尼龙1010应力松弛行为研究

尼龙1010样品在初始应变为1%、2.8%和5.1%的条件下,在不同的恒温环境中分别进行不少于10 h的应力松弛实验,得到20~80℃范围的应力松弛曲线.研究了不同应力、温度下的应力松弛速率、松弛过程的残余应力、活化体积以及相关参数的数学关系.结果表明,尼龙样品在松弛过程中存在一定的形变残余应力,体系存在恒定的长时模量.不同初始应变的尼龙样品松弛过程表现出相似的规律,当松弛速率-d(σ/σ0)/dlnt达到最大值后,在一段时间内聚合物内部活化单元发生松弛,-dσ/dt与作用于样品的有效应力σ*为指数关系.随着松弛过程的进行,应力减小到一定程度后,活化体积V逐渐增加,此时独立的活化单元运动受到限制,聚合物内部依靠多个活化单元的协同运动将内应力逐渐松弛,应力辅助功Vσ*为常数,-dσ/dt与σ*满足幂律关系,幂指数为σ*V/(k T).     

热处理对尼龙1010固态结晶和玻璃态热松驰的影响

本文用DSC首先论证淬火尼龙1010试样在DSC曲线上出现的放热峰是冷结晶峰,然后研究淬火尼龙1010在不同热处理条件下,冷结晶峰和玻璃态热松驰峰的变化规律。实验结果表明,等温结晶时间较短,试样的固态结晶速率较快;等温结晶时间较长,固态结晶速率较慢,这可能与在Tg区域等温所形成的新氢键有关。当升高等温温度时,固态结晶速率加快。在低于Tg的不同温度退火,玻璃态热松弛峰的峰高及热焓在281K达最大值,进而确定对玻璃态热松驰影响最敏感的温度区间是277～284K。     

从静态应力松弛实验求材料准松弛时间谱的一种数值计算方法

避开繁琐困难的函数求解过程，采用数值计算方法，从常规的静态应力松弛实验，直接求被测材料的松弛单元的表现松弛强度．主松弛时间τ０由单－ＭＡＸＷＥＬＬ模型求得，其他松弛时间分别约取为１０（－２）·τ０，１０（－１）·τ０，１０１·τ０，１０３·τ０。应力松弛万程取５参数模型，记为谱的强度ａｉ（或Ａｉ）通过多元线性回归，由最小二乘法确定．对一种天然橡胶试样在不同温度下的松弛曲线进行处理，回归值与原始实验值吻合良好，不同温度下的松弛单元对总松弛的贡献，反映出温度对松弛过程的活化作用．     

聚对苯二甲酸乙二酯非晶态膜片单轴热——拉伸中的结晶与松弛

用动态力学损耗温度谱作为测试手段,研究了非晶态PET膜片在78—112℃温度范围内的单轴拉伸。实验结果说明,在较低温度下所得结晶的拉伸试样,完全由于应变诱发结晶,发生在应力-应变曲线的屈服后应力开始上升的阶段。在较高温度下(90℃或更高)拉伸可得非晶态而且光学各向同性的试样,是由于分子链的小尺度取向在拉伸过程中已完全热松弛所致,而分子链的大尺度取向要通过高弹态流动而松弛,其速率较慢,用拉伸后试样两端固定时的应力松弛进行了观察。在较低温度下应力松弛后仍为非晶态,在较高温度下应力松弛到起始应力的1O％下才开始结晶。FTIR研究表明在这种状态下的结晶有一结晶诱导期,其时间尺度与应力松弛阶段相当。     

分数Maxwell模型应用于PTFE松弛模量的研究

用分数Maxwell模型对聚合物PTFE(Polytetrafluoethylene)的应力松弛过程进行了研究. 分数Maxwell模型的渐近行为是确定其参数的基本依据, 但根据实验数据确定的松弛时间与渐近解成立的条件并不自恰. 通过适当选定松弛时间, 利用起始时段的实验数据确定初始松弛指数和松弛模量, 并适当优化末端松弛指数, 分数Maxwell模型可以对粘弹性应力松弛过程给出非常好的描述.     

