Effect of diphenylsiloxane unit content on relaxation behavior of poly(dimethylsiloxane‐co‐diphenylsiloxane)

The relaxation behaviors of poly(dimethylsiloxane‐co‐diphenylsiloxane)s with different compositions were investigated using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). It is indicated that the content of Ph₂SiO unit, which is closely associated with crystallinity of polysiloxane, has a remarkable influence on its relaxation behavior. Two‐phase (crystalline and amorphous phase) structure in the semicrystalline polysiloxane of the present system can be determined for discussing relaxation behavior. An increase in relaxation strength can be reasoned to a cooperative effect of decrease in fraction of crystalline phase and increase in friction between molecular chains. And enhancements in glass transition temperature (T_g) and effective activation energy for glass transition (E_a(eff)) were ascribed more to the stiffness imposed by Ph₂SiO unit than decrease in fraction of crystalline phase. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1652–1659, 2008     

Interfacial friction between semiflexible polymers and crystalline surfaces

The results obtained from molecular dynamics simulations of the friction at an interface between polymer melts and weakly attractive crystalline surfaces are reported. We consider a coarse-grained bead-spring model of linear chains with adjustable intrinsic stiffness. The structure and relaxation dynamics of polymer chains near interfaces are quantified by the radius of gyration and decay of the time autocorrelation function of the first normal mode. We found that the friction coefficient at small slip velocities exhibits a distinct maximum which appears due to shear-induced alignment of semiflexible chain segments in contact with solid walls. At large slip velocities, the friction coefficient is independent of the chain stiffness. The data for the friction coefficient and shear viscosity are used to elucidate main trends in the nonlinear shear rate dependence of the slip length. The influence of chain stiffness on the relationship between the friction coefficient and the structure factor in the first fluid layer is discussed.     

Direct observation of slow molecular relaxation by high-resolution light scattering spectroscopy

We developed a novel dynamic light scattering system to observe elastic relaxation phenomena with hyper frequency resolution. The principle of the measurement is based on the theory, which describes the dynamic structure factor of fluid under the condition of the frequency dependent compressibility. The dynamic structure factor, which is usually composed of the Brillouin and Rayleigh triplet, is modulated and shows an additional central component that directly reflects the whole aspect of the relaxation. In the experiment, the output from a frequency-doubled cw-YAG laser was incident into the liquid sample and the power spectrum of the light scattered into the backward direction was analyzed by the optical beating spectroscopy technique. The sample is liquid acetic acid that is known to show a strong ultrasonic relaxation around 1 MHz due to the molecular association process. We could find in the observed spectrum, the central component introduced by the phenomenon, whose relaxation frequency and the strength can be obtained from the width and the intensity of the observed central peak, respectively. The results show very good agreement with those previously obtained by the conventional ultrasonic spectroscopy technique.     

The Estimation of Statistical Parameters Determining the Relaxation Times of Nematic Elastomers: A Three‐Chain Network Model

A simplified “three‐chain” network model formed from freely jointed polymer chains consisting of Gaussian elements with fixed mean‐square lengths is proposed for describing local dynamic properties of nematic elastomers. The boundaries of a polymer network are supposed to be fixed when sample volume and shape do not change with ordering. Relaxation times characterising intrachain motions in both isotropic and ordered states are determined by two factors. The first (“dynamic”) factor is related to the friction of chain elements and the second one (“statistical” factor) is determined by statistical mean–square fluctuations of segment projections on the three axes of rectangular frame of reference. The “statistical” factor of relaxation times is calculated here as a function of the order parameter and the parameter characterising the degree of network crosslinking. Statistical factor obtained in the framework of a network model consisting of Gaussian subchains is compared with that calculated here by using freely‐jointed‐rods chain model. Good agreement is shown between statistical factors obtained in the framework of the two chain models considered. This result confirms the validity of describing the dynamics of real rod‐like mesogenic groups in nematic elastomers in terms of a simplified chain model consisting of Gaussian segments with fixed average lengths which do not change with ordering. The influence of “dynamic” factor on the relaxation spectrum of a nematic elastomer is discussed qualitatively.     

