Synthesis and properties of aromatic polyesters and brominated polyesters derived from α,α′-bis(4-hydroxyphenyl)-1,4(or 1,3)-diisopropylbenzene

The interfacial polycondensation technique was used for the preparation of polyarylates and brominated polyarylates. Polyarylates and brominated polyarylates were prepared by mixing a solution of diacid chloride such as terephthaloyl chloride, isophthaloyl chloride, or their mixture in dichloromethane with an aqueous alkaline solution of ,-bis(4-hydroxyphenyl)-1,4(or 1,3)-diisopropylbenzene or ,-bis(4-hydroxy-3,5-dibromophenyl)-1,4(or 1,3)-diisopropylbenzene using triethylbenzylammonium chloride as the phase transfer agent. Moderate to high molecular weight polyarylates with _inh up to 1.27 dL/g were obtained, and most of them could be cast into tough and flexible films depending on the polymer composition. In general, polymers containing more 1,3-isomer or isophthaloyl chloride moieties gave transparent and flexible films and had lower glass transition temperatures and higher solubility. Although these polymers have two isopropylidene linkages in their repeating units, they still exhibit moderately high thermal stability and show no obvious weight loss before 400 °C. The introduction of bromine on the polymer backbone caused a decrease of inherent viscosity, crystallinity, and thermal stability of the polyarylates, while causing an increase in glass transition temperature and a great enhancement of fire retardancy.     

Phase transitions and dimensional and morphological changes in an “Aluminum Hydroxide-Alumina” system under a shock-wave action

A method is proposed to study the sequence of phase transitions in powdered materials under a shock-wave action. It is shown that the aluminum hydroxide-alumina system has the following sequence of phase transformations under a shock-wave action: bayerite boehmite -Al₂O₃ -Al₂O₃. It is found that there are no transitional high-temperature modifications of alumina. A method is developed for obtaining a submicron alumina powder, which allows obtaining materials with a controlled phase composition, including a thermodynamically stable -modification of Al₂O₃. The specific features of the morphological structure and the phase and structural characteristics of powders after a shock-wave action are considered.Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 1, pp. 110–119, January–February, 2005.     

Asymmetric structure analysis of active surface-sites by in situ polarized total-reflection fluorescence EXAFS

An in situ polarization-dependent total reflection fluorescence yield EXAFS system has been developed to analyze the asymmetric structures of catalytically active metal sites on single crystal surfaces. This technique separately reveals the bonding feature parallel and perpendicular to the support surface. The systems of Cu ion on -quartz(0001), Co oxide on -alumina(0001), and Pt₄ on -alumina(0001) were investigated as model surfaces of supported catalytic systems. The location of Cu sites on -quartz(0001), the epitaxial growth mode of Co₃O₄ on -alumina(0001), and the Pt raft structure with metal-support interaction in Pt₄ / -alumina(0001) were observed.     

Shape-selective isopropylation of biphenyl over a highly dealuminated mordenite: effect of propylene pressure

A highly dealuminated H-mordenite (H-M) catalyzed the selective isopropylation of biphenyl to 4,4-diisopropylbiphenyl (4,4-DIPB). The high selectivity is ascribed to the shape-selective catalysis in mordenite pores. The selectivity of 4,4-DIPB decreased during the isopropylation of biphenyl due to isomerization of 4,4-DIPB under low propylene pressure. The increase of propylene pressure suppressed the isomerization in the isopropylation. 4,4-DIPB itself was isomerized over highly dealuminated H-M under low propylene pressure.     

