A carbon single crystal electrode for an electrochemical quartz crystal microbalance study

A highly ordered single crystal carbon material, highly oriented pyrolytic graphite (HOPG) has been successfully employed as a working electrode in an electrochemical quartz crystal microbalance study. RTV silicone rubber is selected to adhere the HOPG film onto the quartz crystal surface. Such modified quartz crystal can oscillate with stable frequency. The electrode modified in this way has good electrochemical properties.

Polyepichlorohydrin polyurethane/poly(methyl methacrylate) interpenetrating polymer networks

Polyurethane (PU) based on polyepichlorohydrin/poly(methyl methacrylate) (PECH/PMMA) interpenetrating polymer networks (IPNs) was synthesized by a simultaneous method. The effects of composition, hydroxyl group number of PECH, NCO/OH ratio and crosslinking agent content in IPNs were investigated in detail. Some other glycols, such as poly(ethylene glycol), poly(propylene glycol) and hydroxyl-terminated polybutadiene, were also used to obtain PU/PMMA IPNs. The interpenetrating and fracture behaviors of the IPNs are explained briefly.

Studies on water-swellable elastomer .1. Synthesis and characterization of amphiphilic polymer

A new amphiphilic polymer i.e., polyethylene glycol (PEG) grafted crystalline neoprene, which was used as compatibilizer to improve the compatibility of elastomer and water-absorbent resin, has been investigated. The synthesis was based on the reaction between chlorine in neoprene and sodium salts of PEG. PEGs with molecular weights of 600 and 2000 were used. The grafting percent and the PEG content were calculated through elemental analysis of chlorine in the resulted copolymers. The maximum grafting percent of copolymers was ca. 24.80%. The molecular parameters such as number-average molecular weight and the average number of grafting chains on one CR backbone were also calculated and discussed. (C) 1996 John Wiley & Sons, Inc.

Toughening mechanism of polymer blends: Influence of voiding ability of dispersed-phase particles

The parameters which effect the cavitation strain of polymer blends toughened with a shear yield mechanism have been studied by analysis of the stress acted on the equatorial plane of dispersed-phase particles. As a result, the cavitation strain of polymer blends depends on the Young's modulus and the Poisson's ratio of the dispersed-phase particles and the matrix and also on the break stress of dispersed-phase particles. We tried to provide a criterion for selecting the materials used as dispersed-phase particles which can effectively enhance the toughness of polymer blends. (C) 1996 John Wiley & Sons, Inc.

EFFECT OF PARTICLE-SIZE ON IMPACT STRENGTH OF POLYMER BLENDS

The effect of particle size on impact strength of polymer blends with ductile fracture was studied. The results are in agreement with the experiments. (C) 1995 John Wiley & Sons, Inc.

TEMPERATURE AND STRAIN-RATE DEPENDENCE OF FRACTURE-TOUGHNESS OF PHENOLPHTHALEIN POLYETHER KETONE

A strong strain-rate and temperature dependence was observed for the fracture toughness of phenolphthalein polyether ketone (PEK-C). Two separate crack-blunting mechanisms have been proposed to account for the fracture-toughness data. The first mechanism involves thermal blunting due to adiabatic heating at the crack tip for the high temperatures studied. In the high-temperature range, thermal blunting increases the fracture toughness corresponding to an effectively higher test temperature. However, in the low-temperature range, the adiabatic temperature rise is insufficient to cause softening and Jic increases with increasing temperature owing to viscoelastic losses associated with the p-relaxation there. The second mechanism involves plastic blunting due to shear yield/flow processes at the crack tip and this takes place at slow strain testing of the single-edge notched bending (SENB) samples. The temperature and strain-rate dependence of the plastic zone size may also be responsible for the temperature and strain-rate dependence of fracture toughness.

FRACTURE-TOUGHNESS OF PHENOLPHTHALEIN POLYETHER KETONE

The static and impact fracture toughness of phenolphthalein polyether ketone (PEK-C) were studied at different temperatures. The static fracture toughness of PEK-C was evaluated via the linear elastic fracture mechanics (LEFM) and the J-integral analysis. Impact fracture toughness was also analyzed using the LEFM approach. Temperature and strain rate effects on the fracture toughness were also studied. The enhancement in static fracture toughness at 70 degrees C was thought to be caused by plastic crack tip blunting. The increase in impact fracture toughness with temperature was attributed two different mechanisms, namely, the relaxation process in a relatively low temperature and thermal blunting of the crack tip at higher temperature. The temperature-dependent fracture toughness data obtained in static tests could be horizontally shifted to match roughly the data for impact tests, indicating the existence of a time-temperature equivalence relationship. (C) 1995 John Wiley & Sons, Inc.

