Fracture toughness of the epoxy/ATPEI-CTBN-ATPEI triblock copolymer/NMA blend system

The shortcoming of epoxy resin is the brittleness of this material though it shows excellent chemical, mechanical and electric properties. To improve fracture toughness of epoxy resin, rubbery materials that show high values in toughness but low values in glass transition temperature and mechanical properties, and thermoplastics that show high values in thermal and mechanical properties but relatively small increase in toughness were blended with epoxy. ATPEI-CTBN-ATPEI triblock copolymer, which consists of rubbery and thermoplastics blocks, was synthesized, and the triblock copolymer was blended with epoxy resin. The effects of parameters such as contents of the triblock copolymer, cure temperature, and contents of catalyst on the morphology of the blend systems were studied. From 30 wt% of the contents of the triblock copolymer, fracture toughness and impact energy absorption of the blend systems were increased significantly. This was due to the generation of nodular morphology in the system.     

Crystallization and morphology in blends of isotactic polypropylene and linear polyethylene

Thermooptical, wide-angle x-ray diffraction and morphological investigations of blends of isotactic polypropylene with linear polyethylene revealed an increased crystallization rate of the polyethylene blend component, compared to crystallization of polyethylene alone. Crystallization behavior of the polyethylene component was markedly dependent on the blend thermal history and on the circumstances of the polyethylene phase—whether it was disperse or continuous. The higher crystallization rate of the polyethylene component was related to the presence of various types of heterogeneous crystallization nuclei in the blend and to the stabilizing action of the solid polypropylene matrix on minute polyethylene crystallites which survived above melting temperature.     

取代基效应（SCS）与乙烯—α—烯烃共聚物的序列结构：Ⅰ,乙烯—丙烯共聚物

本文应用取代基效应方法处理乙丙共聚物的~(13)C NMR谱,第一次得到这个共聚物(CH_3)的取代基参数,在此基础上归属了乙丙共聚物的~(13)C谱,讨论了共聚物序列结构的几种表示方法,进而用一套普适的公式计算了几个共聚物的序列分布,并作了比较。     

Interaction of Domains in Ternary Polymer Melt Blends with Separate Dispersions of the Inner Phases

The morphology evolution in three immiscible ternary polymer systems characterized by separate dispersions of the dispersed phases (i.e., no encapsulation phenomena takes place) was characterized. The components used were three of the following: commercial atactic poly(methyl methacrylate) (PMMA) and polystyrene (PS), crystallizable poly(butylene terephthalate) (PBT) and isotactic polypropylene (PP) and glass microspheres (GMS). In System I PMMA/PS/PP (primary dispersed phase/matrix/secondary, or minor, dispersed phase), all of the components were liquid on blending at 190°C. In System II PP/PS/PBT and System III PP/PSyGMS, at 190°C, the minor PBT and GMS dispersed phases were nondeformable. It was shown that small portions (0.5–1.0 wt%) of the PP minor dispersed phase added to the binary PMMA/PS blend produced a dual action: (a) transition of the PMMA dispersed phase to a cocontinuous one and (b) simultaneous substantial (up to a 6-fold) growth of the degree of dispersion of the blend. Moreover, these effects were accompanied by about a three-fold reduction of the threshold PMMA concentration (C*) at which it formed its own co-continuous phase in the ternary blend compared to that in the PMMA/PS binary mixture. The observed phenomena took place regardless of whether the domains of the minor dispersed phase were liquid (System I) or solid (Systems II and III), and was strongly related to the domain sizes of this phase and blend composition. A mechanism underlying the outlined behavior is proposed.     

EV共聚物序列中的两种结构因素

系统描述了EV共聚物序列中两种结构因素对共聚物主链中亚甲基和次甲基¹³C NMR化学位移的贡献,将SCS方法与半经验方法结合起来,阐明了常数项δ_LE和δ₀的物理意义,提出了以聚乙烯链反式构象化学位移δ_t为基准计算上述亚甲基和次甲基化学位移的公式:δ_c=δ_t+Σn_iS_i+ΣP_jγ_j并在此基础上,讨论了聚乙烯,聚丙烯的特殊情况和乙丙共聚物的链结构.     