Ammonia synthesis over multi‐promoted iron catalysts obtained by high‐energy ball‐milling

The feasibility of producing ammonia synthesis catalysts from highenergy ballmilling of a simple mixture of the constituent oxides has been investigated. The effect of ballmilling the fused oxidic precursor of the industrial KM1 ammonia synthesis catalyst has also been studied. The results show that highenergy ballmilling offers some interesting possibilities for preparing novel catalytic materials. It is observed that ballmilling of the powder oxides mixture leads to formation of solid solutions and the catalytic activity is significantly higher than that of the starting material. Furthermore, ballmilling of fused oxidic KM1 precursor is seen to give rise to more homogeneous promoter distribution and slightly higher activity. The quite small activity increase observed in this case probably reflects the fact that the fusion process has already resulted in a close to optimal promoter distribution. The choice of atmosphere during ballmilling is also seen to offer possibilities for regulating the phase composition.     

Response of the European elm bark beetle,Scolytus multistriatus (Coleoptera: Scolytidae), to isomers and components of its pheromone

Laboratory bioassays (two methods) and field tests demonstrated synergistic action of the three components [(–)-4-methyl-3-heptanol (I); (–)-2,4-dimethyl-5-ethyl-6,8-dioxabicylo[3.2.1]octane (-multistriatin) (II); and (–)--cubebene (III)] of the pheromone bouquet ofScolytus multistriatus. Individually and in pairs the components were slightly attractive; I+II was clearly the most active doublet. Indirect evidence indicates that only one of the four enantiomers of I is active. Of the , , and isomers of II, only the is active. With the addition of compound I, slightly attractive extract from mated females became nearly as active as extract from virgin females.     

Partial oxidation of methane to synthesis gas

Partial oxidation of methane to synthesis gas has been carried out over a number of transition metal catalysts under a range of conditions. It is found that the metals Ni, Ru, Rh, Pd, Ir and Pt, either supported on alumina or present in mixed metal oxide precursors, will bring the system to equilibrium. The yield of CO and H2 improves with increasing temperature in the range 650–1050 K, and decreases with increasing pressure between 1 and 20 atm. An excellent yield (92%) is obtained with a 421 N₂CH₄O₂ ratio at 1050 K and atmospheric pressure, with a space velocity of 4×10⁴ hour^–1.     

Experimental Study of Ignition of a Gasoline–Air Mixture in a Constant‐Volume Combustion Chamber

The characteristics of flamekernel development in a premixed gasoline–air mixture in a cylindrical constantvolume combustion chamber are measured. The experiments are performed with an initial temperature of 393 K, pressure of 6 bar, and equivalence ratio = 0.8 with the use of various ignition systems and spark plugs. The schlieren pictures of the process are presented, and the measured results for flame velocity, heatrelease rate, and mass fraction of the burnt fuel are analyzed.     

Electrosynthesis of 4,4′-dinitroazobenzene on PbO2 electrodes

Parameters which affect the electrosynthesis of 4,4-dinitroazobenzene from p-nitroaniline on platinum and PbO₂ electrodes were investigated and optimum conditions were determined. Maximum conversion efficiency for electrosynthesis was 95% with a pure -PbO₂ electrode. It was found that the electrocatalytic activity of a PbO₂ electrode depends upon its / ratio and its degree of crystallinity. The effects of the added base and water on the conversion efficiency were also elucidated.     

Factors governing the electrochemical synthesis of α-nickel (ii) hydroxide

The electrodeposition of -nickel hydroxide is promoted by the simultaneous chemical corrosion of the electrode by an acidic nitrate bath. Chemical corrosion results in the formation of a poorly ordered layered phase which is structurally similar to -nickel hydroxide and provides nucleation sites for the deposition of the latter. Therefore under conditions which enhance corrosion rates such as low current density (<1.3 mA cm–2), high temperature (60 C), high nickel nitrate concentration ( 1M) and the resultant low pH (1.7), -nickel hydroxide electrodeposition is observed, while -nickel hydroxide forms under other conditions. Further, -nickel hydroxide deposition is more facile on an iron electrode compared to nickel or platinum.     