NMR-STUDY ON THE RELATIONSHIP BETWEEN MISCIBILITY AND ANTIAGING PERFORMANCE OF BLENDS CONTAINING BLOCK-COPOLYMERS

The anti-aging performance of blends of polystyrene (PS), styrene-butadiene triblock copolymers (SBS), and PS/styrene-butadiene (SB)-4A (Carm star SE block copolymer) has been studied by means of C-13 NMR techniques. It is found that the anti-aging performance of these kinds of blends largely depends on their miscibility with PS of different molecular weight M(PS). The larger the quantities of PS solubilized in polybutadiene (PBD) domains, the better the anti-aging performance of the blends. It is also found that the anti-aging performance of these blends has dependence on molecular architectures of the SE block copolymers. For the aged blends, the double bonds of PBD were broken, meanwhile serious cross-linking networks formed in the blends. The proposed anti-aging mechanism is that the PS solubilized in PBD domains can efficiently prevent oxygen molecules from diffusing into PBD domains, therefore, successfully stop the oxidative process of PBD.

TEMPERATURE EFFECT ON IMPACT FRACTURE-TOUGHNESS AND FRACTURE MECHANISM OF PHENOLPHTHALEIN POLY(ETHER KETONE)

Phenolphthalein poly(ether ketone) (PEK-C) was tested using an instrumented impact tester to determine the temperature effect on the fracture toughness K-c and critical strain energy release rate G(c). Two different mechanisms, namely the relaxation processes and thermal blunting of the crack tip were used to explain the temperature effect on the fracture toughness. Examination of the fracture surfaces revealed the presence of crack growth bands. It is suggested that these bands are the consequence of variations in crack growth along crazes that are formed in the crack tip stress field. As the crack propagates, the stress is relaxed locally, decreasing the growth rate allowing a new bundle of crazes to nucleate along which the crack advances.

LOCAL MAIN-CHAIN DYNAMICS OF PHENOLPHTHALEIN POLYETHERSULFONE

Local main chain dynamics of dissolved phenolphthalein polyethersulfone (PES-C) in solution with chloroform-d(1) were examined through C-13 NMR relaxation measurements. Spin-lattice relaxation times and NOE (nuclear Overhauser effects) factors were measured as a function of temperature. The relaxation data were interpreted in terms of main chain segmental motion by using the damped orientational diffusion model (DAMP) and the conformation jump model (VJGM) derived by Valeur, Jarry, Geny, and Monnerie. The simulation method used is N-SIMPLEX, which gives, in this study, a result of the object function less than 10(-4). Correlation times were obtained for the main chain motion of PES-C with these models and the results indicate that the main chain of PES-C are flexible. The comparison between PES-C and 1,2-polybutadiene is proposed. The distribution of the correlation time for the main chain motion by using VJGM model is discussed. The temperature dependence of correlation times for PES-C indicating the dynamical rigidity of its chains is obtained.

STRUCTURE AND PROPERTIES OF MALEATED HIGH-DENSITY POLYETHYLENE

Possible changes in the structure and properties of maleated polyethylene (HDPE-MA) at different degrees of grafting (D.G.) were examined. At the level of 1.6 maleic anhydride (MA)/100 ethylene units E, 70-80% of crystallinity of the parent PE was retaine

ELECTROCHEMICAL SCANNING-TUNNELING-MICROSCOPY

An ECSTM apparatus with an ideal tip using a homemade SSX-1A STM instrument has been constructed. STM and ECSTM tips were made by electrochemical etching and insulating with paraffin, silicon rubber or epoxy resin under an optical microscope. In situ imag

