Mortars for zirconia refractories

Conclusions The composition was developed for a mortar based on zirconium dioxide and orthophosphoric acid intended for laying zirconia refractories. The filler should be stabilized ZrO₂ powder of a particle size below 0.5 mm with 10% monoclinic fine-grain ZrO₂ mixed with orthophosphoric acid added in the proportion of 2–4% in terms of P₂O₅.The mortar was tested with zirconia refractory linings and gave satisfactory results.Owing to its low water retention capacity and short setting time Ca₇Al₆ZrO₁₈ cement cannot be recommended for a zirconia base mortar.Translated from Ogneupory, No. 8, pp. 52–59, August, 1973.     

Kinetik der Fetthärtung und Vergleich verschiedener Katalysatoren

Kinetics of Edible Oil Hydrogenation and Comparison of Different Catalysts The kinetics of selective hydrogenation of edible oils were investigated giving special consideration to geometrical isomerization. The reaction was carried out in a stirred semibatch pressure vessel under constant hydrogen pressure and isothermal conditions. Tests with different catalysts such as nickel, palladium, platinum, rhodium and copper chromite showed considerable differences in selectivity and isomerization behaviour. It could be shown that the major part of the elaidic acid (trans) is formed during the saturation of the linoleic acid to the monoenoic acid. Kinetic measurements with the system soybean oil/copper chromite showed that the hydrogen pressure has the biggest effect on selectivity and isomer distribution. All observed phenomena of the hydrogenation system could be described using a modified Langmuir-Hinshelwood type model. Using this model, observed conversion curves for different oils like rape seed, olive, soybean, sunflower seed and thistle oil could be simulated with good accuracy.     

Impact thermoplastics: Combined role of rubbery phase volume and particle size on toughening efficiency

A relationship has been found for OSA (olefin-acrylonitrile-styrene) polymers between normalized Izod impact strength (ΔI/N) or yield stress (Δσy/N) with mean particle radius. These normalized functions (which analytically include radius and rubbery phase volume) are representative of the toughening effect of a single particle with respect to the styrene-acrylonitrile (SAN) rigid matrix. ΔI/N and Δσy/N increase exponentially as a function of the radius. This approach, for Izod, was also applied to HIPS and toughened nylon reported in the literature and similar results were obtained. In the case of nylon, however, the ΔI/N values are split in two different curves related to the tough-brittle transition described in that literature. Referring to OSA, three samples (with the largest radii more than 0.22 μm) fail in a brittle manner and do not fit the curve of ΔI/N: they fit, however, that of Δσy/N. Further work must be done in order to investigate a decisive role either of interfacial adhesion (eventual lack for these three materials) or of tough-brittle transition mentioned before for shear-yielding deforming materials. In fact, OSA has behavior intermediate between that of nylon and HIPS which deforms by crazing.     

Strength after heating of unfired refractories containing chemical bonding agents

Conclusions Out of all the experimental bonding agents used in the production of unfired magnesite and magnesite-chromite refractories: SDW; MgSO₄,· 7H₂O; MgSO₄·7H₂O + H₃BO₃; (NaPO₃)_n, the greatest strength on heating is provided by the addition of 2% (NaPO₃)_n.An addition of boric acid to the refractories using the MgSO₄,·7H₂O bonding agent helps to strengthen the refractories in the 500–900°C interval; at a higher temperature the refractories with the magnesium sulfate plus boric acid bonding have no advantages in their strength properties over the articles with the magnesium sulfate bonding agent only.The magnesite-chromite articles with the chemical bonding agent have better strength in the 1000–1400°C interval than the magnesite articles. This is explained by the spinelformation reactions which occur at these temperatures.On the basis of these studies (NaPO₃)_n and also MgSO₄,· 7H₂O with an addition of H₃BO₃ can be recommended as chemical bonding agents for unfired magnesite-chromite refractories.Translated from Ogneupory, No. 1, pp. 48–52, January, 1979.     

Photoisomerization of antiaggregation pheromone verbenone: Biological and practical implications with respect to the mountain pine beetle,Dendroctonus ponderosae Hopkins (Coleoptera: Scolytidae)

Release of the antiaggregation pheromone, verbenone, at 3.8 mg/ day from a concentrated source within a multiple-funnel trap completely inhibited response by the mountain pine beetle (MPB),Dendroctonus ponderosae Hopkins, to attractive semiochemical lures. When aerial applications were simulated and verbenone was released at the same rate from beads lying in a 2×2-m area on the forest floor 15–35 cm below a trap, the response of the MPB was inhibited by only 50%. This reduced inhibition may be explained in part by the photoisomerism of verbenone. When exposed to full sunlight on two occasions, the times required for 50% of verbenone vapors to be converted to chrysanthenone were 75 and 100 min, respectively. Trap and tree-baiting experiments indicated no biological activity of chrysanthenone. Rapid photoisomerization could reduce the concentration of verbenone below biologically active levels and would allow the MPB to colonize trees close to already occupied hosts, contributing to the characteristic clumped distribution of MPB attack. The rate of verbenone photoisomerization may vary according to geographic location, stand elevation and density, and should be considered before verbenone is applied to control the MPB and other bark beetles.     