Suppression of the α → β-nickel hydroxide transformation in concentrated alkali: Role of dissolved cations

The presence of dissolved cations such as Al and Zn in alkaline electrolyte (6 M KOH) suppresses the -nickel hydroxide transformation. The uptake of Al (10 mol%) and Zn (30 mol%) exhibited by the active material likely stabilizes the -phase. Dissolved Al is deleterious to the performance of the nickel hydroxide electrode, whereas, dissolved Zn enhances the specific discharge capacity of nickel hydroxide by approximately 25% showing that the mode of metal uptake is different in the two cases.     

Crystal Orientation Dependence of Macropore Formation in n-Si With Backside-Illumination in HF-Electrolyte

The formation of macropores on anodically biased n-type silicon with backside-illumination was investigated as a function of crystal orientation and bias voltage. Specimens were cut from bulk crystals with various orientations from {100} to {111}, polished and subjected to anodic etching in HF. The resulting pores were investigated on cleaved samples by SEM. All pores were found to grow in either a 100 direction or a 113 direction, depending on the misorientation angle. This finding applies also to the branching of a single pore. The results can be understood if the valence for the dissolution reaction is approximately 2.6 in 100 and approximately 4 in the 113 direction, and if all other directions are not allowed for the growth of pores in Si.     

Additional male mediterranean fruitfly (Ceratitis capitata wied.) Attractants from Angelica seed oil (Angelica archangelica L.)

Two sesquiterpene hydrocarbons, -copaene and -ylangene, were isolated from bioactive fractions of angelica seed oil and were shown by field bioassays to be attractive to the male Mediterranean fruit fly. Their relative attractiveness, compared with the(+)-and (–)--copaene enantiomers, are: (+)--copaene>angelica -copaene>angelica -ylangene>(–)--copaene. The enantiomer ratios for the two compounds are: -copaene, 61.4% (+), 38.6% (–); -ylangene, 91.9% (+), 8.1% (–).trans--Bergamotene was also isolated from the same fractions, but in sufficient quantity for bioassay [enantiomer ratio: 95.7% (+), 4.3% (–)].     

Effect of the naturally occurring salt ‘Kanwa’ as a fertilizer on the productivity ofStylosanthes in the subhumid zone of Nigeria

Soil nutrient deficiencies pose a serious limitation to higher crop and forage yields in the Nigerian subhumid zone. Some of the deficiencies may be alleviated by using as a fertilizer a salt mined locally called Kanwa which is traditionally used as a cattle lick. Yields ofStylosanthes hamata cv Verano andS. guianensis cv Cook seed and dry matter increased with Kanwa application at different locations. The effect of Kanwa was enhanced when phosphorus was adequately supplied. Improvements to soil physical properties were proportional to the yield of the legume. The implications of good quality fodder and improved soil conditions in Agro-pastoral Systems in the Nigerian SHZ are discussed.     

Mechanisms of Iron Activation on Fe-Containing Zeolites and the Charge of α-Oxygen

According to previous Mössbauer data [1] -sites formation at the activation of Fe-containing zeolites is accompanied by irreversible self-reduction of the iron, proceeding without participation of an external reducing agent. Reduced Fe²⁺ ions are inert to O₂ but are reversibly oxidized to Fe³⁺ by N₂O, generating the -oxygen species, O, which provide selective oxidation of hydrocarbons.In this work, the mechanism of -sites formation was studied via quantitative measurement of the dioxygen amount desorbed into the gas phase at the step of self-reduction. A prominent role of the zeolite matrix chemical composition has been revealed. For example, with zeolites of Al–Si composition (FeZSM-5 and Fe-), heating to 900 °C in a closed vacuum space leads to irreversible evolution of O₂, which is accompanied by the immediate formation of -sites. Similar heating of B–Si and Ti–Si zeolites also leads to dioxygen evolution; however, this evolution is reversible and is not accompanied by formation of -sites. Activation of these zeolites occurs only in the presence of water vapor. Stoichiometric measurements showed that in terms of charge one regular O^2- ion, removed at the activation, is equivalent to two -oxygen atoms. So, -oxygen is identified as an ion-radical species O ^-., whose unique oxidation properties still distinguish it from the generally observed O^-. radicals.The mechanism of -sites formation is proposed, in which the process of strong chemical stabilization of reduced Fe²⁺ atoms in the zeolite structure is a key step, making impossible the reoxidation of the iron with O₂.     