SYNTHESIS AND CHARACTERIZATION OF POLYMER-SUPPORTED LANTHANIDE COMPLEXES AND BUTADIENE POLYMERIZATION BASED ON THEM

Poly(styrene-acrylic acid)-lanthanide (Ln.PSAA) and poly(ethylene-acrylic acid)-neodymium (NdPEAA) complexes have been prepared and characterized. The infrared and X-ray photoelectron spectra indicate that the lanthanide complexes possess the bidentate carboxylate structure Ln-O-C(R)-O (see structure B in text). The catalytic behavior of the complexes has been described. The catalytic activities of Nd.PSAA and Nd.PEAA are much greater than that of the corresponding low molecular weight catalyst for butadiene polymerization. The activities of various individual lanthanide elements are quite different from one another. Neodymium shows the highest activity. Europium, samarium and the heavy elements exhibit very low or no activities. The cis-1,4 content of the polybutadiene obtained is not affected by different lanthanide elements in the series. The complex with the intermediate content of the functional group has a higher activity than the others. The polymer-supported lanthanide complexes having different constitutions have different catalytic activities. When the molar ratio of lanthanide to the functional group is ca. 0.2, the activity of the complex is in the optimum state. The activity is influenced by the dispersion of the lanthanide metal immobilized on the polymer chain. Catalytic activity can be improved by adding other metals to the catalyst system.

MICROSTRUCTURE ANALYSIS OF 3 SEGMENTED COPOLYMERS CONTAINING POLYDIMETHYLSILOXANE BY SOLID-STATE HIGH-RESOLUTION NMR

The microstructure of two bicomponent and one tricomponent segmented copolymers, based on polydimethylsiloxane, poly(p-hydroxystyrene) or/and polysulfone, were investigated using an extended Goldman-Shen pulse sequence, proton spin-spin relaxation measurements, and C-13 and Si-29 NMR spectra. The results indicate that there exist four phases with different sizes, components and morphological structure in the segmented copolymers studied in this work, i. e., a rigid-chain phase of very slow motion, a rigid-chain-rich phase of slow motion, a flexible-chain-rich phase of fast motion and a flexible-chain phase of faster motion. The sizes of different domains, calculated from the spin diffusion rates, are about 50-100 angstrom for the flexible-chain-rich phase of fast motion and 200-300 angstrom for the flexible-chain phase of faster motion. The relative quantities of polydimethylsiloxane in the flexible-chain phase of fast motion are slightly different in different kinds of segmented copolymers.

