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.     

Dynamical considerations of network properties

Elasticity is discussed as an aspect of viscoelasticity, which is described by the tube model. The effects of both crosslinks and entanglements contribute to this model and a discussion of how these effects can be quantified is given. At high enough concentration, entanglements ensure the existence of elastic effects even without crosslinks, and a theory is presented on how this dynamical phase change comes about.     

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.     

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     

Inorganic–organic hybrid materials with zirconium oxoclusters as protective coatings on aluminium alloys

Inorganic–organic hybrid materials are attracting a strong scientific interest mainly for their outstanding inherent mechanical and thermal properties, which can be traced back to the intimate coupling of both inorganic and organic components. By carefully choosing the experimental parameters used for their synthesis, chemically and thermally stable acrylate-based hybrid material embedding the zirconium oxocluster Zr₄O₄(OMc)₁₂, where OMcCH₂C(CH₃)C(O)O, can be deposited as UV-cured films on aluminium alloys.

In particular, the molar ratios between the oxocluster and the monomer, the polymerisation time, the amount of photo-initiator and the deposition conditions, by using an home-made spray-coating equipment, were optimised in order to obtain the best performing layers in terms of transparency and hardness to coat aluminium alloy (AA1050, AA6060 and AA2024) sheets. Furthermore, it was also evaluated whether the hybrid coatings behave as barrier to corrosion.

Several coated samples were prepared and characterised. Environmental scanning electronic microscopy (ESEM) and scratch test were used to investigate the morphology of the films and to evaluate their scratch resistance, respectively. Electrochemical impedance spectroscopy (EIS) was performed in order to evaluate if the coatings actually protect the metallic substrate from corrosion.

In order to measure shear storage modulus (G′) and loss modulus (G″) of the materials used for coatings, bulk samples were also obtained by UV-curing of the precursors solution. Dynamical mechanical thermal analysis (DMTA) was performed in shear mode on cured disks of both the hybrid materials and pristine polymer for comparison. The values of T_g were read off as the temperatures of peak of loss modulus. The length and mass of all the samples were measured before and after the DMTA analysis, so that the shrinkage of the materials in that temperature range was exactly evaluated.     

Method to Characterize the Air Flow and Water Removal Characteristics During Vacuum Dewatering. Part II—Analysis and Characterization

This is part II of a study reported earlier on a method to characterize the air flow and water removal characteristics during vacuum dewatering. This article presents experimental data and analysis of results from the use of a cyclically actuated vacuum dewatering device for removing moisture from wetted porous materials such as paper with the intermittent application of vacuum and accompanying air flow though the material. Results presented include sheet moisture content as a function of residence time and hence water removal rate under a variety of process conditions. Also, experimental results on air flow through the wet porous structure and hence the role and importance of air flow during vacuum dewatering are presented. Vacuum dewatering process conditions include exit solids content between 11 and 20% solid under applied vacuum conditions of 13.5 to 67.7 kPa (4 to 20 in. Hg). Regression analysis indicated that the exit sheet moisture content exhibited a nonlinear relationship with residence time with exit solids reaching a plateau after a certain residence time. Final moisture content correlated linearly with the average overall flow rate of air through the paper sample and the basis weight of the material.     

Effect of Wall Surface Properties at Different Drying Kinetics on the Deposition Problem in Spray Drying

Current methods in alleviating the wall deposition problem in spray drying emphasize mainly controlling the stickiness of the drying particles and less attention is placed on the properties of the dryer wall. In this experimental study, the effect of wall surface properties on the deposition mechanism has been investigated. Properties considered in classifying different wall materials were surface energy, roughness, and dielectric properties. The model solution contained sucrose, representing low-molecular-weight sugars commonly encountered in spray drying of fruit and vegetable juices. The effect of wall properties on deposition was explored at different drying rates producing particles of different surface rigidity. Larger surface roughness produced higher deposition fluxes for particles with high impact velocity and moisture. Surface energy and surface roughness were found to have no significant effect for dry rigid particles at the middle and bottom elevation of the drying chamber. However, material with lower surface energy (Teflon) exhibited less deposition for rubbery particles at such elevations. Analysis shows that dielectric wall material (Teflon) tends to enhance deposition of dry particles because of attrition at the surface. Higher wall temperature was found to produce slightly more deposition. The results of this work give a general indication of the effect of wall material on the deposition problem and provide the fundamental understanding for further studies along this line. Proper selection of dryer wall material will provide potential alternatives for reducing the deposition problem.     

Synthesis of TiO<Subscript>2</Subscript> Hybrid Molecular Imprinted Polymer for Ethofumesate Linked by Silane Coupling Agent

TiO₂ hybrid molecular imprinted polymer (MIP) for ethofumesate using methacrylic acid (MAA) as the functional monomer and silane coupling agent 3-(trimethoxysilyl) propylmethacrylate (KH570) as organic–inorganic connective bridge was synthesized via photo-excitation method. Hydrogen bond was proved to act between MAA and ethofumesate for pre- and post-polymerization binding properties as testified by UV spectrometric method. KH570 modified TiO₂ nanoparticles were prepared via sonochemical reaction, which can accelerate hydrolysis, increase collision chance for the reactive system and improve the dispersion of the nanoparticles. Scanning electron microscope (SEM), transmission electron microscope (TEM), binding and the adsorption kinetics experiments as well as thermogravimetric analysis (TGA) were employed for characterization. The results indicated that the hybrid MIP revealed a larger surface area and more ordered imprinting cavities with improved thermal stability compared to organic-only MIP. Furthermore, faster adsorption kinetics and enhancive adsorption capacity were achieved, which made it promising in chemical sensor applications.     

Improved Matrix-Filler Adhesion

Enhanced matrix-filler adhesion is realized after filler treatment with a surface treatment process. The hydrosol/coupling agent treatment was applied to a wide range of inorganic and organic fillers, and adhesion to a variety of matrix resins was improved. Scanning Electron Microscopy (SEM) was used to determine the locus of failure in the filled systems. The locus of failure shows the relative degree of adhesion between the filler and the polymer matrix. Significant improvement in adhesion in humid environments is also observed.