聚氧乙烯月桂醚在含醇的非水体系中的热力学性质的微量量热法研究

对于非离子表面活性剂聚氧乙烯月桂醚(Brij-35)/N,N-二甲基甲酰胺(DMF)/长链醇(庚醇,辛醇,壬醇,癸醇)体系,利用滴定微量量热仪测定了胶束形成过程的热功率-时间曲线.根据热力学理论,测定了临界胶束浓度和胶束形成热(ΔHmθ),计算了热力学函数(ΔGmθ和ΔSmθ).讨论了温度、醇中的碳原子数、醇的浓度与临界胶束浓度和热力学函数之间的关系.结果表明:聚氧乙烯月桂醚(Brij-35)/DMF/长链醇体系:(1)在含有相同浓度的各种醇的体系中,ΔHmθ和ΔSmθ的值随着温度的升高而增大;CMC,ΔGmθ的值随着温度的升高而降低;(2)在相同温度及相同浓度的醇体系中,CMC,ΔHmθ,ΔGmθ和ΔSmθ的值都随着醇中碳原子数的增加而降低;(3)在相同温度及相同醇的体系中,CMC,ΔHmθ,ΔSmθ和ΔGmθ的值随着醇的浓度的增加都减小.     

丁二酸二异辛酯磺酸钠在长链醇/N,N-二甲基甲酰胺体系中临界胶束浓度和热力学函数的微量量热法研究

用微量量热法研究了丁二酸二异辛酯磺酸钠(AOT)在N,N-二甲基甲酰胺(DMF)/长链醇(正戊醇、正己醇、正庚醇、正辛醇)体系中的临界胶束浓度(CMC)和热力学函数( , 和 ). 并分析讨论了醇的浓度、醇中的碳原子数及温度与CMC及热力学参数之间的关系. 结果表明, 在AOT/长链醇/DMF体系中, 当醇中的碳原子数相同且醇的浓度相同时, CMC, , 随温度的升高而增大, 而 随温度的升高而降低|当温度相同且醇中的碳原子数相同时, CMC, , 和 随醇浓度的增加都降低|而当温度相同且醇的浓度相同时, CMC, , 和 随醇中碳原子数的增加都降低.     

大分子溶致凝聚过程中的几个分界浓度

按照现代高分子凝聚态物理学观点,高分子溶液按浓度分为:极稀溶液、稀溶液、亚浓溶液、浓溶液、极浓溶液5个层次,各层次间的分界浓度分别称为动态接触浓度、接触浓度、缠结浓度和全高斯链浓度,其中全高斯链浓度由本文作者命名。文中给出各分界浓度的定义,介绍各分界浓度的物理意义,特别说明命名全高斯链浓度的依据。同时详细讨论了不同浓度溶液中大分子链的构象及其变化、链间相互作用的本质和微观图像、以及溶液浓度变化对溶液性质的影响。     

柱阵列中高分子的爬行过程

利用Monte Carlo算法模拟了嵌入柱阵列中高分子的爬行过程.模拟结果显示窄间距的柱阵列可以有效地抑制嵌于其中的高分子链的长度涨落,并使得高分子链的弛豫时间符合爬行理论给出的标度律.通过对比爬行理论与模拟得到的链端关联函数可知,柱阵列中的爬行过程与高分子熔体中的爬行过程存在着微妙的差别.在柱阵列中高分子的链端无法完全消灭原有的管道,从而导致了链端关联函数被爬行理论低估.本文给出的二维自回避格点模型则可以很好地描述柱阵列中高分子的爬行过程.     

对流扩散传质滞后的电极过程中之非Poisson涨落与非Nernst浓度极化

根据对流扩散传质滞后的恒稳电极过程中边界层的物理图像, 提出了该类电极过程的简化随机模型, 建立了相应的浓度极化的随机热力学理论, 揭示了非Nernst浓度极化来自于随电流密度增大电极化学反应体系涨落分布的非Poisson化与对中心极限律的偏离, 进一步阐明了与滞后的扩散步骤共存的对流传质对非Nernst浓度极化的效应及其规律. 同时, 给出了对流引起的非Nernst浓度极化的随机热力学算例.     