热带西太平洋边缘晚第四纪以来的古环境研究

利用取自热带太平洋边缘的5个柱状岩芯Ph05-5、WP3、MD2908、Z14-6和WP7，通过对其微体古生物和生物地球化学成分的分析，结合浮游有孔虫氧、碳同位素数据、AMS14C测年结果和已有的研究资料，分别研究了热带西太平洋边缘晚第四纪以来的钙质超微化石群落特征、碳酸盐旋回、超微化石氧碳同位素特征、古生产力和上层海水结构演化以及高分辨率东亚夏季风指标，并探讨了碳酸盐旋回、古生产力和上层海水结构演化、全新世东亚夏季风强弱变化的控制机制，以及钙质超微化石下透光带属种Florisphaera profunda的相对百分含量变化在热带太平洋边缘的古环境指示意义及不同环境条件下的控制机制。 西菲律宾海Ph05-5岩芯和台湾东南部WP3岩芯中CaCO3和钙质超微化石碳酸盐溶解指数、初级生产力指标的变化显示约190 kyr BP以来CaCO3含量整体上都表现为冰期高、间冰期低的“太平洋型”旋回特征，但菲律宾以东海区在末次冰期（MIS 4~2期）内部又显示出间冰段含量高、冰段含量低的“大西洋型”旋回特征。碳酸盐旋回的主要控制因素在菲律宾以东海区是碳酸盐溶解作用，而台湾东南海区则是初级生产力变化引起的钙质生物输入量的波动。 西菲律宾海Ph05-5岩芯中190 kyr BP以来的钙质超微化石δ18O值在末次间冰期（MIS 5e）和全新世明显低于末次冰期（MIS 5d~2）和倒数第二次冰期（MIS 6）。超微化石δ18O值与浮游和底栖有孔虫δ18O值都呈明显的正相关关系，但是超微化石的δ18O平均值重于表层浮游有孔虫Globigeriniodes rubber，轻于中层Neogloboquadrina dutertrei。超微化石δ13C值变化与其绝对丰度变化表明西菲律宾海区大约在MIS 6和MIS 5e期，表层海水初级生产力相当稳定且显著低于其它各时期；约从MIS 5d期开始表层初级生产力显著上升，并一直持续到末次冰期；在MIS1、2期，表层初级生产力有所下降，但仍高于MIS 6和MIS 5e期。 Ph05-5岩芯中钙质超微化石下透光带属种F. profunda相对百分含量和浮游有孔虫转换函数的温跃层深度变化表明西太平洋暖池北缘约190 kyr BP 以来，营养跃层和温跃层冰期（MIS 6期和5d~2期）浅，间冰期（MIS5e）和全新世深，MIS5e期是最近两个冰期旋回中营养跃层和温跃层深度最深的时期。F. profunda百分含量初级生产力转换方程计算结果和与钙质超微化石绝对丰度的变化显示冰期初级生产力高，间冰期和全新世初级生产力低， MIS5e期初级生产力最低。此外，Δδ13C C. wullerstorf-coccolith和Δδ13C C. wullerstorf-N. dutertrei差值的变化也说明190 kyr BP以来冰期表层输出生产力高于间冰期，其中最为突出的特征也是MIS5e期为生产力输出的最低值期。上层海水结构和生产力的上述变化特征与现代La Niňa事件爆发时的海洋环境相当类似，该海区MIS5e期可能是La Niňa事件频繁爆发的一段时期，可以与现代La Niňa现象类比。同时，根据Wyrtki提出的信风张弛理论推测MIS5e期，由于La Niňa事件的频繁爆发黑潮主流应该是增强的。 热带西太平洋暖池核心区WP7岩芯中250 kyr BP以来的初级生产力在间冰期明显低于冰期，间冰期生产力相对稳定，冰期(MIS6，4和2)生产力升降幅度较大；冰期向间冰期过渡的冰消期内生产力的降低是相对缓慢的，而间冰期向冰期过渡时生产力的增加是迅速的。初级生产力指标的交叉频谱分析显示出偏心率、斜率、岁差（半岁差）、30kyr和50kyr周期。说明暖池区晚第四纪以来古生产力变动除了受全球冰量变动控制以外，低纬区的岁差驱动也是主要控制因子。约250 kyr BP以来古生产力的变化与Vostok冰心的CO2记录在30kyr周期上高度相关，低CO2值与高生产力相对应，印证了大洋初级生产力在全球碳循环中扮演了重要的“吸收者”的角色，30kyr周期是赤道太平洋地区生物生产力ENSO式变化特征的体现，这也证明了低纬地区生物泵在控制大气CO2浓度方面的重要作用。另外，在岁差周期段，底栖有孔虫U+B含量和N. dutertrei δ13C代表的生产力变动领先于有孔虫δ18O代表的冰体积变化约2.6~7kyr（0.5kyr,2.6 kyr,4.2 kyr, 7kyr），表明在千年时间尺度上日射是该区生产力变化的直接驱动力，两极冰体积变化（δ18O）没有明显的影响低纬气候波动。 对热带西太平洋边缘海区WP7、Ph05-5、WP3和Z14-6四个岩芯中晚第四纪以来超微化石下透光带属种F. profunda相对百分含量变化进行横向对比研究表明，F. profunda百分含量分布并非简单受水深控制，而是由海水上层复杂的生态因素所决定；F. profunda相对百分含量变化曲线与浮游有孔虫N. dutertrei氧同位素曲线呈不同程度的相关性，N. dutertrei 氧同位素越轻，对应的F. profunda相对百分含量越高；冲绳海槽中部的Z14-6岩芯中F. profunda相对含量变化的主控因子是黑潮流的强弱变化；WP7和Ph05-5两个岩芯中F. profunda相对含量变化与低纬地区暖池变化特征密切相关。 6800 yr BP以来台湾东北部MD2908岩芯中F. profunda相对百分含量变化与太阳黑子数量呈明显的反相关关系，而且3700 yrBP以来更为明显。由于F. profunda相对百分含量变化与该地区东亚夏季风引起的降雨量密切相关，所以推测6800 yr BP以来东亚夏季风受太阳活动影响，其中的纽带是IZCT的纬向位置变动。