Exploring low temperature Li+ ion conducting plastic battery electrolyte

We report blend-based plastic polymer electrolyte (i.e., polyethylene oxide (PEO)–polydimethyl siloxane (PDMS)–lithium hexafluorophosphate (LiPF₆)) with substantial improvement in DC conductivity at ambient and subambient temperatures when compared with literature reports. Conductivity variation with salt concentration, investigated within ±30 °C range, indicates an optimum conductivity of 5.6?×?10^?5 S cm^?1 at 30 °C for Ö/Li ~10 with a further lowering by one order at 0 °C and it remains unaltered at ?10 °C. Enhanced conductivity in this blend electrolyte, though lower than two copolymer counterparts, is attributed to very low glass transition temperatures of the host polymers. X-ray diffraction (XRD) and scanning electron microscopy (SEM) suggest an effective blending between the two polymers with an effective interaction between the Li salt and the blend polymer matrix. Raman spectroscopy results indicated that cation (Li⁺) coordination occurs at the C=Ö site in PEO out of the two electron-rich sites (i.e., CÖ and Si–Ö–Si) in the PEO–PDMS blend. The blend electrolytes are predominantly ionic (t _ion ~97 %).     

PVPh/PEO共混物动力学演化过程的NMR研究

聚合物共混物中链段的慢取向运动与其玻璃化转变行为和宏观力学性质密切关联,而基于化学位移各向异性重聚的~(13)C CODEX(centerband-only detection of exchange)固体核磁共振(SSNMR)技术能够有效表征共混物中链段的慢取向运动.该文利用~(13)C CODEX NMR技术详细研究了相容性聚合物共混物聚乙烯基苯酚/聚氧乙烯(PVPh/PEO)中的刚性组分PVPh在较宽温度范围内的慢取向运动特性与玻璃化转变过程的关联.研究表明,在玻璃化转变起始温度以下,PVPh主链的分子运动被冻结,而侧基存在b-松弛的慢取向运动;在玻璃化转变起始温度附近,PVPh主链具有明显的慢取向运动,而且主链和侧基是一种协同的分子运动.该文利用NMR技术揭示了共混物中的玻璃化转变起止温度分别对应于高分子主链慢取向运动CODEX信号的开始和极大值处的温度.     

Phase Structure Characterization by SALS of In Situ Compatiblized Binary Polymer Blends and Its Relation to Rheology

Phase structures of polypropylene (PP)/polystyrene (PS) blends, in situ compatiblized by a Friedel–Crafts alkylation reaction with anhydrous aluminum chloride (AlCl₃) as a catalyst, were investigated by small angle light scattering (SALS). The invariant Q, the content of compatible domain between the two phases, i.e., the interphase volume fraction, and the interphase thickness of the in situ compatiblized binary polymer blends were determined by Rayleigh scattering, as well as the phase structure parameters, such as correlation distance and average chord lengths. The results showed that the obtained blend is a partially compatible system. The invariant Q, the interphase volume fraction, and the interphase thickness all can be used to characterize the in situ interfacial compatiblization of the blends and all showed a nonlinear dependence on the in situ formed copolymer content. Further investigations revealed that the contribution of the interfacial modification to the zero shear viscosity of the in situ compatiblized blends showed exponential decay with the increasing invariant Q and showed exponential growth with the increasing volume fraction and thickness of the interphase in the blends. The nonlinear relations between the three phase structure parameters and the in situ formed copolymer content, as well as the nonlinear relations between the three phase structure parameters and the contribution of the interfacial modification to the zero shear viscosity of the blends, might be closely related to the in situ formation of the copolymer and its effect at the interfacial surface in the blends.     