微量量热法研究阴离子表面活性剂在DMA/长链醇体系中CMC和热力学函数

在N,N-二甲基乙酰胺(DMA)/长链醇非水溶液体系中, 利用微量量热仪, 研究阴离子表面活性剂十二烷基羧酸钠(SLA)、十二烷基硫酸钠(SDS)的临界胶束浓度(CMC)和热力学函数. 本文在十二烷基羧酸钠, 十二烷基硫酸钠的N,N-二甲基乙酰胺溶液中, 分别加入长链醇(庚醇、辛醇、壬醇、癸醇), 测定体系的热功率-时间曲线. 借助热力学理论, 由测得曲线, 进一步得到临界胶束浓度和热力学函数(ΔH_m⁰, ΔG_m⁰和ΔS_m⁰). 讨论了温度、醇的碳原子数目、醇的浓度与热力学参数之间的关系. 结果表明, 对十二烷基羧酸钠或十二烷基硫酸钠的DMA溶液, 在含有相同浓度的各种醇的体系中, CMC, ΔH_m⁰和ΔS_m⁰的值随着温度的升高而增加, 而ΔG_m⁰的值随着温度的升高而降低. 在相同温度及相同浓度的醇体系中, CMC, ΔH_m⁰,ΔG_m⁰和ΔS_m⁰的值都随着醇中碳原子数目的增加而降低. 在相同温度及相同醇的体系中, CMC, ΔG_m⁰的值随着醇的浓度的增加而增大, 而ΔH_m⁰, ΔS_m⁰的值随着醇的浓度的增加而减少.     

侧链液晶离聚物对PA1010/PP共混体系的增容作用

将聚酰胺（PA1010）、聚丙烯（PP）和热致型侧链液晶离聚物（SLCI）进行熔融共混，采用FTIR，SEM，DSC，WAXD研究测定了共混物中的相互作用，用形态结构，热行为和结晶行为，系统地研究了SLCI对PA101／PP共混物的增容作用。结果表明，SLCI有效地改善了PA1010／PP共混物的形态结构，增强了PA1010与PP链间的相互作用，使PA1010／PP熔点升高，结晶度提高。     

高分子链在微通道剪切流中的迁移机制及浓度的影响

提出了剪切流中高分子链在微通道内的迁移机制.该机制采用珠-簧链模型表示高分子链,高分子链受剪切作用而被拉伸,相邻珠子之间的流体力学相互作用产生了对称的扰动流场,由于在通道壁面附近对称的流场被破坏,壁面与高分子链间的流体力学相互作用使高分子远离壁面,在强受限时,这种壁面诱导的流体力学相互作用会被屏蔽掉.利用耗散粒子动力学数值模拟了高分子链在微通道压力流中的迁移行为.数值模拟结果表明,在受限较弱时,高分子链向远离壁面的方向迁移,并随着流场增强,远离壁面的趋势越强;在受限较强时,高分子链不会发生远离壁面的行为.实验研究了长链高分子λ-DNA在壁面附近的迁移行为,实验结果及模拟结果与迁移机制预测的结果相吻合,验证了迁移机制的正确性.高分子链浓度会影响高分子链的迁移行为,当高分子链浓度较大时,高分子链在通道宽度方向不会发生迁移现象,意味着随着浓度的增大,壁面与高分子链间的流体力学相互作用会逐渐被屏蔽.     

线性和非线性聚合物的相分离

分子共混物从20世纪60年代开始,引起很多科学家的兴趣.加工过程中,聚合物相分离过程中的热力学和动力学起了重要的作用,赋予了共混物一定的形貌,提供了很多人们需要的功能.关于聚合物的相分离问题,近年来无论在实验还是在理论上都得到了很大的发展.聚合物相分离的热力学是以Flory-Huggins的平均场理论为基础,动力学以CHC(Cahn-Hilliard-Cook)的线性理论为基础.在本文中,我们对亚稳相分离SD(Spinodal Decomposition)的热力学和动力学都进行了考察.描述了测量二元共混物的浓度涨落的静态散射实验,给出了在二元共混物体系的SD的近期理论计算.首先,从普适的Langevin方程推导CHC理论,从而给出CHC的唯象的平均场理论的微观图象.然后介绍模式耦合计算,从而将SD理论扩展到非线性区域.通过将短期SD分解与高分子共混物的对比揭示了定量计算的本质.最后,讨论了一些近年来在剪切场下相行为的研究以及该领域可能的发展方向.     

