颗粒介质弹性的弛豫

颗粒介质是复杂的多体相互作用体系, 其弹性源自内部的力链结构, 弹性能量处在亚稳态, 具有复杂的弛豫行为. 在常规作用下, 颗粒介质往往呈现明显的弹性弛豫. 应力松弛是应变恒定时应力的衰减现象, 弹性弛豫是应力松弛的主要原因. 在前期工作基础上, 从弹性势能面和双颗粒温度热力学角度分析了弹性弛豫的机理, 量化了弹性应力演化不可逆过程; 基于双颗粒温度热力学计算得到了弹性能、颗粒温度和应力的演化, 其中应力松弛的计算结果与实验结果基本一致, 讨论了颗粒温度初值和输运系数的影响. 指出, 开展力链结构及其动力学研究是揭示宏观弹性弛豫机理的关键.     

Fabrication of continuous fiber-reinforced thermoplastic composites with structural gradient from sheath-core type bicomponent fibers

Sheath-core type bicomponent fibers of polypropylene (PP) as a sheath component and thermotropic liquid crystalline polymer (TLCP) as a core component were prepared by the highspeed melt spinning process. Continuous fiber reinforced thermoplastic composites, in which TLCP acts as a reinforcing fiber and PP as a matrix polymer, were fabricated by the compression molding of these fibers. In the melt spinning, the attainable highest take-up velocity of TLCP was improved by co-processing with PP. Tensile modulus and strength of the TLCP component in the PP/TLCP bicomponent fibers increased with an increase in the take-up velocity. Comparison of wide-angle X-ray diffraction patterns of starting bicomponent fibers and fabricated composites indicated that the orientation relaxation of TLCP did not occur in the compression molding process. Accordingly, the tensile modulus and strength of the PP/TLCP composites were similar to those of the bicomponent fibers. Continuous fiber reinforced thermoplastic composites with various types of fiber content distributions were fabricated from the bicomponent fibers in which sheath-core composition was changed gradually in the spinning process. In the three-point bending test, the composites with two different types of symmetric structural gradients, one with higher TLCP fiber content near the surfaces than in the center and the other with higher TLCP content in the center than near the surfaces, exhibited different flexural moduli even though the overall TLCP contents were comparable. In the three-point bending test of a composite with asymmetric structural gradient, the yielding behavior and maximum flexural load varied depending on the direction of load application although the initial flexural moduli were similar.     

Quantitative structural characterization of the deformation and shrinkage of isotactic polypropylene fibers and films

A quantitative determination has been made of the structural elements which control deformation and shrinkage processes in isotactic polypropylene fibers and films. It is found that strain processes such as fabrication draw and shrinkage are controlled by the noncrystalline region of this highly crystalline polymer. Quantitative structure-property correlations are obtained for the polymer, which reveal the interactions between temperature, strain, and orientation. The thermal activation energy of the noncrystalline chains is also determined from these solid-state structure measurements.     

Computer simulation of nanoindentation into polymer films

We present computer simulations of nanoindentation into amorphous polymer films. The bulk polymer is treated through a united atom model in connection with molecular dynamics methods. The dynamics of the indenter is modeled as overdamped, such that the indentation velocity is proportional to the difference between the external force acting onto the tool and the resistance force built up in the polymer film. We concentrate on the initial, kinetic stage of the indentation process and give results for the motion of the indenter, the deformation field of the polymer film, the stress field, and the field of total monomer energy. We propose an effective coefficient as a new measure for the resistivity of a surface against indentation. Its value can be determined in an experiment with constant indentation velocity. In addition, we investigate the free drift behavior when the external driving force has been set to zero and the tool is expelled from the polymer film. For different polymer chain lengths, the tool’s motion is exponential in time and we determine the relaxation scale.     