Role of precipitation bath components in the manufacture of viscose fibres

Conclusions An analysis has been made of data on structure formation processes in spinning viscose fibres and of the connection of the primary structure with the properties of the finished fibres and yarns.It has been shown that the attainment of high physicomechanical and operational properties of viscose fibres is possible by preventing premature crystallization of the cellulose in the freshly-spun gel-fibre.Retardation of the cellulose crystallization process in spinning viscose fibres is advisably effected as a result of reducing the activity of water in the precipitation bath.Translated from Khimicheskie Volokna, No. 1, pp. 8–13, January–February, 1986.     

Well-defined polymer precursors synthesized by RAFT polymerization of N,N-dimethylacrylamide/N-acryloxysuccinimide: random and block copolymers

N,N-dimethylacrylamide (DMA) and N-acryloxysuccinimide (NAS) were copolymerized by the reversible addition–fragmentation chain transfer (RAFT) polymerization technique, to obtain random and block copolymer precursors onto which different side-groups may be statistically grafted via the reactive NAS units. These reactive copolymers have interesting applications in various fields such as coatings and paints, water purification and biology. Random poly(DMA-co-NAS) copolymer chains were synthesized with a 75/25 molar ratio, high conversion, an excellent molecular weight (MW) control from 5000 to 130 000 g mol⁻¹, and low polydispersity index (M_w/M_n<1.1). Poly(DMA-b-NAS) block copolymers were synthesized by a two step method, in which a poly(DMA) homopolymer was prepared first and then used as macro-chain transfer agent to polymerize NAS. For example, a poly(DMA-b-NAS) sample was obtained with an average molecular weight of 44 300/7400 g mol⁻¹ corresponding to 447 DMA and 44 NAS units. Such block copolymers had not yet been synthesized by any controlled polymerization technique. They can be used to prepare polymers with exactly the same backbone and an increasing number of different side groups (e.g. hydrophobic, ionic or fluorescent).     

Radical entry mechanisms in redox-initiated emulsion polymerizations

The mechanisms and kinetics of radical entry in emulsion polymerizations utilizing redox initiation are investigated using polymerization rate data obtained by reaction calorimetry and electrospray mass spectroscopy analysis of initiator-derived aqueous-phase products. These data have been used to evaluate an initiation scheme for redox-initiated emulsion polymerizations of common monomers such as styrene and methyl methacrylate based around the oxidant, tert-butyl hydroperoxide. Redox initiators are broadly classed by the solubility of their radical products: Hydrophilic radicals enter by propagating to a critical degree of polymerization to become surface-active whilst more hydrophobic radicals may enter particles directly. When direct entry is applicable (the hydrophobic case), initiation efficiency will always be very high.     

Thermal analysis of montmorillonites modified with quaternary phosphonium and ammonium surfactants

The thermal stability of seven organically modified montmorillonites (‘organoclays’) has been investigated using differential thermal analysis, differential scanning calorimetry, and thermogravimetry in conjunction with X-ray diffractometry. Six organoclays were synthesised by replacing the interlayer inorganic cations, initially present, with quaternary phosphonium and ammonium surfactant cations. The samples modified with tetrabutylphosphonium (TBP), and butyltriphenylphosphonium (BTPP) ions have an appreciably higher thermal stability than the octadecyltrimethylammonium (ODTMA)-modified clays. Thus, in the case of TBP- and BTPP-modified montmorillonites, the onset temperature of decomposition is close to 300 °C. Samples modified with hexadecyltributylphosphonium (HDTBP) ions have a lower onset temperature of decomposition of 225 °C. In comparison, the onset temperature for ODTMA-montmorillonites (obtained at different concentrations of ODTMA-bromide) ranges from 158 to 222 °C, being highest where the concentration of intercalated surfactant is lowest. The onset temperature for a commercial alkylsilane-treated quaternary ammonium-modified organoclay (S-BEN N-400FP) is 207 °C. The basal spacing of the TBP- and BTPP-modified clays is 1.7–1.8 nm, indicating a monolayer arrangement of quaternary phosphonium ions in the interlayer space, while the value of 2.5 nm for HDTBP-montmorillonite indicates a more open structure. The ODTMA-modified samples have basal spacings ranging from 1.9 to 2.1 nm, indicative of a bilayer to pseudo-trilayer arrangement. The exceptionally high basal spacing of 3.4 nm for the S-BEN N-400FP organoclay might be due to interlayer penetration of organosilane hydrolysis products during synthesis. The thermal properties of organoclays are apparently related to the nature of the surfactants and their arrangement in the interlayer space of montmorillonite.     

High-strength ceramic from zirconium dioxide with an additive of the oxides of yttrium and iron

Translated from Steklo i Keramika, No. 3, p 26, March 1991.