侧链为长链烷基醚的聚硅氧烷的合成及其药物控制释放性能的研究

通过硅氢加成法合成了侧链为长链烷基醚的聚硅氧烷及共聚物，研究了其相转变性质以及由其组成的共混硅橡胶薄膜对避孕药物（左旋十八甲基炔诺酮）的释放性能．结果表明：聚硅氧烷的熔融温度随侧链烷基的增长而提高；共聚硅氧烷的熔融温度随较长烷基的比例增加而提高；聚硅氧烷的侧链烷基呈侧向有序性排列．药物分子透过薄膜的速率及其温度依赖性与共混膜中侧链烷基的有序状态有关，即由晶态转变为非晶态时，药物的透过速率加快     

SCATTERING FUNCTION OF POLYMER BLENDS

For a system of flexible polymer molecules, the concepts of two concentrations, namely the segmental and the molecular concentrations, have been proposed in this paper. The former is equivalent to the volume fraction. The latter can be defined as the number of the gravity centers of macromolecules in a unit volume. The two concentrations should be correlated with each other by the conformational function of the polymer chain and should be discussed in different thermodynamic equations. On the basis of these concepts it has been proved that the Flory-Huggins entropy of mixing should be the result of the mixing “ideal gases of the gravity centers of macromolecules“. The general correlation between the free energy of mixing and the scattering function (structural factor) of polymer blends has been studied based on the general fluctuation theory. When the Flory-Huggins free energy of mixing is adopted, the de Gennes scattering function of a polymer blend can be derived.     

Termination rate constant in free-radical polymerization

The specific rate constant for the termination reaction between two flexible polymer molecules with active chain ends has been considered in relation to the segmental diffusion of chain ends in solution. The probability of reaction between two chain ends per unit time when the centers of gravity of two polymer molecules are at a distance of separation has been calculated by using the Smoluchowski equation and a Gaussian distribution of chain ends. The time during which two polymer molecules are in contact has also been calculated by using the diffusion equation and the potential energy function for intermolecular interaction. The rate constant may then be completely expressed as a complex function of the intramolecular linear expansion factor, molecular weight, and the frictional properties of the reacting polymers' segment. This expression predicts that the rate constant is inversely proportional to solvent viscosity, decreasing with increasing molecular weight to some extent, and is affected by the excluded volume effect and chain flexibility. The complete expression for the rate constant has been simplified and the result compared with experimental data. Close agreement is found between the calculated rate constants and those experimentally obtained.     

Adam-Gibbs based model to describe the single component dynamics in miscible polymer blends under hydrostatic pressure

We present in this work a new model to describe the component segmental dynamics in miscible polymers blends as a function of pressure, temperature, and composition. The model is based on a combination of the Adam-Gibbs (AG) theory and the concept of the chain connectivity. In this paper we have extended our previous approach [D. Cangialosi et al. J. Chem. Phys. 123, 144908 (2005)] to include the effects of pressure in the component dynamics of miscible polymer blends. The resulting model has been tested on poly(vinyl methyl ether) (PVME)/polystyrene (PS) blends at different concentrations and in the temperature range where the system is in equilibrium. The results show an excellent agreement between the experimental and calculated relaxation times using only one fitting parameter. Once this parameter is known the model allows calculating the size of the relevant length scale where the segmental relaxation of the dielectrically active component takes place, i.e., the so called cooperative rearrangement region (CRR) in the AG framework. Thus the size of the CRR for PVME in the blends with PS has been determined as well as its dependence with pressure, temperature, and concentration.     

