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.     

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.     

Municipal solid waste conversion to energy

In recent years it has been recognised by an increasing number of nations that there is considerable energy potential within MSW. As a result many countries have established R,D& D programmes to examine methods of exploiting this potential. The IEA's MSW Conversion Activity was set up in 1986 to provide an infrastructure for sharing information and co-ordinating work in this area internationally. This Activity was extended in 1989 and currently a total of 9 nations participate in it.

To cope with the wide scope of the area (encompassing both biological and thermal processing of MSW) the Activity was divided into three subgroups or Expert Working Groups (EWGs). Each of these dealt with a distinct area of expertise:

1. •Downstream effects of source separation and screening of MSW

2. •Sampling and analytical protocols

3. •Landfill gas

In addition to these groups a central secretariat based at Harwell (UK) has provided guidance, established and administered databases of contacts and produced a series of national reports.

This paper describes the achievements of the Activity and discusses work proposed for the future.     

Photo-reversible Reaction in Polymer Langmuir-Blodgett Films

Preparation of photoreactive Langmuir-Blodgett (LB) films was carried out using polymers/oligomers prepared from long-chain dialkyl esters of di-and tetra-olefins and having cyclobutane rings in the main chain. These polymers/oligomers formed stable monolayers on a water surface when mixed with arachidic acid. These monolayers could be deposited onto a substrate successfully forming Y-type films. The oligomer LB films were polymerized on irradiation. The polymer LB films showed a photo-reversible process between polymers and oligomers, depending on wavelength of the irradiating light. On the basis of spectral data and molecular weight change, this behaviour was found to be caused by cleavage and formation of cyclobutane rings.     

Rapid analysis of polymer homologues and additives with SFE/SFC-MS coupling

A rapid and easy analysis method for polymers is presented. The method involves sample preparation by SFE, separation of the extracted compounds by SFC and simultaneous quantitative detection by FID, as well as identification of unknowns by MS. The applications illustrate how structural research work and routine polymer analysis can be done with this time saving method.     

Dispersion—flocculation studies on a Goethite-clay system

Dispersion–flocculation studies on a Goethite–clay system using flocculants were carried out as a function of flocculant concentrations, pH of slurry, time of agitation and dispersant dosage. Also, the effects of pH and polymer concentrations on the adsorption behaviour of the system were investigated. Results show that well flocculated goethite was preferentially obtained from 4% goethite/kaolinite clay suspensions, with 50 ppm causticised starch in the slurry at pH values of 3–11·5 and with 50 ppm polyacrylamide at pH values of 3–8. Good flocs were also obtained on flocculation of the goethite suspension with 50 ppm polyacrylamide at pH values of 5–7, while the kaolinite suspension did not respond to the same dosage of causticised starch in the same pH range. Results further reveal that for the goethite/kaolinite suspension, the best results was obtained with 50 ppm polyacrylamide at pH values of 7–10. Based on the data generated in the study, it was concluded that causticised starch is a better flocculant than polyacrylamide for goethite suspensions although polyacrylamide is an excellent flocculant for kaolinite suspensions.     

Phase equilibria of quasi-binary systems consisting of multicomponent polymers 1 and 2. IV: Poly(ethylene oxide)/poly(propylene oxide) systems

To confirm the reliability of the theory of phase equibria of multicomponent polymer 1/multicomponent polymer 2 systems (i.e. quasi-binary systems) and the method of computer experiment based on this theory (Brit. Polym. J., 23 (1990)285; 23 (1990)299; Polym. Int., 29 (1992)219), could point curves (CPC), two-phase volume ratios ( R ) and critical solution points (CSP) have been determined experimentally for the quasi-binary mixtures of poly(ethylene oxide) (M¯_w = 647, M¯_w/M¯_n = 1.15; M¯_w and M¯_n, the weight-average and numberaverage molecular weights, respectively) and poly(propylene oxide) (M¯_w = 2028, M¯_w/M¯_n = 1.08; and M_w = 2987, M_w/M_n = 1.13). The hydroxyl end groups of both polymers were methoxylated in advance by the Cooper & Booth method (Polymer, 18 (1977)164). The thermodynamic interaction parameter between both polymers, χ₁₂, and the concentration dependence parameters for the above quasi-binary systems were determined by the method proposed in a previous paper (Brit. Polym. J., 23 (1990)299). CPC, R and CSP values calculated on the basis of the theory are in good agreement with the values determined experimentally.     

Optical data storage by novel photoelectrochromic polymer

A novel elastic polymer containing 4,4′-bipyridinium salts with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate as part of the main chain was synthesized. The cast film showed persistent and reversible colour changes due to photoinduced electron transfer upon excitation of an ion-pair charge-transfer band (_ex >365 nm) in vacuo. The lifetime of the coloured state markedly depended on temperature. The optically written data were stored without decay below 0°C and were erased thermally at elevated temperatures. The colour changes were reversibly repeatable for many times.     

Thermodynamic state of reinforced interpenetrating polymer networks

The free energies of mixing of two networks in the interpenetrating polymer network based on crosslinked polyurethane and poly(ester acrylate) have been determined by the vapour sorption method. It was established that the constituent networks in the IPN are not miscible. The introduction of fillers of different chemical nature increases the compatibility. The thermodynamic affinity of the fillers to the individual networks and IPN was estimated. It was established that when the free energy of interaction of one or both components of the IPN with the filler is negative, reinforcement leads to the formation of a compatible and equilibrium system. For fillers having no affinity to the polymers, compatibilization is observed, which is connected with slowing down of phase separation in the system in the presence of filler.     

铝电解电容器用橡皮塞中铁的测定

主要研究了用硫氰酸钾作显色剂，用分光光度法测定橡皮塞中铁含量的方法。并对国产和进口橡皮塞做了比较，为铝电解电容器质量水平的提高提供一条新思路。