Studies of water penetration into LDPE--calcium lactate composite

Penetration of water into low-density polyethylene-calcium lactate composite is studied with NMR techniques. The presence of filler speeds up the water uptake by the polymer matrix and facilitates polyethylene degradation. Spatial distribution of absorbed water molecules within the composite visualised with MRI corroborates differences in dynamical behaviour of the absorbed water molecules revealed by T2 measurements.     

Intrinsic impurities in glass alkali-vapor cells

We report NMR measurements of metallic (133)Cs in glass cells. The solid-liquid phase transition was studied by observing the NMR peaks arising from these two phases; surprisingly, many cells yielded two additional NMR peaks below the melting point. We attribute these signals to two distinct impurities which can dissolve in the liquid alkali metal and affect its chemical shift. Intentional contamination of cesium cells with O(2) confirms this hypothesis for one peak. The other contaminant remains unknown but can appear in evacuated cells. Similar effects have been seen in (87)Rb cells.     

抗冲共聚聚丙烯中二甲苯可溶物的链结构与性能研究

抗冲共聚聚丙烯(IPC)是聚丙烯与乙烯-α-烯烃共聚产物在反应釜内形成的原位共混物,乙烯-α-烯烃无规共聚物(橡胶相)作为聚丙烯增韧剂,增韧能力受其组成、玻璃化转变温度(T_g)的影响很大。目前工业界主要采用二甲苯可溶物来表征IPC中橡胶相的含量。该研究采用红外光谱(FTIR)、核磁共振(NMR)和热分析(DSC)等方法对两种不同催化剂制备的IPC的二甲苯可溶物,进行了组成、链结构及热性能对比研究,结果显示二甲苯可溶物中除了乙烯-丙烯无规共聚物外,还含有少量的具有可结晶乙烯序列的乙烯-丙烯多嵌段共聚物,且两个样品中的乙烯-丙烯多嵌段共聚物中可结晶乙烯序列长度存在差别;两个样品中乙烯、丙烯单元在分子链上无规分布的程度比较接近;丙烯序列PPP的含量相对低且乙烯共聚单元含量高的样品具有更低的Tg,这将有利于其对聚丙烯抗冲击韧性的提高。     

Heterogeneous dynamics at the glass transition in van der Waals liquids, in the bulk and in thin films

It has been shown over the last few years that the dynamics close to the glass transition is strongly heterogeneous, both by measuring the diffusion coefficient of tagged particles or by NMR studies. Recent experiments have also demonstrated that the glass transition temperature of thin polymer films can be shifted as compared to the same polymer in the bulk. We propose here first a thermodynamical model for van der Waals liquids, which accounts for experimental results regarding the bulk modulus of polymer melts and the evolution of the density with temperature. This model allows us to describe the density fluctuations in such van der Waals liquids. Then, by considering the thermally induced density fluctuations in the bulk, we propose that the 3D glass transition is controlled by the percolation of small domains of slow dynamics, which allows to explain the heterogeneous dynamics close to T _g. We show then that these domains percolate at a lower temperature in the quasi-2D case of thin suspended polymer films and we calculate the corresponding glass transition temperature reduction, in quantitative agreement with experimental results of Jones and co-workers. In the case of strongly adsorbed films, we show that the strong adsorption amounts to enhance the slow domains percolation. This effect leads to 1) a broadening of the glass transition and 2) an increase of T _g in quantitative agreement with experimental results. For both strongly and weakly adsorbed films, the shift in T _g is given by a power law, the exponent being the inverse of that of the correlation length of 3D percolation. Received 21 March 2000 and Received in final form 4 December 2000     