Local and chain dynamics in miscible polymer blends: A Monte Carlo simulation study

Local chain structure and local environment play an important role in the dynamics of polymer chains in miscible blends. In general, the friction coefficients that describe the segmental dynamics of the two components in a blend differ from each other and from those of the pure melts. In this work, we investigate polymer blend dynamics with Monte Carlo simulations of a generalized bond fluctuation model, where differences in the interaction energies between nonbonded nearest neighbors distinguish the two components of a blend. Simulations employing only local moves and respecting a no bond crossing condition were carried out for blends with a range of compositions, densities, and chain lengths. The blends investigated here have long time dynamics in the crossover region between Rouse and entangled behavior. In order to investigate the scaling of the self-diffusion coefficients, characteristic chain lengths N(c) are calculated from the packing length of the chains. These are combined with a local mobility mu determined from the acceptance rate and the effective bond length to yield characteristic self-diffusion coefficients D(c)=muN(c). We find that the data for both melts and blends collapse onto a common line in a graph of reduced diffusion coefficients DD(c) as a function of reduced chain length NN(c). The composition dependence of dynamic properties is investigated in detail for melts and blends with chains of length N=20 at three different densities. For these blends, we calculate friction coefficients from the local mobilities and consider their composition and pressure dependence. The friction coefficients determined in this way show many of the characteristics observed in experiments on miscible blends.     

Local segmental relaxation in bidisperse polystyrenes

Dynamic mechanical results are reported for segmental relaxation of monodisperse polystyrenes (PSs) with molecular weights of 0.7, 3, 18, and 104 kg/mol and bidisperse PSs created from blending pairs of these materials. The data for the monodisperse polymers confirm previous findings; namely, there is an increase in the glass‐transition temperature normalized temperature dependence of the segmental relaxation times (fragility) with increasing molecular weight, along with a breakdown of the correlation between the fragility and the breadth of the relaxation function. For both the monodisperse and bidisperse PSs, the glass‐transition temperature is a single function of the average number of chain ends, independent of the nature of the molecular weight distribution. It is also found that these materials exhibit fragilities that uniquely depend on the number‐average molecular weight, that is, on the concentration of chain ends. In blends with linear PS, cyclic PS with a low molecular weight behaves as a high polymer, similar to its neat behavior, reflecting the overriding importance of chain ends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2604–2611, 2004     

Polymer chain diffusion in polymer blends: A theoretical interpretation based on a memory function formalism

The diffusion of polymer chains in miscible polymer blends with large dynamic asymmetry—those where the two blend components display very different segmental mobility—is not well understood yet. In the extreme case of the blend system of poly(ethylene oxide) (PEO) and poly(methyl methacrylate)(PMMA), the diffusion coefficient of PEO chains in the blend can change by more than five orders of magnitude while the segmental time scale hardly changes with respect to that of pure PEO. This behavior is not observed in blend systems with small or moderate dynamic asymmetry as, for instance, polyisoprene/poly(vinyl ethylene) blends. These two very different behaviors can be understood and quantitatively explained in a unified way in the framework of a memory function formalism, which takes into account the effect of the collective dynamics on the chain dynamics of a tagged chain. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1239–1245     

Structural relaxation processes in polyethylene glycol/CCl4 solutions by Brillouin scattering

We present results of a Brillouin scattering experiment on solutions of poly(ethylene glycol) of mean molecular mass 600 g/mol (PEG600) in CCl4. The relaxation process detected has been assigned to conformational rearrangements of the polymeric chains, triggered by reorientation of the side groups. The concentration dependencies of the hypersound velocity and normalized absorption are compared against the indications from several models proposed in the literature. The concentration evolution of the system is described in terms of two distinct regimes. At high polymer content, the system is dominated by the structure of the dense polymer, where polymer-polymer interactions, together with excluded volume effects, induce the existence of a preferred local arrangement resulting in a narrow distribution of the relaxation times, with the average value of the relaxation time following a simple Arrhenius temperature dependence. As the concentration decreases, the original structure of the hydrogen bonded polymer network is destroyed, and a number of different local configuration coexist, giving rise to a wider distribution of relaxation times or to a multiple relaxation. At low concentrations, the experimental data are well fitted assuming a Vogel-Fulker-Tammon behavior for the average relaxation time. In addition, the observed deviation from the ideal behavior for the refractive index and the density suggests that CCl4 does not behave as an inert solvent, and due to polarization effects, it can develop local hetero-associated structures via electrostatic interaction with the O-H end groups of the polymeric chains. The hypothesis has been successfully tested by fitting the concentration behavior of the hypersonic velocity to a recent three-component model, suitable to describe the concentration dependence of sound velocity in moderately interacting fluids. The indication of the model furnishes a very high value for the association constant of the PEG600, confirming the literature indication that, in polymeric systems capable of developing long liner aggregates via hydrogen bonding interaction, the Brillouin probe is insensitive to the true length of the polymeric chains. The Brillouin scattering experiment just sees an effective hydrogen bonded aggregate that is huge relative to the length of the single polymeric chain and becomes sensitive only to the density fluctuations of the local segmental motions.     