Effects of Nematic Ordering on the Relaxation Spectrum of a Polymer Network with Included rod‐like Particles: Mean‐Field Approximation

Summary: Equilibrium and local dynamic properties of ordered polymer networks with included rod‐like particles are considered using a simplified network model. Lagrange multipliers in the equations of motion of rigid rods are replaced by their averaged values. This approximation corresponds to modelling rod‐like particles by elastic Gaussian springs with mean‐square lengths independent of the orientational order. Nematic‐like interactions between network segments and rods are taken into account in terms of the Maier‐Saupe mean‐field approximation. Nematic ordering of rods induces network segments ordering and changes the relaxation spectrum of the network. The relaxation spectrum of the ordered network splits into two main branches for parallel and perpendicular components of chain segments with respect to the director. Relaxation times of a polymer network are calculated as functions of the wave number for the corresponding normal mode and of the order parameter taking into account both the dynamic factor (determined by friction effects) and the statistical factor (related to mean‐square fluctuations of segment projections). We compare the relaxation spectra of ordered unstretched polymer networks with fixed boundaries with those for polymer networks at free boundaries. A polymer network with free boundaries is stretched along the director. This produces additional fine structure of the two main branches in the relaxation spectrum.

Cell of a three‐chain network model with included rods.     

Solution structure of folic acid. Molecular mechanics and NMR investigation

The structure of folic acid in solution was investigated by nuclear magnetic resonance (NMR) and theoretical calculations. Dynamical information and geometrical constraints were obtained by carbon-13 relaxation study, homo-nuclear NOESY spectra and hetero-nuclear 1H-13C NOE experiments. This set of experimental data was used for the molecular mechanics and molecular dynamic calculations. The accuracy of the final structure was established by the R(NMR) factor, which was calculated comparing the experimental NOESY cross-peaks intensities and the corresponding values simulated by using the complete relaxation matrix analysis (CORMA) approach.     

Association of polybutadiene living anions in cyclohexane

Simultaneous measurements of static and dynamic light scattering were made for cyclohexane solutions of living polybutadiene (PB) anion to characterize PB components existing in the solutions. There were two relaxation modes in the relaxation time spectra obtained by dynamic light scattering. The static structure factor and hydrodynamic radius of the major fast relaxation component obtained are explained by the unimer‐tetramer equilibrium model. The same model is also consistent with the data of the propagation reaction rate of the PB living anion in cyclohexane. The slow relaxation component is only minor (less than 1 wt %), but has a large radius of gyration of ca. 200 nm, and is assigned to aggregates consisting of a huge number of PB living anion chains. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1401–1407, 2005     

Relaxation in Poly(alkyl methacrylate)s: Crossover Region and Nanophase Separation

Relaxations in a poly(alkyl methacrylate) series are systematically influenced by chemical modifications like the variation of side‐chain length, random copolymerization, or molecular weight. Recent results concerning the influence of chemical modifications on special parts of the relaxation chart are reviewed. The discussion is focused on two points: (i) The influence of chemical modifications on the crossover region of dynamic glass transition, where the relaxation times of α relaxation and Johari Goldstein mode β approach each other, is discussed. A general crossover scenario with a separate onset of cooperative α relaxation is observed for all lower members of this series. High temperature process a above and cooperative α relaxation below the crossover are shown to be distinct processes. Chemical modifications related to an increase in free volume shift this scenario mainly to lower frequency and temperature. Further details depend on the specific modification. (ii) The nanophase separation of incompatible main‐ and side‐chain parts in all higher members of the poly(alkyl methacrylate) series is discussed. This effect is concluded from the coexistence of two dynamic glass transitions in these homopolymers, the conventional a (or α) process and an additional low temperature glass transition α_PE . It is shown that the low T_g process is related to cooperative motions in the polyethylene‐like side‐chain parts. The existence of static nanodomains in the range 0.5 to 1.5 nm is confirmed by means of wide and small angle X‐ray scattering data. The estimated nanodomain size is compared with the size of dynamic heterogeneities estimated independently from calorimetric data for the polyethylene‐like glass transition using the fluctuation approach.     

High frequency dynamics and structural relaxation process in liquid ammonia

The dynamic structure factor S(Q,omega) of liquid ammonia has been measured by inelastic x-ray scattering in the terahertz frequency region as a function of the temperature in the range of 220-298 K at a pressure P=85 bars. The data have been analyzed using the generalized hydrodynamic formalism with a three term memory function to take into account the thermal, the structural, (alpha) and the microscopic (mu) relaxation processes affecting the dynamics of the liquid. This allows to extract the temperature dependence of the structural relaxation time (tau(alpha)) and strength (Delta(alpha)). The former quantity follows an Arrhenius behavior with an activation energy E(a)=2.6+/-0.2 kcal/mol, while the latter is temperature independent suggesting that there are no changes in the interparticle potential and arrangement with T. The obtained results, compared with those already existing in liquid water and liquid hydrogen fluoride, suggest the strong influence of the connectivity of the molecular network on the structural relaxation.     

