Mechanical properties and transition temperatures of copolymers of N-n-alkylacrylamides and vinylidene chloride

Mechanical and solution properties, melting transitions, torsional stiffness temperatures, T_f, and selected modulus-temperature curves are presented for copolymers of the N-n-alkylacrylamides with vinylidene chloride. Copolymers were prepared at 60°C across the range of compositions, using as comonomers N-n-butyl-, octyl-, dodecyl- and oleyl-acrylamide, which have amorphous side-chains, and N-n-octadecyl acrylamide and n-octadecyl acrylate whose side-chains are crystalline. The mechanical properties reflected the effect of the decline in backbone crystallinity and the simultaneous development of strong intermolecular interactions in the amorphous stage. Copolymers were stiff or showed brittle failure across the compositional range except when intermolecular forces were reduced (with n-octadrcyl acrylate) and side-chain crystallization eliminated (with N-oleylacrylamide). These systems and the n-dodecylacrylamide copolymers had yield strengths less than brittle strengths and substantial elongations. Backbone crystallinity was eliminated at about 15 mole % amide and side-chain crystallinity vanished at less than 10 mole % of the amide in the N-n-octadecylacrylamide series. No depression in side-chain melting point occurred with dilution by segments of vinylidene chloride. Over-all decline in the flex-temperature was the normal monotonic function of composition except that values increased in magnitude at high vinylidene chloride contents, the effect presumably being caused by the presence of crystallinity. An empirical equation was developed which permitted the calculation of T_f for any N-n-alkylacrylamide composition with any number of carbon atoms in the side-chain, above 3.     

Nonaqueous poly(methyl methacrylate) dispersions: radical dispersion polymerization in the presence of AB block copolymers of polystyrene and poly(dimethyl siloxane)

Well defined AB block copolymers of polystyrene (PS) and poly(dimethyl siloxane) (PDMS) have been prepared with PS molecular weights in the range 8 800 to 43 600 and PDMS molecular weights in the range 2 400 to 48 000. Provided the PS and PDMS molecular weights have a ratio within the range 0.5 to 4.0, these block copolymers stabilize particles of poly(methyl methacrylate) in n-alkanes. The particle size over the range 0.1 to 0.5 μm may be varied by performing dispersion polymerizations of methyl methacrylate as a function of monomer content of the seed stage and as a function of the concentration, molecular weight and composition of the block copolymer. From silicon analyses of the poly(methyl methacrylate) particles, values of the surface area stabilized per PDMS chain were established. The results indicate complete surface coverage of the particles.     

Development of optical anisotropy in vitrains during carbonization

The purpose of this work was to examine the possible significance in the formation of metallurgical coke of the anisotropic spherical mesophase exemplified by that found during the carbonization of pitch-like materials, and to ascertain if the various types of optical anisotropy found in coke could form a basis for the characterization of cokes produced from different coals. Vitrains from a wide range of coals were carbonized at temperatures from 370 to 1000 °C and the types and amounts of optical anisotropy in the resulting semi-cokes and cokes were determined from microscopic examination, the anisotropic components being classified according to grain size of the granular mosaics and appearance. The anisotropy developed directly from the isotropic phase, appearing initially as a fine-grained mosaic. With increasing carbonization temperature, this fine-grained mosaic was transformed into progressively coarser-grained anisotropy, the extent of this transformation depending on the rank of the vitrain. It is therefore concluded that the formation, growth and coalescence of anisotropic spherical bodies, such as occurs during the carbonization of pitch, is not a necessary precursor of the mosaic anisotropy in coke. The type and amount of anisotropy developed provide a quantitative means of characterising different cokes.     

Oxidation and Fracture Strength of High-Purity Reaction-Bonded Silicon Nitride

Reaction-bonded Si₃N₄ (RBSN) made from high-purity Si powder is unusually resistant to degradation caused by exposures to air for up to 50 h at temperatures up to 1400°C. The weight gain during oxidation of this SiH₄-originating RBSN is approximately 10 times less than conventional RBSN. Contrary to normally observed strength degradations, room-temperature strengths of this high-purity, oxidized RBSN (avg = 435 MPa, max. = 668 MPa) remained at their unusually high, as-processed levels after 1000° and 1400°C oxidizing exposures. Fracture toughness values were unaffected by oxidation ( K _IC= 2.3 to 2.4 MPa · m^1/2). This superior oxidation resistance results from the high purity and the small diameter pore channels (0.01 to 0.06 μm) achieved in this SiH₄-originating RBSN.     

Pressureless low temperature sintering of nanocrystalline zirconia ceramics via dry powder processing

Pressureless sintering approaches provide a simple avenue to manufacture dense ceramic parts with minimal processing equipment, but current pressureless sintering techniques have yet to demonstrate capabilities of producing dense ceramics while maintaining sub-50 nm grain sizes. Nanocrystalline yttria stablized zirconia ceramics were process from 4 mol% yttria stablized zirconia (4YSZ) nanopowders with a crystallite size of 7.5 nm using dry cold isostatic pressing (CIP) where powders are dried immediately prior to green compact formation and CIP vacuum bagging. It is shown that CIP pressures >75 000 psi (517 MPa) effectively remove pores larger than 100 nm and that pressureless sintering occurs at reduced temperatures for green densities ≥50%. Though the sintering kinetics are shown to be similar to other zirconia nanopowder sintering studies, the small initial crystallize size and reduced sintering temperature allowed densities as high as 97.2%, while retaining a ceramic grain size at or below 40 nm. Produced nanocrystalline 4YSZ ceramics with a grain size of 30.3 nm and a density of 96.3% had Vicker's hardnesses as high as 14.2 GPa and Vicker's indentation fracture resistance of 3.43 MPa·, demonstrating that simple processing approaches can be refined to fabricate nanocrystalline ceramics while maintaining high hardness and indentation fracture resistance.     

Chromium distribution between liquid iron and molten basic slags

An equilibrium study was made of the distribution of chromium and oxygen between liquid iron, containing less than 1 pct Cr, and simple slags of the CaO(MgO)-SiO₂-FeO-Cr₂O₃ type in the temperature range 1526° to 1734°C The effects of slag oxidation, temperature, and basicity were observed.     

An adaptive discrete-time ILC strategy using fuzzy systems for iteration-varying reference trajectory tracking

In this article, a novel fuzzy systems based on adaptive Iterative Learning Control (ILC) strategy is presented to deal with a class of non-parametric nonlinear discrete-time systems which perform iteration-varying reference trajectory tracking. Using the technique of fuzzy systems to compensate for the non-parametric uncertainty of the discrete-time system dynamics, the proposed adaptive ILC scheme can well track the iteration-varying reference trajectory beyond the initial time points. The convergence of the fuzzy systems based adaptive ILC algorithm is guaranteed by theoretical analysis, and a numerical example is given to illustrate the effectiveness of the adaptive ILC scheme.