固体高分辨13C NMR研究γ线辐照对结晶聚乙稀聚集态结构的影响

结晶聚乙烯(PE)经⁶⁰Coγ线辐照后,用固体高分辨¹³C NMR CP/DD MAS方法观测解析了辐射效果与具有片晶结构的结晶相,结晶-橡胶状无定形界面相以及橡胶状无定形相的聚集态结构的关系。考察了各相中的¹³C核自旋-晶格弛豫和自旋-自旋弛豫行为及辐照对其影响。得到辐照后产生交联,破坏,相转变及晶型变化等有意义的结果,对PE的辐照效应和机制的探讨提供了核磁共振的新实验证据。     

129Xe NMR studies of the dynamics of xenon in siliceous ZSM-12 zeolite

The adsorption of xenon in siliceous zeolite ZSM-12 has been studied by static, magic angle spinning and 2D-EXSY¹²⁹Xe NMR. Anisotropic lines were observed with parameters dependent on the Xe loading and the temperature of the experiment. The observed dependence of the isotropic chemical shift is at variance with the predictions of the mean-free-path model, which casts further doubt on the applicability of this model to the interpretation of Xe NMR data in porous systems. Based on the continuous changes of anisotropic parameters with the loading, we conclude that there are several adsorption sites for xenon in the pores. A qualitative model for the distribution and rapid exchange of the xenon atoms between several sites is discussed. The observed lines arise from a dynamic average of the chemical shift tensors for the different types of site weighted by their populations. 2D-EXSY spectra show two kinds of slow exchange of Xe: (a) particle to particle and, (b) particle to interparticle gas phase.     

Morphology,phase structure,and properties of polyolefin/hydrogenated oligocyclopentadiene blends

The paper discusses the influence of an amorphous oligomer (namely hydrogenated oligocyclopentadiene — HOCP) on the morphology and the phase structure of its blends with several polyolefins as a function of composition and crystallization conditions. In particular the following polyolefins were studied: high-density polyethylene (HDPE), isotactic polypropylene (IPP), poly(l-butene) (PB-1), and poly(4-methyl pentene-1) (P4MP1). The blends under investigation are complex polymer systems. In fact, in dependence on temperature, blend composition, and cooling rate, they assume different morphologies and consequently show different thermal and mechanical behaviors. In the solid state the blends form a generally three-phase system: a crystalline phase of polyolefin and two amorphous phases, one rich in the amorphous polyolefin and the other in HOCP. The crystallization process and the properties are determined by the morphology and the phase structure, as well as by the physical state of the HOCP-rich phase.     

Characterization of Filler-rubber Interaction,Filler Network Structure,and Their Effects on Viscoelasticity for Styrene-butadiene Rubber Filled with Different Fillers

For styrene-butadiene rubber (SBR) compounds filled with the same volume fraction of carbon black (CB), precipitated silica and carbon–silica dual phase filler (CSDPF), filler-rubber interactions were investigated thru bound rubber content (BRC) of the compounds and solid-state ¹H low-field nuclear magnetic resonance (NMR) spectroscopy. The results indicated that the BRC of the compound was highly related to the amount of surface area for interaction between filler and rubber, while the solid-state ¹H low-field NMR spectroscopy was an effective method to evaluate the intensity of filler-rubber interaction. The silica-filled compound showed the highest BRC, whereas the CB-filled compound had the strongest filler-rubber interfacial interaction, verified by NMR transverse relaxation. The strain sweep measurements of the compounds were conducted thru a rubber process analyzer; the results showed that the CSDPF-filled compound presented the lowest Payne effect, which is mainly related to the weakened filler network structure in polymer matrix. The temperature sweep measurement, tested by dynamic mechanical thermal analysis, indicated that the glass transition temperature did not change when SBR was filled with different fillers, whereas the storage modulus in rubbery state and the tanδ peak height were greatly affected by the filler network structure of composites.     