高聚物玻璃化转变温度和分子参数的关系 Ⅰ.高聚物链柔性与T_g的关系

本文采用晶格模型,以动力学链段长度作为统计单元大小,推导了高聚物玻璃化温度T_8和链静态刚性因子σ~2(T_8),链动态刚性因子β(T_8)以及聚合度DP等分子参数之间的关系。具体讨论了链柔性对T_8的影响。理论预测和几十种聚合物的实验数据能较好吻合,分析结果表明T_8值基本上取决于高聚物链σ(T_8)大小。     

Computational study of the texture formation in mesophase pitch‐based carbon fibres

This paper studies the thermal relaxation phenomena after melt‐extrusion of a rigid discotic uniaxial nematic mesophase pitch using mathematical modelling and computer simulation. The Ericksen and Landau–de Gennes continuum theories are used to investigate the structure development and texture formation across mesophase pitch‐based carbon fibres. The two‐dimensional model captures five types of transverse patterns, which match the commonly observed textures for mesophase pitch‐based carbon fibres. They are: random, zig‐zagged radial, radial, quasi‐onion and onion. These textures represent the various combinations possible from the interplay between structure (i.e. texture) development and cooling during the fibre spinning process. During the thermal relaxation after the cessation of extensional flow the discotic nematic molecules store elastic free energy decays. The distorted nematic molecular profiles reorient to release the stored elastic free energy. The difference in time scales for molecular reorientation and thermal relaxation result in different transverse textures. The rate at which the fibres are cooled is the main factor in controlling the structure development. A slow cooling rate would permit the nematic discotic molecules to reorient to a well‐developed (radial or onion) texture. The random texture is a result of rapid quenching. The numerical results are consistent with published experimental observations.     

Physical aging of epoxy polymers and their composites

Exposure to extended periods of sub‐T_g temperatures causes physical changes in the molecular structure of epoxy resins and epoxy‐based materials to occur. These physical aging mechanisms include the reduction in free volume and changes to the molecular configuration. As a result, mechanical, thermodynamical, and physical properties are affected in ways that can compromise the reliability of epoxy‐based engineering components and structures. In this review, the physical changes in the molecular structure of epoxies are described, and the influence of these changes on the bulk‐level response is detailed. Specifically, the influence of physical aging on the quasistatic mechanical properties, viscoelasticity, fracture toughness, thermal expansion coefficient, volume relaxation, enthalpy relaxation, endothermic peak temperature, fictive temperature, and moisture/solvent absorption capability is reviewed. Also discussed are relationships between relaxation functions, crosslink density, composite reinforcement, and epoxy/copolymer blending and the physical aging response of epoxies. Finally, the concepts of thermal and mechanical rejuvenation are discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

环氧交联网T_g转变的tanδ-T曲线解析

本文系统地研完了预聚物分子量、固化剂配比和固化条件对环氧交联网T_g松弛内耗峰松弛时间分布的影响。本实验和理论研究结果首次证明了环氧交联网T_g松弛过程具有单一松弛时间描述的线性标准固体的特征,与预聚体分子量、固化剂配比和固化条件无关。此结果可用环氧交联网的两相结构特征加以解释。     

Relaxation time scales in collective dynamics of liquid alkali metals

In this paper the investigation of the dynamical processes of liquid alkali metals is executed by analyzing the time scales of relaxation processes in liquids. The obtained theoretical dynamic structure factor S(k,omega) for the case of liquid lithium is found to be in excellent agreement with the recently received inelastic x-ray scattering data. The comparison and interrelation with other theories are given here. Finally, an important part of this paper is the confirmation of the scale uniformity of the dynamic processes in liquid alkali metals predicted by some previous molecular dynamic simulation studies.     