聚2,6-萘二甲酸乙二醇酯β松弛的热释电研究

本文用短路热释电方法研究了聚萘酯(PEN)的β松弛过程。极化场强和电极效应的实验结果表明,PEN的TSC图谱中50℃的β松弛过程是偶极松弛过程。并且此松弛峰电流值随样品结晶度的增加而降低。用“初始升高法”计算得到其松弛活化能约为0.34eV,且不受结晶度变化的影响。这些实验结果说明β松弛是非晶区小链段的局部运动。     

多组分聚合物体系的动态流变行为与其相行为的关系

对多组分聚合物体系相行为所采用的常规研究方法都存在不可避免的缺陷。而用动态流变学方法研究具有独特的优点,其理论依据是：对具有临界相行为(LCST、UCST)或微相分离行为的多组分聚合物体系,在小应变状态下的动态流变行为对体系在相分离过程中形态和结构的形成与演化极其敏感,非均相结构的产生使体系在长时松弛区域表现出与均相聚合物体系不同的粘弹松弛行为,即弹性显著增加、松弛时问明显增长以及时-温叠加原理失效,偏离经典的线性粘弹理论模型。本文综述了用Han曲线、Cole-Cole曲线、时-温叠加失效和G′-T曲线等动态流变学方法对多组分聚合物体系相行为的研究进展。     

氧离子导体钼酸镧β→α相变非等温动力学的确定

为了研究氧离子导体钼酸镧La_2Mo_2O_9在853K左右存在的可逆固-固相变过程,采用差热分析(DTA)测量不同冷却速率下高温β相到低温α相的DTA曲线,运用FWO法、Ozawa迭代法、Criado-Ortega法以及atava-esták法求算相变过程的表观活化能E、指前因子A和最概然动力学机理函数G(x)"动力学三因子"。研究结果显示:β→α相变的表观活化能与转化分数有关,其值随转化分数的增大而逐渐减小,该结果表明该相变不属于一步简单反应,其过程和机理都较为复杂。不同温度区间β→α相变的G(x)不同,816~812K时,G(x)为[-ln(1-x)]2/5,对应lg A为68.28;809~804K时,G(x)为[-ln(1-x)]2/3,对应lg A为42.07。     

基于弹性统计理论的硅橡胶纳米复合材料本构关系的建立

基于考虑了悬垂链的橡胶弹性统计模型,通过引入应变放大因子,建立了硅橡胶纳米复合材料的基于微观机制的本构关系,其中利用硅橡胶分子信息(分子量M、乙烯基含量wt_(Vi)%)、乙烯基反应程度(q)估算获得本构方程中的交联点间链段分子量(Mc),网络链(network strands)体积分数(Φ)等参数,通过拟合确定了与纳米粒子相关的部分参数(初始应变放大因子X_0,极限应变放大因子X_∞,衰减因子z),对掺杂白炭黑的单组分及长短链配合硅橡胶拉伸应力-应变数据进行拟合,在采用相同X_∞,z值情形下,拟合曲线仍能与实测值符合较好(拟合的Adj.R-Square值分别为0.99576、0.99596)。基于微观物理机制的本构关系能够成为联系微观分子结构参数与宏观应力的桥梁,本文工作有望为更有针对性地改进和优化硅橡胶的性能提供依据。     

基于回归分析模型与随机过程模型的硅橡胶泡沫应力松弛预测对比

本文针对硅橡胶泡沫的应力松弛实验数据,基于二阶Prony级数,采用非线性回归分析方法(曲线拟合法)、基于Wiener过程的贝叶斯方法、基于Gamma过程的贝叶斯方法进行参数估计从而分别建立预测模型,通过对比三种建模方法的预测值与实验值的偏差,比较了三种建模方法的效果。结果发现,采用曲线拟合的方法进行参数估计,其预测偏差要大于基于Wiener、Gamma随机过程的贝叶斯方法,表明由于考虑了性能退化过程存在的不可避免的随机性,随机过程模型可以更好地预测硅橡胶泡沫的应力松弛趋势,同时由于应力松弛过程是单调增加的,基于非负的Gamma过程的随机过程模型的预测偏差要小于基于Wiener过程的模型。本文工作可为基于高分子材料性能退化数据的退化预测模型的建模提供一种较好的参数估计方法,有助于提高预测结果的准确性。     

Stress relaxation in carbon-black-filled styrene–butadiene rubber

The tensile stress relaxation of carbon-black-filled SBR was studied in the linear viscoelasticity region as a function of temperature and volume fraction of fillers. Time—temperature superposition was valid, and master relaxation curves were obtained. Carbon black increases the modulus of the compound, especially in the rubbery region, and the time range over which the glass-rubber transition occurred. The shift factor is divided into three regions; an Arrhenius dependence in rubbery and glassy states, and Williams-Landel-Ferry (WLF) dependence in the transition region. The apparent activation energy in the rubbery state increases with the volume fraction of carbon black (or silica) and is unaffected by the structure of the filler. The increase in activation energy is caused by the attachment of rubber chains to the carbon surface. At 30% elongation, the activation energy for carbon-black-filled rubber has a value of 32 kcal/mole, independent of structure and concentration of the filler.     