Kinetics and Mechanism of Copolymerization of α-terpineol with Methylmethacrylate in Presence of Azobisisobutyronitrile as an Initiator

The radical copolymerization of -terpineol with methyl-methacrylate in xylene at 80±0.1C for 50 minutes in the presence of azobisisobutyronitrile (AIBN) follows ideal kinetics and results in the formation of a functional and random copolymer. The activation energy is 33 KJ/mole. The IR spectrum and NMR spectra of the copolymer(s) shows the bands at 1750 and 3400 cm^–1 for ester group of methylmethacrylate and alcoholic group of -terpineol and peaks at 3 to 4 for methoxy group and at 6.5 to 7.5 due to alcoholic group of methylmethacrylate and -terpineol repectively. The values of reactivity ratios, calculated by Kelen–Tüdos method, are r ₁ (MMA) = 0.18 and r ₂ (-terpineol) = 0.046. The Alfrey-Price; Q–e parameters for -terpineol has been calculated as 0.149 and 2.486. The mechanism of copolymerization has been elucidated and it is concluded that the double bond present in the monocyclic ring of -terpineol is an active site for copolymerization and the alcoholic group of -terpineol remain to give functional copolymer.     

Localization of Deformation in Copper Single Crystals During Explosive Collapse

It is established that highrate axisymmetric loading of single crystals by the method of explosive collapse of a hollow thickwalled cylinder causes deformation that involves all active closepacked slip systems. The spatial distribution of macroscopic sites of strain localization is determined by the crystallography of the active systems in singlecrystalline samples. The established correlation between the observed shear bands in the microstructure of copper single crystals and {111} active slip <110> systems of facecentered cubic (FCC) crystals and their symmetric arrangement show that deformation at a rate of 5 · 10⁴ sec^-1 occurs according to the crystalline structure of the materials.     

Investigation of sex pheromone components of female asian corn borer,Ostrinia furnacalis (Hübner) (Lepidoptera: Pyralidae) in Taiwan

(E)-12-Tetradecenyl acetate (E12–14OAc), (Z)-12-tetradecenyl acetate (Z12–143nOAc), and tetradecanyl acetate (14OAc) were extracted and identified as major chemical components from female tips of the Asian corn borer,Ostrinia furnacalis (Hübner) (Lepidoptera: Pyralidae) in Taiwan, with a combined wash ratio of 483715 and an individual female ratio of 453916. The average amount ofE12-,Z12–14OAc and 14OAc in each female gland was 6.6±4.6, 5.8±3.5, and 2.4±1.7 ng/female, respectively. The mixture of these three synthetic chemicals not only gave strong activities in male antennae but also could catch significantly more males than virgin females in field-trapping tests. The field test also showed no significant difference in trapping ability among the three-component Taiwan formulations, the two-component Taiwan formulation (Z12–14OAc andZ1214OAc, 5347), and the Japan formulation (Z12–14 OAc andE 12–14OAc, 3:2).     

Unexpected products of the allyldiethylamine hydroformylation homogeneously catalyzed by rhodium complexes

Attempts to carry out the hydroformylation of allyldiethylamine homogeneously catalyzed by rhodium complexes led to unexpected formation of N,N,N,N-tetraethyl-1,4-diaminobutane and 4-(diethylamino)-1-butanole as final products. The role of the catalyst on the product formation and the reaction mechanism are briefly discussed.     

Acetone conversion to isobutene in high selectivity using zeolite β catalyst

The catalytic activity of the proton forms of zeolite and ZSM-5 are compared for the conversion of acetone. Zeolite demonstrates markedly enhanced selectivity to isobutene and selectivities of >80% can be achieved for conversions up to 65%. In contrast high selectivities to isobutene with ZSM-5 can be attained only at very low conversions (5%).