at about 17.3–18.1 and 15.9–18.2?nm along the z-axis of the nanotorus for ions and water molecules, respectively. The magnitude of the MF induced by cyclotron motions of water molecules and ions, respectively, decreases and increases in the nanotorus with freed carbon atoms.