酞侧基聚芳醚酮的应力松弛与屈服行为的模型解析

根据不同温度下酞侧基聚芳醚酮（ＰＥＫ—Ｃ）的应力松弛曲线及时－温等效原理，得到了ＰＥＫ—Ｃ在任意参考温度下的总曲线．应用Ｋｏｈｌｒａｕｓｃｈ—Ｗｉｌｌｉａｍｓ－Ｗａｔｔｓ（ＫＷＷ）模型定量解释了应力松弛现象的温度依赖性，并通过ＫＷＷ模型建立了应力松弛现象与屈服行为间的相关性．     

Thermo-oxidative degradation of Nylon 1010 films: Colorimetric evaluation and its correlation with material properties

The thermo-oxidative aging behaviors of Nylon 1010 films were studied by various analytical methods, such as measuring the chromaticity, relative viscosity, carbonyl index, UV absorbance at 280 nm and elongation at break of the aged films. The thermo-oxidative aging plots of the results obtained via these various methods at different temperatures are subjected to the time-temperature superposition analysis, which are found to be well superposed. The b^* values are used as X axis and the other results, i.e., relative viscosity, carbonyl index, UV absorbance at 280 nm and elongation at break, are used as Y axis, respectively. The relationship between the b^* values and the other results is obtained, from which we can derive the changes of physical and chemical properties at different b^* values. Since the b^* values can be quickly determined by using a portable spectrophotometer, the on-line evaluation of the thermo-oxidative aging of Nylon 1010 can be realized.     

A method for the evaluation of the activation energy from relaxation experiments

A method is proposed for calculating the activation energy over the entire temperature range from relaxation measurements at two frequencies as a function of temperature by taking into account the entire experimental curve. The method is independent of the distribution of relaxation times, but assumes the validity of the time-temperature superposition principle.     

Force spectroscopy of quadruple H-bonded dimers by AFM: dynamic bond rupture and molecular time-temperature superposition

We report on the application of the time-temperature superposition principle to supramolecular bond-rupture forces on the single-molecule level. The construction of force-loading rate master curves using atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) experiments carried out in situ at different temperatures allows one to extend the limited range of the experimentally accessible loading rates and hence to cross from thermodynamic nonequilibrium to quasi-equilibrium states. The approach is demonstrated for quadruple H-bonded ureido-4[1H]-pyrimidinone (UPy) moieties studied by variable-temperature SMFS in organic media. The unbinding forces of single quadruple H-bonding (UPy)2 complexes, which were identified based on a polymeric spacer strategy, were found to depend on the loading rate in the range of 5 nN/s to 500 nN/s at 301 K in hexadecane. By contrast, these rupture forces were independent of the loading rate from 5 to 200 nN/s at 330 K. These results indicate that the unbinding behavior of individual supramolecular complexes can be directly probed under both thermodynamic nonequilibrium and quasi-equilibrium conditions. On the basis of the time-temperature superposition principle, a master curve was constructed for a reference temperature of 301 K, and the crossover force (from loading-rate independent to -dependent regimes) was determined as approximately 145 pN (at a loading rate of approximately 5.6 nN/s). This approach significantly broadens the accessible loading-rate range and hence provides access to fine details of potential energy landscape of supramolecular complexes based on SMFS experiments.     

Effect of crosslink density on the pressure relaxation response of polycyanurate networks

The effect of crosslink density on the pressure-volume-temperature (PVT) behavior and on the pressure relaxation response for two polycyanurate networks is investigated using a custom-built pressurizable dilatometer. Isobaric cooling measurements were made to obtain the pressure-dependent glass transition temperature (T_g). The pressure relaxation studies were carried out as a function of time after volume jumps at temperatures in the vicinity of the pressure-dependent T_g, and the pressure relaxation curves obtained were shifted to construct master curves by time-temperature superposition. The reduced pressure relaxation curves are found to be identical in shape and placement, independent of crosslink density, when T_g is used as the reference temperature. The horizontal shift factors used to create the master curves are plotted as a function of the temperature departure from T_g (T − T_g), and they agree well with their counterparts obtained from the shear response. Moreover, the retardation spectra are derived from bulk compliance and compared to those from the shear. The results, similar to our previous work on polystyrene, indicate that at short times, the bulk and shear responses have similar underlying molecular mechanisms; however, the long-time mechanisms available to the shear response, which increase with decreasing crosslink density, are unavailable to the bulk response. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2477–2486, 2009     

A note on ‘sub-Tg relaxation processes in poly(cyclohexylmethacrylate)’

We have critically examined the various relaxation processes occurring in poly(cyclohexylmethacrylate) using dielectric spectroscopy. In addition to the α- and γ-processes found earlier by other workers, we have detected a secondary (β-)process in the temperature range of 293-353 K with an activation energy of about 73 ± 5 kJ/mol.     