Microcrack dynamics in a polymer composite material during friction

The dynamics of microcracks in the surface layers of a polymer and a polymer composite during friction is studied by triboluminescence (TL). The samples are prepared from poly(phenylene sulfide) (PPS) and a composite consisting of PPS reinforced by carbon fibers. An analysis of the spectra shows that TL appears during the relaxation of the electron excitation of the free radicals that form upon the breakage of chemical bonds in carbon fibers and PPS molecules. TL consists of bursts corresponding to microcrack nucleation, and the burst intensity corresponds to the microcrack surface area. Microcracks form in time intervals of several tens of microseconds rather than continuously. Within these intervals, microcracks form in series sequentially, one by one, at a time step of 3?C4 ??s. Each series consists of several (up to 30) microcracks that also form sequentially, in 20-ns intervals. The sequential nucleation of microcracks and microcrack series is explained by stress redistribution in fracture zones in PPS and the composite.     

The twice-renormalized Rouse formalism of polymer dynamics: Segment diffusion, terminal relaxation, and nuclear spin-lattice relaxation

The twice-renormalized Rouse formalism, a refined version of Schweizer’s renormalized Rouse treatment of chain dynamics in entangled polymers, is presented. The time scale of validity is extended to include the terminal chain relaxation and center-of-mass diffusion. In clear contrast to the laws concluded from other polymer dynamics concepts (such as the reptation (tube) model or the polymer mode-mode coupling formalism), the predictions perfectly coincide with all the results of recent spin-lattice relaxation dispersion and diffusion experiments as well as with computer simulations. On the other hand, the twice-renormalized Rouse formalism fails to explain the rubber-elastic plateau of stress relaxation. It is inferred that this is a consequence of the single-chain nature of the present approach not accounting for the fact that viscoelasticity is largely a manifestation of collective multichain modes. In the rigorous sense, no such multichain treatment has yet been established to our knowledge. The necessity to consider interchain cooperativity in any real comprehensive polymer dynamics theory is concluded from low-frequency spin-lattice relaxation data, which are shown to reflect fluctuations of long-distance intermolecular dipole-dipole interactions.     

Linear nonstationary optical dimensional resonances in atomic nanostructures

The existence of linear nonstationary optical resonances in a diatomic nanostructural object with a dipole-dipole atomic interaction has been proved. A new solution to the joint system of modified Bloch optical equations and nonlocal field equations is obtained for time intervals much shorter than the times of phase and energy relaxation. Formulas for effective polarizabilities of the object’s atoms, which have a set of dimensional resonances, are derived. The frequencies of these resonances significantly differ from the eigenfrequencies of the object’s atoms, and their properties depend on the interatomic distance, light-pulse duration, initial atomic inversions, and the orientation of the object’s axis relative to the direction of incidence of the external light wave.     

氢对纯镍弹性模量的影响

用静电激发调频检测法对比测量了纯镍试样电解充氢和人为部分应力松弛后在室温时效过程中杨氏模量随时间的变化。结果表明:在人为部分应力松弛后的时效过程中,杨氏模量逐渐升高,其稳态值比初始值升高0.87％;而在充氢后的时效过程中,氢不断地从试样中逸出,同时杨氏模量也不断地降低,其稳态值比充氢后的瞬时值低2.87％;即,氢原子能明显地增高纯镍的弹性模量。 关键词：     

Non-newtonian flow for concentrated polymer systems

The modified Graessley theory with the three-dimensional Maxwell model can well explain some of the nonlinear viscoelastic behavior of concentrated polymer systems at least qualitatively with the assumption of a box-type relaxation spectrum for the equilibrium state.

The relaxation spectrum of concentrated polymer systems in shear flow is obtained by means of Graessley's theory. It is assumed that the characteristic time for the entanglement formation is the same order as that for its breakage and that the spectral density of the relaxation spectrum in the flow system is proportional to the number of entanglements between two molecules. The spectral density decreases approximately proportionally to 1/γ for relaxation times larger than 1/γ The non-Newtonian viscosity and other viscoelastic properties, such as the so-called stress overshoot and the stress relaxation, are calculated by using the obtained relaxation spectrum. Our theory explains very well the experimental results in many cases. Good agreement with experimental results is found if we assume that the so-called box-type relaxation spectrum in the equilibrium state has a finite gradient of the order of ?0.5 in the edge region of larger relaxation time on log-log plots.     