EPR spin labelling studies of molecular dynamics in elastomer-silica composites

Novel methods of nitroxyl spin labelling suitable for molecular dynamics studies within the interface regions of SBR elastomer/silica composites have been developed and used together with the nitroxyl spin probe technique. Fast and slow motional components have been identified within the interface regions and the corresponding rotational diffusion tensors have been measured as a function of the temperature and the SiO₂ concentration. The fast rotational frequency is found to be orders of magnitude slower than that measured in the absence of SiO₂. This difference is suggested to arise from a closer packing of the macromolecules near the silica surface caused by the van der Waals bonding interactions. Increase of the SiO₂ concentration results in a decrease of the molecular mobility. This effect has been imputed to the overlapping of the bonding interaction regions. Spin probe measurements in the SBR-SiO₂ matrices using TEMPO, strongly suggest that the hindrance to chain segmental motion induced by the SiO₂-SBR interactions propagates beyond the interface regions thus involving the bulk polymer matrix. It is suggested that the information on the segmental chain dynamics obtained through the spin labelling and spin probe measurements can be developed as a method for investigating the polymer/filler interactions within the reinforcing mechanism by the filler.     

Fluctuation‐assisted crystallization of an iPP/PEOc polymer alloy prepared on a single multicatalyst reactor granule

The new fluctuation‐assisted mechanism for nucleation and crystallization in the isotactic polypropylene/poly(ethylene‐co‐octene) alloy has been studied. We found that the liquid–liquid phase separation (LLPS) had a dominant influence on the crystallization kinetics through the nucleation process. After LLPS, the nucleation of crystallization mainly occurred at the interface of the phase‐separated domains. It is because that the concentration fluctuations of the LLPS induced the motion of polymer chains and possibly some segmental alignment and/or orientation in the concentration gradient regions through interdiffusion, which could assist the formation of nuclei for crystallization. In other words, the usual nucleation energy barrier could be overcome (or at least partially) by the concentration fluctuation growth of LLPS in the unstable regions. This could be viewed as a new kind of heterogeneous nucleation and could be an addition to the regular nucleation and growth mechanism for crystallization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 166–172, 2009     

Dynamics of a poly(isoprene)/poly(vinyl ethylene) blend revisited: Component polymer relaxation and blend behavior

Motivated by recent molecular dynamics simulation studies of miscible blends of dynamically disparate polymers, we have revisited the experimentally measured dielectric relaxation in a 50/50 blend of poly(isoprene) and poly(vinyl ethylene) (PI/PVE). In contrast to efforts to explain the dielectric loss in PI/PVE blends in terms of a distribution of local environments leading to a broad distribution of segmental relaxation times (the so-called concentration fluctuation model), our analysis indicates that there is no evidence for significant broadening of the relaxation processes in the component polymers upon blending. Rather, we find that the dielectric loss of the 50/50 PI/PVE blend can be represented as a sum of α- and β-relaxation processes for the component polymers represented with Havriliak-Negami functions whose shape and relaxation strength are consistent with those obtained for the pure PI and PVE melts. The α-relaxation process for the PVE component was found to be dramatically influenced by blending, moving to much higher frequency with moderate narrowing, while the α-relaxation process for the PI component shifted to somewhat lower frequency with slight broadening, consistent with our MD simulations of a model blend and 2D NMR measurements on PI/PVE blends. In contrast, the β-processes in the PVE and PI components were found to be essentially uninfluenced by blending, with the latter accounting for the significant high-frequency loss observed in the PI/PVE blend.