Polymer-filler interaction and control of structure in barium sulphate-filled blends of polypropylene

The structure of barium sulphate-filled immiscible blends with a polypropylene (PP) matrix can be controlled with respect to the occlusion of the filler with the aid of maleic anhydride-grafted polypropylene (PP-g-MAH) through the formation of an interlayer around the filler particles. Here we analyze the interlayer and the mechanism of interlayer formation in a blend with a poly(methylmethacrylate) (PMMA) dispersed phase and compare the results with previous studies, which concerned PP blends with polystyrene (PS) and poly(styrene-co-acrylonitrile) (SAN) minority phases. The main analytical tools were scanning electron microscopy (SEM), dynamic mechanical analysis (DMA) and Fourier Transform Infrared Spectroscopy (FTIR). The filler is occluded in the PMMA polymer in the PP/PMMA/BaSO₄ (60/20/20 vol.%) blend, but is occluded in the PP phase at the addition of a sufficient amount of PPg-MAH. The reason for the formation of the latter structure is a PP-g-MAH layer surrounding the filler particles, and the most likely mechanism behind this phenomenon is judged to be specific weak interactions between carbonyl groups in the graft copolymer and Ba²⁺ ions at the filler surface.     

129Xe NMR study of the homogeneity and the size distribution of small sodium metal particles in NaY zeolite

NaY zeolite samples loaded with sodium metal by vapor phase deposition have been investigated using¹²⁹Xe NMR spectroscopy. At low sodium concentration, the¹²⁹Xe NMR spectrum showed three resonance lines which clearly indicate the existence of distinct domains in the zeolite sample. Such an observation suggests that the diffusion of the xenon atoms into each domain only occurs with respect to the NMR time scale (2.9 ms). As the sodium concentration increases, observation of a single broad line indicate a macroscopic homogenization of the system. The shift of this line is explained in part due to a paramagnetic interaction between the xenon atoms and the unpaired electrons of particles containing an odd number of sodium atoms. The linewidth is due to the distribution of the local magnetic fields partially averaged by the rapid motion of the xenon atoms and to the statistical distribution of the sodium particles in the supercage cavities. The paramagnetic interaction vanishes with the oxidation of the sample leading to a narrowing and a shift of the line to higher magnetic fields.     

Solvent‐Assisted Interfacial Tension Deformation of Spherical Particles for the Fabrication of Non‐Spherical Particle Arrays

A facile and efficient approach is developed for the fabrication of asymmetric non‐spherical polymer particle arrays. A specific amount of solvent is provided to interact with the spherical polymer particles to intensify the segmental mobility, thus suppressing the viscosity and the glass transition temperature of the polymer particles. The spherical polymer particles in the rubbery state are deformed into non‐spherical particle arrays at the gas/liquid interface. The upper parts of the polymer particles that protrude out of the liquid phase undergo deformation by interfacial tensions at the three‐phase contact line, allowing the formation of a ridge of polymer with a protrusion on the top surface. Simultaneously, the lower parts of the polymer particles submerged under the liquid phase are subjected to enormous surface tension at the contact points, leading to a non‐linear coalescence behavior of the neighboring polymer particles.     

Morphological,Thermal, and Electrical Characterization of Syndiotactic Polypropylene/Multiwalled Carbon Nanotube Composites

In this work, syndiotactic polypropylene/multiwalled carbon nanotubes (MWCNT) nanocomposites, in various concentrations, were produced using melt mixing. The influence of the addition of MWCNT on the morphology, crystalline form, and the thermal and electrical properties of the polymer matrix was studied. To that aim, scanning electron microscopy, Raman spectroscopy, X-ray diffraction, differential scanning calorimetry, and dielectric relaxation spectroscopy were employed. Significant alterations of both the crystallization behavior and the thermal properties of the matrix were found on addition of the carbon nanotubes: conversion of the disordered crystalline form I to the ordered one, increase of the crystallization temperature and the degree of crystallinity, and decrease of the glass transition temperature and the heat capacity jump. Finally, the electrical percolation threshold was found between 2.5–3.0 wt.% MWCNT. For comparison purposes, the results of the system studied here are also correlated with the findings from a previous work on the isotactic polypropylene/MWCNT system.