HDPE/CB高分子导电复合体系的单轴形变与压阻行为

根据基体形变及其与渗流网络结构之间的关系,研究了高密度聚乙烯(HDPE)/炭黑(CB)复合材料压阻行为的发生机制及其影响稳定性的力学因素.结果表明,单轴压阻行为的产生源于材料受外力变形而导致的渗流网络微结构变化,且这种变化强烈依赖于填料含量.当填料含量较低时(渗流阈值附近),体系电阻率随压力升高而表现为电阻正压力系数行为;当填料含量较高时,体系电阻率随压力升高显现电阻负压力系数效应.完全卸载的零压力下,电阻基线随压缩循环随循环次数增大而发生漂移,这种漂移与轴向残余压缩应变有关,可以通过增加循环次数来加以稳定.交联可以减小残余压缩应变,并抑制高填充复合体系电阻基线的漂移.     

聚氯乙烯/炭黑导电复合体系的压阻行为

研究了聚氯乙烯/炭黑(PVC/CB)导电复合体系在单轴压力作用下的压阻行为,发现CB含量对电阻-机械响应具有显著的影响.当CB含量低于渗流阈值时,PVC/CB复合材料呈现PPC效应;而高于渗流阈值时,呈现NPC效应.在渗流阈值附近,单轴压缩可诱导NPC效应的出现,或者抑制PPC效应.     

等规聚丙烯/炭黑等温结晶过程中流变与导电行为的关联与同步测试

采用流变-导电行为同步测试方法,研究了等规聚丙烯(iPP)/炭黑(CB)复合体系的等温结晶行为,发现当CB体积含量φCB远高于渗流转变上限时,其体系的流变行为与导电性能均在某一特征时间处发生突变,电阻突变的特征时间短于动态储能模量(G′)或法向应力(FN)突变的特征时间,表明结晶诱导期存在CB粒子运动,促使CB粒子在晶粒尺寸增长期形成渗流网络;另一方面,与静态方法相比较,动态方法所测特征时间较短,表明动态方法对体系结晶结构变化的响应较静态方法更为灵敏.     

炭黑填充聚甲基乙烯基硅氧烷硫化胶的阻温特性与电阻弛豫

研究了炭黑填充硅橡胶硫化胶的热循环以及热处理过程中的导电行为,发现在热循环中阻温关系曲线逐渐向低电阻方向移动,而在恒温下发生电阻弛豫现象;分析了硫化胶的导电机制,讨论了阻温关系发生移动的原因.     

流变-导电同步测试法研究炭黑填充高密度聚乙烯的等温结晶行为

采用流变-导电同步测试法,研究炭黑(CB)填充高密度聚乙烯(HDPE)在124.3～125.3℃范围的等温结晶行为,发现应变、频率与预降温速率均显著影响等温结晶过程中动态流变与导电行为.动态储能模量(G')与电阻均在结晶过程中发生显著变化.其中,CB粒子在熔体中发生扩散,造成原有逾渗网络结构破坏,导致复合体系电阻在结晶诱导期内增大.随结晶度增加,G'在结晶诱导期附近开始显著增大,其临界时间对应1%～2%相对结晶度;同时,CB粒子在无定形区相互聚集而形成渗流网络结构,使得复合体系电阻显著降低.电阻的变化被认为与CB粒子在熔体中的迁移以及在HDPE晶体生长过程中的聚集行为有关,且比依时性动态流变行为更敏感.     

单轴压力对高密度聚乙烯/碳黑导电复合材料电阻特性的影响

研究了高密度聚乙烯/炭黑导电复合材料在单轴压力作用下电阻的变化规律.结果表明,在低压力下,复合材料电阻随压力增加而降低;而在较高压力下则随压力增大而升高,分别呈现出所谓的“电阻负压力系数”和“电阻正压力系数”效应.电阻的压力依赖性以及由压缩引起的电阻不可回复性,被认为与外力作用下导电网络的重组与破坏有关.由此提出了导电复合材料单轴压力作用-电阻相互关系的唯象模型.     

乙烯类聚合物-炭黑复合物的PTC效应

本文以低密度聚乙烯(LDPE)和乙烯-醋酸乙烯酯共聚物(EVA)为基材,炭黑(CB)为导电微粒,探讨了聚合物-炭黑复合物的结构对正温度系数效应(PTC)增强与减弱的影响和炭黑含量与PTC效应的关系以及交联结构对PTC现象的稳定作用.     