Relaxation of Translational Energy in Binary Mixtures of Dilute Gases Composed of Hard Spheres

Analytical expressions for the relaxation time τ necessary for the equilibration of translational energies of components in binary mixtures of dilute gases composed of hard spheres are derived. An expression for the collision number Z describing the mean number of collisions of one particle during the relaxation time is also given. The derivation has been performed for the very beginning of the relaxation and we choose the initial translational energy of the sort which is in excess to be equal to zero. Computer results obtained by a direct simulation method of solution of the Boltzmann equation do not only confirm these results but also show them to be valid for a relatively long part of the equilibration.     

The Preparation and Study on Ultrahigh Molecular Weight Polypropylene Gel‐spun Fibers

A novel polypropylene (PP) fiber was prepared by using gel spinning/crystallization from dilute solutions of ultrahigh molecular weight isotactic polypropylene (i‐UHMWPP), and subsequently drawing at various temperatures. The influence of drawing temperature on the properties of the resulted fibers was investigated. We found that the draw‐ability and mechanical as well as crystallization properties of the fibers obtained were dramatically improved with increasing drawing temperature. When the drawing temperature is below the α‐crystal relaxation temperature of PP, which was measured by wide‐angle X‐ray diffraction (WAXD) analysis as 100–120°C, the fibers are characterized by lower crystallinity and smaller crystals with less perfection, resulting in brittle fracture and subsequently poor mechanical durability. With drawing at temperatures above the α‐crystal relaxation temperature of PP, a novel UHMWPP fiber with Young's modulus of 27 GPa and tensile strength of 1.3 GPa was obtained. Higher crystallinity and larger crystals with better perfection and orientation were observed in this fiber.     

Sliding friction with polymer brushes

Using high-resolution shear force measurements, we examine in detail the frictional drag between rubbing surfaces bearing end-tethered polymeric surfactants (brushes). The drag attains a maximum on initial motion, attributed to elastic stretching of the chains, which falls by a cascade of relaxations to a value characteristic of kinetic friction. This has a very weak velocity dependence, attributed to chain moieties dragging within a self-regulating, mutual interpenetration zone. When sliding stops, the shear stress across the polymer layers decays logarithmically with time, consistent with the relaxation of a network of dangling ends.     

Stress relaxation through ageing heat treatment – a comparison between in situ and ex situ neutron diffraction techniques

The effect of ageing heat treatment on the relaxation of residual stress in a water quenched polycrystalline nickel-base superalloy has been measured using neutron diffraction. Two separate experiments have been conducted; the first experiment was an ex situ study in which samples were individually processed with varying degrees of age time before measurement. The second experiment was an in situ heat treatment, which required heating and then holding the sample at ageing temperature while measuring strain using neutron diffraction. The in situ experiment was carried out twice using the same setup to assess the repeatability of the technique and found to be repeatable within experimental error. The agreement between in situ and ex situ experiments was found to be reasonable, particularly the manner in which the stresses relaxed with time. In both studies it was found that initial stress relaxation was rapid, approximately 200 MPa in 15–30 min, after this a slower linear relaxation remained for the rest of the ageing heat treatment. This behaviour suggests creep may be the means by which stress relaxation takes place in this material during ageing.     

Water Desorption Kinetics of Polymer Composites with Cellulose Fibers as Filler

The water desorption kinetics of polymer composite systems with hydrophilic cellulose fibers from recycled paper (PSP) filler embedded in various polymer matrices (hydrophobic thermoset epoxy resin [EP] and thermoplastic polypropylene [PP], and hydrophilic thermoplastic poly[vinyl alcohol] [PVA]) was studied. Polymer composites test pieces containing 0, 3, 6, 9, and 30 wt. % of fibers were prepared. Adhesion between fibers and polymer matrices was improved by utilization of maleic anhydride grafted polypropylene (MAPP) coupling agent in the case of thermoplastic matrices (both PP and PVA). Water desorption tests were conducted after immersing test pieces in a distilled water bath at room temperature for 24 h. Study of the water desorption kinetics proved the expected enhanced absorption of the resulting composites after incorporation of cellulose fibers. A difference between two similar types of PVA by measurement of the desorption kinetics was found.     

