Recovery of gold cyanide using inherently conducting polymers

Removal of gold from basic solutions containing [Au(CN)₂]^? has been demonstrated using the inherently conducting polymer polypyrrole. Polymers containing sulfonated aromatic dopants have been found to display a significant ability to remove gold from such solutions. Experiments performed in solutions containing both gold and copper cyanide complexes indicate that the recovery process is not highly selective. However, the polypyrroles used display significantly faster rates of gold recovery than activated carbon. © 2003 Society of Chemical Industry     

Segmented polymer networks containing amino‐dendrimers

Polymer networks in which poly(propylene imine) dendrimers (Astramol?) are connected to each other by linear polytetrahydrofuran (polyTHF) segments, were prepared by two methods. The first method was a one‐step procedure in which bifunctionally living polyTHF, obtained by initiation of the THF polymerization with trifluoromethane sulfonic anhydride (triflic anhydride), was reacted with an amino‐dendrimer. This reaction was very fast but did not allow formation of the end products. The second method was a two‐step procedure. In a first step, living polyTHF, prepared with acryloyloxybutyl triflate as initiator, was grafted on an amino‐dendrimer, to form a star‐like, acrylate‐terminated polyTHF multi‐macromonomer with the dendrimer as core. In a second step, networks were obtained by Michael addition between the acrylate end‐groups and unreacted amino‐groups of the dendrimer. This cross‐linking reaction occurred spontaneously upon heating of the solution of the multi‐macromonomer with gelation times varying from a few minutes to a few hours, depending on the temperature and the composition of the prepolymers. With this method it was possible to prepare networks in the form of coatings or films. © 2003 Society of Chemical Industry     

Spin probe study of semi‐interpenetrating polymer networks based on polyurethane and polymethacrylate functional prepolymers

The motional transition and heterogeneity of semi‐interpenetrating networks (SIPNs) based on polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups were studied by the electron spin resonance (ESR) spin probe method. The concentration of functional groups in both prepolymers varied from 0 to 0.45 mmol g^?1. Spin‐probed SIPNs show that the temperature‐dependent spectra are sensitive to polymer interactions imposed by functional groups. These interactions determine the free volume distribution in the matrix and temperature at which motional transition takes place. The fraction of free volume increases with functional group concentration and reaches its maximum at 0.25 mmol g^?1. Further increases in the functional group concentration reduce the free volume. The results of the networks with strong interactions are discussed in terms of the interference of the plasticizing effect of the PU component and the formation of possible cluster cross‐links, which restricts segmental motions. Copyright © 2003 Society of Chemical Industry     

Chemische Zusammensetzung und Mikrostruktur polymerabgeleiteter Gläser und Keramiken im System Si–C–O. Teil 2: Charakterisierung der Gefügeausbildung mittels hochauflösender Durchstrahlungselektronenmikroskopie und Feinbereichsbeugung

Chemical Composition and Microstructure of Polymer‐Derived Glasses and Ceramics in the Si–C–O System. Part 2: Characterization of microstructure formation by means of high‐resolution transmission electron microscopy and selected area diffraction Liquid or solid silicone resins represent the economically most interesting class of organic precursors for the pyrolytic production of glass and ceramics materials on silicon basis. As dense, dimensionally stable components can be cost‐effectively achieved by admixing reactive filler powders, chemical composition and microstructure development of the polymer‐derived residues must be exactly known during thermal decomposition. Thus, in the present work, glasses and ceramics produced by pyrolysis of the model precursor polymethylsiloxane at temperatures from 525 to 1550 °C are investigated. In part 1, by means of analytical electron microscopy, the bonding state of silicon was determined on a nanometre scale and the phase separation of the metastable Si–C–O matrix into SiO₂, C and SiC was proved. The in‐situ crystallization could be considerably accelerated by adding fine‐grained powder of inert fillers, such as Al₂O₃ or SiC, which permits effective process control. In part 2, the microstructure is characterized by high‐resolution transmission electron microscopy and selected area diffraction. Turbostratic carbon and cubic β‐SiC precipitate as crystallization products. Theses phases are embedded in an amorphous matrix. Inert fillers reduce the crystallization temperature by several hundred °C. In this case, the polymer‐derived Si–C–O material acts as a binding agent between the powder particles. Reaction layer formation does not occur. On the investigated pyrolysis conditions, no crystallization of SiO₂ was observed.     

Molecular correlations in sheared thermotropic copolyesters showing banded textures

Banded textures produced in a thermotropic liquid crystal polymer by shearing between glass slides are examined by using both transmission electron and polarized light microscopy. The periodic variation in director orientation about the shear axis, as measured by light microscopy, is shown to be distinctly different from that indicated by electron diffraction. Measurements of birefringence and observation of Zernicke phase contrast indicate periodic variations in optical properties of the polymer, in step with the bands. Such effects are accounted for in terms of a synchronous rotation of the planar aromatic groups about the molecular chain axes. Evidence for an out-of-plane component of molecular orientation is also presented.     