基于纳米压痕技术的炭黑/聚丙烯复合材料力学性能研究

利用纳米压痕技术对炭黑填充聚丙烯基(CB/PP)复合材料的弹性模量、硬度及蠕变行为等力学性能进行了实验研究。结果表明,炭黑颗粒对CB/PP复合材料具有强化作用,随着炭黑含量的增加,复合材料的弹性模量和硬度增加。实验得出了纯PP及CB/PP复合材料蠕变应力指数和蠕变特征松弛时间,结果表明炭黑含量的增加增大了复合材料的蠕变应力指数,并且提高了硬度和抗疲劳性能。同时炭黑含量增加,复合材料的蠕变特征松弛时间减小,表明炭黑颗粒有效阻碍了聚合物分子链的移动。     

CB在PET-PE复合材料中的选择分散及电性能

用Haake转矩流变仪制备了聚对苯二甲酸乙二酯-聚乙烯-炭黑(PET-PE-CB)复合材料.通过溶解性试验、扫描电镜测试对CB在PET-PE多相体系中的选择性分散进行了研究,考察了CB分布对电性能的影响.结果表明:CB倾向于分布在PET相,改变CB填充量、基体配比以及加料次序对CB微观分布的影响不大.当m(CB)/m(PET-PE)=0.07时,出现渗滤现象.固定炭黑含量,当PET的质量分数由20%增加到60%时,材料的体积电阻率下降了6个数量级,一次性加料更有利于形成导电通路,可以获得较低的体积电阻.     

炭黑表面含氧量对HDPE—CB复合物导电性能的影响

通过硝酸氧化处理炭黑（CB）,使其表面含氧量（氧元素与碳元素的摩尔百分比）由1．0％（CB1）提高到7．0％（CB2）。分别以CB1和CB2为填料,以高密度聚乙烯（HDPE）为基体,制备了两种导电复合材料。与碳粒子填充极性聚合物相反,表面含氧量高的CB2填充HDPE复合物的渗流阈值低。采用SEM、动态电渗流效应和Payne效应分析了两种炭黑在HDPE中的分散和凝聚特征。结果表明：CB2在HDPE中分散更不均匀,更容易凝聚形成网络。炭黑在非极性HDPE中凝聚形成导电网络的能力随炭黑表面含氧量的增加而提高。     

填充粒子对复合型导电硅橡胶电阻温度特性的影响

研究了炭黑填充复合型导电硅橡胶的电阻温度特性,分析了升温过程中导电硅橡胶电阻特性的详细变化过程。研究了导电粒子和白炭黑含量对导电硅橡胶电阻温度特性的影响,测量了在不同热处理温度下电阻率的变化及加力时电阻的驰豫时间。分析了热处理对电阻特性影响的机理。     

Compression stress relaxation in carbon black reinforced HNBR at low temperatures

Findings of a study of stress relaxation behaviour of hydrogenated nitrile butadiene rubber (HNBR) at nominal compressive strains up to 0.4 and temperatures above and below the glass transition temperature T_g are reported. Two formulations of a model HNBR with 36% acrylonitrile content and carbon black (CB) loading of 0 and 50 phr were investigated. The relaxation function of HNBR is found to be independent of strain at temperatures right above the T_g or at times longer than 10⁻³ s for the deformations employed. CB imparts higher long-term stiffness and also larger relaxation strength at times longer than 10⁻⁴ s to the HNBR, but it does not affect the relaxation behaviour of the rubber in the time span from 10⁻³ – 10⁴ s. In addition, the relationship between the strain energy function of HNBR and temperature is demonstrated to have a complex concave-downward shape which is affected by two competing contributions of entropy elasticity and the stress relaxation.     

Stress Cracking and Photodegradation: The Combination of Two Major Causes of HIPS Failure

Summary: This work investigates the effects of photodegradation on the stress cracking resistance of high impact polystyrene (HIPS). Injection moulded samples were exposed to the ultraviolet light for various times in the laboratory prior to solvent contact. The bars were then stressed with several different loads in a tensile testing machine under the presence of several types of alcohols (mostly butanol). During this period, the stress relaxation was monitored and, after unloading, the ultimate properties were evaluated. Complementary tests were done by size exclusion chromatography, and scanning electron microscopy. The results indicated that both photodegradation and butanol causes significant modification in HIPS properties, with reduction in mechanical properties. The previously degraded samples showed a higher level of stress relaxation and a greater loss in tensile strength in comparison to the undegraded ones. The synergistic action of photodegradation and stress cracking in polystyrene may be a consequence of the chemical changes caused by oxidation and the reduction in molecular sizes.     