Quantitative structural characterization of the mechanical properties of isotactic polypropylene

This investigation introduces quantitative morphological criteria for defining the structural state of a polymer sample and develops a general structural state deformation model for characterizing mechanical behavior. This general model discards the present fragmented view of the autonomy of observed mechanical processes (yielding, fracture, recovery, etc.) and brings the fabrication process, the mechanical tests, and even the construction of the sample (fiber or film) into focus as simply different aspects of a single process of deformation. The fabrication, fracture, yielding, and recovery behavior of two series of uniaxially drawn isotactic polypropylene films and two series of drawn isotactic polypropylene fibers, totaling thirty different structural states, have been deter-mined. The structural state of each of these samples is known quantitatively. The measurements were made over a range of strain rates from 1 to 1,000,000%/min and temperatures from 23° to -196°C. This study has resulted in new quantitative relationships between mechanical properties and morphological structure and has developed a deeper insight into the underlying deformation mechanisms that are occurring.     

Statistical Aspects of Tensile Fracture of Isotactic Polypropylene

The fracture behavior of isotactic polypropylene (iPP) specimen with double-notched shape under a fixed elongation speed at room temperature is described. Over 100 tensile tests were performed, and the statistic fracture data were obtained for the tensile condition. The statistical data of fracture were obtained by examining the time to fracture, the ultimate stress, and the tensile toughness (determined from the area under the nominal stress–strain curve from the origin to the fracture point). The probability density distributions for time to fracture, the ultimate stress, and the tensile toughness approximately followed the normal Gaussian statistics. Using a linear relationship between stress and elongation time near the fracture point, we can apply a static Kalman filter system to the present fracture data to determine a conditional probability density function. As a consequence, this application makes it possible to predict the probability of fracture of iPP under any static condition.     

Pulsed NMR Spectroscopy of Structural Changes in Chemically Modified Polypropylene

The structure of the polypropylene compositions obtained as a result of modification by multicomponent systems has been studied by the method of pulsed NMR spectroscopy. The times of relaxation were analyzed in a wide temperature range. The character of the occurring changes at the level of supermolecular structure is described. It is shown that the amplifications manifesting themselves upon modification of polypropylene by mixtures based on 2,4-toluene diisocyanate (TDI) and -caprolactam (-CL) are associated with the change in the character of intermolecular interaction and with the formation of a more ordered structure of the polymer.     

Induction time as a measure for heterogeneous spherulite nucleation: Quantitative evaluation of early-stage growth kinetics

A theory is proposed indicating that the induction time characterizes the nucleation process in polymer crystallization. A microscopic method has been developed to monitor early stages of the spherulite growth. Using the method, based on photometric measurement of the depolarized light intensity during isothermal crystallization from the melt, nonzero nucleation induction time values were found for polypropylene (PP). From comparison of the theory with the experimental results obtained from polypropylene crystallization, it follows that the formation of PP crystal nuclei on admixtures is affected both by the formation of the first crystalline layer and by the size of the critical nucleus.     

Lactone polymers. V. Viscoelastic properties of poly-ε-caprolactone and poly-ε-thiocaprolactone

The viscoelastic properties of crystalline poly-ε-caprolactone and poly-ε-thiocaprolactone have been characterized and compared by stress relaxation and dynamic mechanical studies. The glass transition temperature of poly-ε-thiocaprolactone was shown to be -40°C at 1 Hz and appeared to be independent of the degree of crystallinity. The rate of viscoelastic relaxation for each polymer was independent of linear strain rate of a decade range. The density of each polymer over a wide temperature range was used to reduce the individual time-dependent modulus values to an arbitrary reference temperature. This reduction of stress relaxation data to a standard mechanical state obviated the requirement of vertical shift factors for construction of the respective master curves. The distribution of relaxation times was correlated with the glass transition and the crystalline melt temperature range for each polymer.