Dynamic Bonds Mediate π-π Interaction via Phase Locking Effect for Enhanced Heat Resistant Thermoplastic Polyurethane

Stimulus-responsive polymers containing dynamic bonds enable fascinating properties of self-healing, recycling and reprocessing due to enhanced relaxation of polymer chain/network with labile linkages. Here, we study the structure and properties of a new type of thermoplastic polyurethanes (TPUs) with trapped dynamic covalent bonds in the hard-phase domain and report the frustrated relaxation of TPUs containing weak dynamic bond andπ-πinteraction in hard segments. As detected by rheometry, the aromatic TPUs with alkyl disulfide in the hard segments possess the maximum network relaxation time in contrast to those without dynamic bonds and alicyclic TPUs. In situ FTIR and small-angle scattering results reveal that the alkyl disulfide facilitates stronger intermolecular interaction and more stable micro-phase morphology inπ-πinteraction based aromatic TPUs. Molecular dynamics simulation for pure hard segments of model molecules verify that the presence of disulfide bonds leads to strongerπ-πstacking of aromatic rings due to both enhanced assembling thermodynamics and kinetics. The enhancedπ-πpacking and micro-phase structure in TPUs further kinetically immobilize the dynamic bond. This kinetically interlocking between the weak dynamic bonds and strong molecular interaction in hard segments leads to much slower network relaxation of TPU. This work provides a new insight in tuning the network relaxation and heat resistance as well as molecular self-assembly in stimulus-responsive dynamic polymers by both molecular design and micro-phase control toward the functional applications of advanced materials.     

Structure and dynamics of MG rubber studied by dynamic mechanical analysis and solid‐state NMR

Methyl‐methacrylate‐grafted natural rubber was prepared by free radical polymerization of methyl methacrylate in natural rubber latex, and their structure and dynamics were investigated by dynamic mechanical analysis and solid‐state nuclear magnetic resonance (NMR). Samples were prepared by chemical initiation and high‐energy radiation. The changes of glass transition temperature and tan δ max with different total poly(methyl methacrylate (PMMA) content are reported. The effect of the change in composition in copolymers on tan δ peak width, tan δ max, and area under the tan δ curve are used to understand the miscibility and damping properties. Solid‐state ¹³C‐NMR measurements were carried out to determine several relaxation time parameters, such as rotating frame and laboratory frame proton and carbon relaxation times. Cross polarization times and carbon relaxation times were interpreted based on the changes in the molecular motion. Proton relaxation times were interpreted based on the heterogeneity of the matrix. Results confirmed phase separation and a presence of an interfacial region. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1141–1153, 1999     

Viscoelastic properties of decrosslinked irradiation‐crosslinked polyethylenes in supercritical methanol

The viscoelastic properties of decrosslinked irradiation‐crosslinked polyethylenes using a supercritical methanol were investigated via oscillatory dynamic shear measurements. Decrosslinked polymers at a low reaction temperature exhibited solid‐like rheological properties, as evidenced by a small slope at G′ and G″, a long relaxation time, slow stress relaxation behavior, and considerable yield stress. In contrast, decrosslinked polymers at a high temperature exhibited liquid‐like rheological properties that included a large slope in G′ and G″, a short relaxation time, fast stress relaxation behavior, and nonyield stress. The difference in the viscoelastic properties of the decrosslinked polyethylenes was attributed to the difference in the gel content with the reaction temperature. A higher gel content induced stronger solid‐like viscoelastic properties. Hence, the rheological measurements were useful for analyzing the molecular structure of decrosslinked polymers using a supercritical fluid. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1265–1270, 2010     

Preparation and properties of novel fluorosilicone thermoplastic vulcanizate with cross‐linking–controlled core‐shell structure

A new fluorosilicone thermoplastic vulcanizate (TPV) composed of poly(vinylidene fluoride) (PVDF), silicone rubber (SR), and fluororubber (FKM) was successfully prepared through dynamic vulcanization. The morphological structure of the TPVs had core‐shell elastomer particles dispersed in a continuous PVDF matrix. Furthermore, the cross‐linking of core‐shell structure was controlled by adopting different curing agent. The effect of cross‐linking–controlled core‐shell structure on the morphology, crystallization behavior, stress relaxation test, solvent‐resistant properties of the obtained TPVs were investigated. It was found that the shell cross‐link had a significant influence on the crystallinity of the PVDF phase. The core‐shell bicross‐linked TPV was found to provide the lowest rate of relaxation. An obvious stress softening phenomenon was observed in the uniaxial loading‐unloading cycles in tension. The bicross‐linked TPV had good solvent resistant properties. The tensile strength of the bicross‐linked TPV was still 12 MPa even after immersed in butyl acetate for 48 hours.     

Molecular mobility of poly(vinylidene fluoride) in the anisotropic state

The effect of uniaxial orientational drawing and subsequent isometric annealing on the molecular mobility of poly(vinylidene fluoride) was studied by dielectric spectroscopy and dynamic mechanical analysis. The influence of orientation, the polymorphic composition of the crystalline phase, and the structure of disordered regions on dielectric and mechanical relaxation in isotropic and oriented samples was investigated.