Network topology and the theory of rubber elasticity

The earliest investigations on rubber elasticity, commencing in the 19th century, were necessarily limited to phenomenological interpretations. The realisation that polymers consist of very long molecular chains. commencing c. 1930, gave impetus to the molecular theory of rubber elasticity (1932-). according to which the high deformability of an elastomer, and the elastic force generated by deformation, stem from the configurations accessible to long molecular chains. Theories of rubber elasticity put forward from 1934-1946 relied on the assumption that the junctions of the rubber network undergo displacements that are affine in macroscopic strain. The theory of James and Guth (1947) dispensed with this premise, and demonstrated instead that the mean positions of the junctions of a ‘phantom’ network consisting of Gaussian chains devoid of material properties are affine in the strain. The vital significance of the distinction between the actual distribution of chain vectors in a network and their distribution if the junctions would be fixed at their mean positions went unnoticed for nearly 30 years. Experimental investigations, commencing with the incisive work of Gee in 1946. revealed large departures from the relationship of stress to strain predicted by the theories cited. This discrepancy prompted extensive studies, theoretical and experimental, during succeeding years. Inquiry into the fundamentals of polymer networks, formed for example by interlinking very long polymer molecules, exposed the need to take account of network imperfections, typically consisting of chains attached at only one end to a network junction. Various means were advocated to make corrections for these imperfections. The cycle rank ζ of the network has been shown (1976) to be the fundamental measure of its connectivity, regardless of the junction functionality and pattern of imperfections. Often overlooked is the copious interpenetration of the chains comprising typical elastomeric networks. Theories that attempt to represent such networks on a lattice are incompatible with this universal feature. Moreover, the dense interpenetration of chains may limit the ability of junctions in real networks to accommodate the fluctuations envisaged in the theory of phantom networks. It was suggested in 1975 that departures from the form predicted for the elastic equation of state are due to constraints on the fluctuations of junctions whose effect diminishes with deformation and with dilation. Formulation of a self-consistent theory based on this suggestion required recognition of the non-affine connection between the chain vector distribution function and the macroscopic strain in a real network, which may partake of characteristics of a phantom network in some degree. Implementation of the idea was achieved through postulation of domains of constraint affecting the equilibrium distribution of fluctuations of network junctions from their mean positions. This led in due course to a theory that accounts for the relationship of stress to strain virtually throughout the ranges of strain accessible to measurement. The theory establishes connections between structure and elastic properties. This is achieved with utmost frugality in arbitrary parameters.     

Synthesis and characterisation of copolyesters from poly(ethylene terephthalate) and poly(hexamethylene terephthalate)

Copolyesters containing poly(ethylene terephthalate) and poly(hexamethylene terephthalate) (PHT) were prepared by a melt condensation reaction. The copolymers were characterised by infrared spectroscopy and intrinsic viscosity measurements. The density of the copolyesters decreased with increasing percentage of PHT segments in the backbone. Glass transition temperatures (T_g). melting points (T_m) and crystallisation temperatures (T_c) were determined by differential scanning calorimetry. An increase in the percentage of PHT resulted in decrease in T_g, T_m and T_c. The as-prepared copolyesters were crystalline in nature and no exotherm indicative of cold crystallisation was observed. The relative thermal stability of the polymers was evaluated by dynamic thermogravimetry in a nitrogen atmosphere. An increase in percentage of PHT resulted in a decrease in initial decomposition temperature. The rate of crystallisation of the copolymers was studied by small angle light scattering. An increase in percentage of PHT resulted in an increase in the rate of crystallisation.     

Facile modifications of polyimide via chloromethylation: II. Synthesis and characterization of thermocurable transparent polyimide having methylene acrylate side groups

From chloromethylated polyimide, a useful starting material for modification of aromatic polyimides, a thermocurable transparent polyimide having acrylate side groups was prepared. In the presence of 1,8‐diazabicyclo[5,4,0]undec‐7‐ene, chloromethylated polyimide was esterified with acrylic acid to synthesize poly(imide methylene acrylate). The polymer was soluble in organic solvent, which makes it possible to prepare a planar film by spin coating. The polymer film became insoluble after thermal treatment at 230 °C for 30 min. Optical transparency of the film at 400 nm (for 1 µm thickness) was higher than 98 % and not affected by further heating at 230 °C for 250 min. Adhesion properties measured by the ASTM D3359‐B method ranged from 4B to 5B. Preliminary results of planarization testing showed a high degree of planarization (DOP) value (>0.53). These properties demonstrate that poly(imide methylene acrylate) could be utilized as a thermocurable transparent material in fabricating display devices such as TFT‐LCD. Copyright © 2004 Society of Chemical Industry     

High char‐yielding poly[acrylonitrile‐co‐(itaconic acid)‐co‐(methyl acrylate)]: synthesis and properties

Polyacrylonitrile terpolymers of various compositions consisting of acrylonitrile (AN), itaconic acid (IA) and methyl acrylate (MA) were synthesized by solution polymerization in dimethylsulfoxide. Increase in concentration of either IA or MA retarded the overall polymerization rate and the polymer molecular weight. The system consisting of AN + MA and varying IA concentration was more prone to retardation in comparison with the system composed of AN + IA with variable MA concentration. The retardation factors were quantified. Minor quantities of MA boost the reactivity of IA in the terpolymer system. The terpolymer was richer in MA vis‐à‐vis the feed. The thermal characteristics of the terpolymer were examined as a function of its composition. In contrast to the copolymer of AN and IA requiring 1–1.5 mol% IA, the terpolymer required an IA content of approximately 2.5 mol% for optimum thermal stability. The polymer with 90 mol% AN, 2.5 mol% IA and 7.5 mol% MA exhibited reasonably good char‐forming characteristics and thermal stability. The overall crystallinity and crystallite size of the polymers were found to decrease on incorporation of the comonomers. The ‘aromatization index’ of the copolymer increased with the temperature of pyrolysis through re‐organization of the tetrahydropyridine ladder structure. Copyright © 2005 Society of Chemical Industry     

低压直流供电电路中高压直流的产生

在由低压直流电源供电的电路中,往往电路的某些部位需要使用高于电源所供的电压,将电源所供的低压转换为较高的电压,常用的方法有3种:自举升压、电感升压、逆变升压。结合实际应用电路对各种升压方法从器件选择、升压原理、升压结果等诸方面进行分析、探讨,解决了总体供电电压不变时,局部高压产生的关键性问题。它对电子电器电路的设计人员有一定的启发作用,对优化电路、遴选器件有较强的参考价值。