An approach to one‐dimensional conductive polymer composites

A substantial approach to one‐dimensional (1D) electrically conductive composites was proposed which was based on the thermodynamic analysis of electric‐field‐induced particle alignment in a nonpolar thermoplastic polymer matrix. The process condition window was based on the real‐time exploration of dynamic percolation under different electric fields with carbon black (CB)‐filled polyethylene as a model. The CB content was the main factor of the process condition. Its upper limit was set as the critical percolation concentration at the thermodynamic equilibrium state without an electric field to eliminate the possibility of conductive network formation perpendicular to the electric‐field direction, whereas its lower limit the critical percolation concentration at the thermodynamic equilibrium state under a critical electric field (E*). A composite with CB content in this window, isothermally treated in an electric field not less than E*, showed conductivity in the electric‐field direction about 10⁵ times larger than that in the perpendicular direction. A 1D cluster structure in the direction of the electric filed was confirmed with scanning electron microscopy morphology observations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 184–189, 2005     

交流阻抗谱在聚乙烯/碳黑导电复合材料导电机理研究中的应用

用交流阻抗谱论证了聚乙烯/碳黑(PE/CB)导电复合材料的网络导电机理,分析了热处理过程对复合材料电性能的影响。通过在不同频率和低电压下测定热处理前后及不同长度的导电复合材料样品的导电能力(A)、导电方式(B)和电阻值(Ra Rc),证明了材料内部存在着直通碳链、小间隙的碳链和大间隙的碳链,呈现三维网络导电结构。     

Electrical properties and conductive mechanisms of immiscible polypropylene/Novolac blends filled with carbon black

Carbon black (CB)-filled immisicible thermoplastic/thermosetting polymer blends consisting of polypropylene (PP) and Novolac resin were reported in this paper. The PP/Novolac/CB blends with varied compositions and different processing sequences were prepared by melt-mixing method. The CB distribution, conductive mechanism and the relationship between morphology and electrical properties of the PP/Novolac/CB blends were investigated. Scanning electron microscopy (SEM), optical microscopy and extraction experiment results showed that in PP/Novolac blends CB particles preferentially localized in the Novolac phase, indicating CB has a good affinity with Novolac resin. The incorporation of CB changed the spherical particles of the dispersed Novolac phase into elongated structure. With increasing Novolac content, the elongation deformation of Novolac phase became more obvious and eventually the blends developed into co-continuous structure, which form double percolation and decrease the percolation threshold. When CB was initially blended with PP and followed by the addition of Novolac resin, the partial migration of CB from PP to the Novolac phase was possibly occurred. The addition of Novolac to PP evidently increases the storage modulus G′, loss modulus G″ and complex viscosity η^∗. The addition of CB to PP/Novolac blends further increase η^∗, and it increases with increasing CB loading, which was related to the change of composite morphology.     

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.     

STUDY ON INTERMITTENT SHEAR FLOW AND RELAXATION BEHAVIOR OF THERMOTROPIC LIQUID CRYSTALLINE POLYMER

Intermittent shear flow including start-up flow and small oscillatory amplitude time sweep or stress relaxation after cessation of shear flow was used to study the rheological behavior and internal structure of thermotropic liquid crystalline polymer (TLCP). There are two kinds of intermittent shear flow: all start-up flows are in the same direction (intermittent flow forward: IFF) and start-up flows change their directions alternately (intermittent flow reversal: IFR). The results show that the stress of start-up flow of IFF and IFR in the test process is not superposed, indicating different changes of internal structure of thermotropic LCP (TLCP). Two main factors affect structure changes in the experimental time scale. One relates to long-term texture relaxation process, the other is an interchain reaction that becomes important after 30 min. The two factors raise the stress of IFF, but express complex effects for the stress of IFR. The latter factor becomes very important at long time annealing process. The relaxation behavior was also studied by the application of wide range relaxation spectrum calculated from the combined dynamic modulus, which gave three characteristic relaxation times (0.3, 10 and 600 s) ascribable to the relaxations of less-phase orientation, domain orientation, and domain deformation, respectively. The result also shows that the domain coalescence (texture relaxation), a long relaxation time, is a much slow process and lasts beyond 2400 s of the test time.     

Insights into the Payne Effect of Carbon Black Filled Styrene-butadiene Rubber Compounds

As a widely used reinforcing filler of rubber, carbon black(CB) often enhances the nonlinear Payne effect and its mechanism still remains controversial. We adopt simultaneous measurement of rheological and electrical behaviors for styrene-butadiene rubber(SBR)/CB compounds and CB gel(CBG) during large deformation/recovery to investigate the contribution of conductive CB network evolution to the Payne effect of the compounds. In the highly filled compounds, the frequency dependence of their strain softening behavior is much more remarkable than that of their CB network breakdown during loading, while during unloading the unrecoverable filler network hardly affects the complete recovery of modulus, both revealing that their Payne effect should be dominated by the disentanglement of SBR matrix. Furthermore,the bound rubber adjacent to CB particles can accelerate the reconstruction of continuous CB network and improve the reversibility of Payne effect. This may provide new insights into the effect of filler network, bound rubber, and free rubber on the Payne effect of CB filled SBR compounds.