Mechanosynthesis of complex oxides and preparation of mixed conducting nanocomposites for catalytic membrane reactors

Nanopowders of LaGaO₃- and LaMnO₃-based complex perovskites (P) and ceria-based fluorites (F) were prepared by mechanosynthesis. Compatible nanocomposites F + P and P + P with mixed ion and electron conducting (MIEC) properties were prepared and sintered at moderate temperatures up to dense ceramics. The obtained materials were studied by means of XRD, SEM, TEM, electrical conductivity measurements, temperature programmed (TP) reduction/oxidation and preliminary estimations of permeability were obtained. A new strategy based on the advantages of the mechanochemical ceramic approach is proposed to design multilayer ceramic membranes for CMR. Casting technology and one-step sintering were used for the production of thin film membranes with MIEC properties on porous substrates. The coarse fraction of as-milled powders from agglomerates with density 70% was used for the porous substrate, and fine fractions of aggregates with sizes <1 μm were used in preparation of composites for thin dense films. Ceria-based composites prepared by the Pechini route and/or mechanochemical method are proposed as materials for protecting thin films.     

Effect of phosphate esters on PVC flammability from a multi-test viewpoint

Many tests have been developed to provide relative flame/smoke data. In spite of the proliferation of such tests and test equipment, many chemical and polymer producers, as well as fabricators, use only one technique to evaluate the flame/smoke properties of a polymer system. This paper demonstrates the importance of multi-method testing to rate the efect of phosphate esters and various fillers on PVC flammability and smoke generation.     

Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.     

Morphology and microstructure of autoclaved clinker and slag-lime pastes in presence and in absence of silica sand

Development of microstructure in four hydrothermal reactions has been undertaken using scanning electron microscopy. These are clinker, clinker-sand, slag-lime and slag-lime-sand hydrothermal reactions. The microstructure of clinker hydration products displayed crumpled foils and tabular masses of calcium silicate hydrates; few cubic crystals of hydrogarnet appeared only during the initial stage of the reaction. In clinker-sand mixture the C-S-H phase was the only product identified. In slag-lime hydration the microstructure displayed both of the hydrogarnet crystals and the C-S-H phase. The hydration of slag-lime-sand mixture (an optimum composition) was associated with the formation of ill-crystallized tobermorite and crystalline 11A tobermorite as the main products.     

Molecular weight distribution of the graft copolymer comprising mixtures of styrene and acrylamiae on cellulose acetate film by means of gel permeation chromatography

Styrene portion of the radiation-induced graft copolymer comprising styrene and acrylamide was separated by acid hydrolysis and the effects of various grafting parameters (e.g., reaction time, reaction temperature, solvents, monomer composition, etc.) on molecular weight distribution were evaluated by means of gel permeation chromatography. When a single monomer or mixture of two monomers are grafted, the molecular weights is found to increase, but polymer dispersity decreases with the increase of reaction time or reaction temperature except at a higher reaction time due to the continuous enlargment of the growing chain through increased swelling and molecular motion of the trapped radicals. At higher reaction time the degradation of the graft chains lead to lower molecular weight and higher polymer dispersity. Effects of solvents (e.g., methanol, ethanol, and t-butanol) on the molecular weight and molecular weight distribution were discussed on the basis of swelling property and chain transfer constants of the solvents. Styrene-type graft radical being long lived compared to acrylamide type, gave long-chain styrene graft with the increase of styrene content in the reaction mixture. A comparison of the effect of one-and two-component systems on a molecular weight distribution is also discussed.     

Formation of carbon nanofibers via carbon monoxide disproportionation

Experimental results suggesting that carbon nanofibers are formed from amorphous carbon released at several compact active sites are reported. It was shown that the sites in question are catalyst crystal lattice defects formed at the crystallite contact boundaries.     

An algorithm for deducing an effective sieve residue from the rate of powder passage through a sieve

The effect of non-ideal aperture distribution of a sieving surface on the sieve residue has been the object of many experimental studies. Unfortunately, the sieving kinetics of many sieving techniques do not result in a simple probability relationship between the size distribution function of the powder and the sieve aperture distribution function. If one specifies a certain type of sieving kinetics, then one can apply probability theory to the rate of movement of powder through the sieve and the size aperture distribution function of the sieve. Under such specified sieving conditions it can be shown that it is possible to deduce a size characteristic parameter of the powder being sieved, which in this publication is described as the kinetic residue of the sieve. An algorithm for the automatic computation of the kinetic residue from the rate of powder sieving is described. The possible implementation of this algorithm to automate sieve analysis is explored.     

Strength properties of chamotte concretes based on phosphate binders

Conclusions The authors have investigated the strength properties of chamotte concretes based on phosphate binders over a wide range.They have shown the dependence of the compressive strength of the concretes on the type of phosphate binder used, the heat treatment temperature of the concrete, and its test temperature. Maximal compressive strength is exhibited by concretes roasted at 1450°C.They have established a relation between the physicochemical transitions taking place in a phosphate binder during heating and the strength characteristics of the concrete.Simultaneous introduction of phosphate binder and clay to the extent of 10–20% into chamotte concretes increases their strength at 20°C and during heating.Translated from Ogneupory, No. 6, pp. 32–36, June, 1979.     

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.