Glassy dynamics and mechanical response in dense fluids of soft repulsive spheres. II. Shear modulus, relaxation-elasticity connections, and rheology

We apply the quiescent and mechanically driven versions of nonlinear Langevin equation theory to study how particle softness influences the shear modulus, the connection between shear elasticity and activated relaxation, and nonlinear rheology of the repulsive Hertzian contact model of dense soft sphere fluids. Below the soft jamming threshold, the shear modulus follows a power law dependence on volume fraction over a narrow interval with an apparent exponent that grows with particle stiffness. To a first approximation, the elastic modulus and transient localization length are controlled by a single coupling constant determined by local fluid structure. In contrast to the behavior of hard spheres, an approximately linear relation between the shear modulus and activation barrier is predicted. This connection has recently been observed for microgel suspensions and provides a microscopic realization of the elastic shoving model. Yielding, shear and stress thinning of the alpha relaxation time and viscosity, and flow curves are also studied. Yield strains are relatively weakly dependent on volume fraction and particle stiffness. Shear thinning commences at values of the effective Peclet number far less than unity, a signature of stress-assisted activated relaxation when barriers are high. Apparent power law reduction of the viscosity with shear rate is predicted with a thinning exponent less than unity. In the vicinity of the soft jamming threshold, a power law flow curve occurs over an intermediate reduced shear rate range with an apparent exponent that decreases as fluid volume fraction and/or repulsion strength increase.     

Some connections between viscoelastic properties of PVC and plasticized PVC and molecular kinetics

A coupling model that has been shown in the past to be capable of relating macroscopically measured relaxation parameters to molecular ones has been presented. In this article the coupling model is applied to the analysis of stress relaxation data collected by Cama and Sternstein on PVC and plasticized PVC. The Kohlrausch-Williams-Watts form, exp — (t/τ*)^1?n, using n = 0.77 is found to be capable of describing the stress relaxation master curve at temperatures below the glass transition, T_g. From the temperature-independent apparent activation energy found by Cama and Sternstein, the primitive activation energy of the α-relaxation was calculated to be 7.5 kcal/mol, which is a reasonable value for the energy barrier to internal rotational isomerism in PVC. Support for this value is found from the data on two plasticized PVCs with different T_gs and apparent activation energies. By applying the coupling model in a similar manner, the primitive activation energies were found to be 8.5 kcal/mol for PVC plasticized with 6 pph dioctylphthalate and 7.7 kcal/mol for PVC plasticized with 6 pph tricresyl phosphate. Within experimental uncertainties, the three primitive activation energies can be considered to be the same. This finding is consistent with the physical basis for primitive activation energy and its identification with the internal rotation barrier, which should be independent of the type and amount of plasticizer in the system. Analysis of Cama and Sternstein's data on the effect of repeated stress aging on stress relaxation of quenched samples of PVC and plasticized PVC show that the coupling constant n increases systematically with each successive stress-aging cycle until it approaches the value for slow-cooled samples. These results are consistent with the notion that stress-aging changes the structural state of the glass in ways similar to physical aging.     

Pressure relaxation of polystyrene and its comparison to the shear response

Isothermal pressure relaxation as a function of temperature in two pressure ranges has been measured for polystyrene using a self-built pressurizable dilatometer. A master curve for pressure relaxation in each pressure regime is obtained based on the time–temperature superposition principle, and time–pressure superposition of the two master curves is found to be applicable when the master curves are referenced to their pressure-dependent T_g. The pressure relaxation master curves, the shift factors, and retardation spectra obtained from these curves are compared with those obtained from shear creep compliance measurements for the same material. The shift factors for the bulk and shear responses have the same temperature dependence, and the retardation spectra overlap at short times. Our results suggest that the bulk and shear response have similar molecular origin, but that long-time chain mechanisms available to shear are lost in the bulk response. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3375–3385, 2007