Silicon Nitride Derived from an Organometallic Polymeric Precursor: Preparation and Characterization

Partially crystalline Si₃N₄, with nanosized crystals and a specific surface area greater than 200 m²/g, is obtained by pyrolysis of a commercially available vinylic polysilane in a stream of anhydrous NH₃ to 1000°C. This polymer does not contain N initially. Crystallization to high-purity α-Si₃N₄ proceeds with additional heating above 1400°C under N₂. The changes in crystallinity, powder morphology, infrared spectra, and elemental compositions, for samples annealed from 1000° to 1600°C under N₂, are consistent with an amorphous-to-crystalline transformation. Although macroscopic consolidation and local densification occur at 1400°C, volatilization and accompanying weight loss limit bulk densification. The effect of temperature on specific surface area is examined and related to the sintering process. These results are applicable to pyrolysis, decomposition, and crystallization studies of ceramics synthesized by polymeric precursor routes.     

Fourier transform infrared study of high-purity maceral types

A suite of density-differentiated macerals from several coals was analysed by Fourier transform infrared spectroscopy to obtain information on the nature and magnitude of the variations exhibited by the various maceral fractions. The most characteristic change between maceral groups was the variation in aliphatic hydrogen content, with exinite ? vitrinite ? inertinite. Since the separation technique (density gradient centrifugation) generally provided a number of fractions within a maceral group region, some of these were also analysed. In a series of density fractions from a low rank vitrinite, it was found that the aliphatic hydrogen content decreased as the density increased. The inertinites also exhibited a decrease in aliphatic hydrogen. The inertinite C—O bands had extinction coefficients different from those of vitrinites or exinites. The data suggest that quite profound variations in organic structure as determined by FT-i.r. spectroscopy can exist within a maceral group, so that for the most critical work on coals it is necessary to take this into account.     

Enlargement of the micropores of a caking bituminous coal by controlled oxidation

In a study of the enlargement of pores of coals it has been found that treatment of a bituminous coal (PSOC No. 371, from the Pennsylvania State University Coal Section) with a 5:95 O₂:N₂ stream 4 h at 400 °C increases the surface area as measured by nitrogen adsorption at 77K by a factor of at least 50 to a value 52 m² g^?1. The increase in pore size was accompanied by a 9.7% weight loss. Simultaneously, the area as measured by carbon dioxide at 195K increased from 61 to 136 m² g^?1 and that measured by carbon dioxide at room temperature increased from 125 to 237 m² g^?1. Attempts to enlarge the pores by oxidation with hydrogen peroxide or ozone were unsuccessful. A Pittsburgh coal subject to a small percentage of oxygen in nitrogen or steam at 300 to 400 °C showed a surface area as measured by nitrogen adsorption of less than 1 m² g^?1 both before and after such pretreatment. This same coal with a 5:95 O₂:N₂ stream for 4 h at 450 °C showed a surface area of 110 m² g^?1 measured by nitrogen adsorption at 77K.     

Cuticular hydrocarbons ofReticulitermes virginicus (Banks) and their role as potential species- and caste-recognition cues

The cuticular hydrocarbon components of four castes ofReticulitermes virginicus (Banks) have been identified and quantitated. Components identified includen-alkanes; 2-, 3-, 11-, 13-, and 15-methyl-alkanes; 11,15-dimethylalkanes, (Z)-9-alkenes; (Z,Z)-7,9-dienes; and (E/Z)-6,9-dienes ranging in carbon number from C₂₁ to C₄₀. All caste forms ofR.virginicus contained the same components, but showed caste-specific proportions. Comparison of these hydrocarbons with those of the sympatric termiteR. flavipes (Kollar) suggest that cuticular hydrocarbons might serve as species- and caste-recognition cues. A bioassay was developed to test this species-recognition hypothesis, with the experimental results supporting the hypothesis.Isoptera: Rhinotermitidae.     

Preparation of Silicon Carbide/Aluminum Nitride Ceramics Using Organometallic Precursors

Solid solutions of 2H -SiC/AlN can be prepared at temperatures less than 1600°C by rapid pyrolysis ("hot drop") of mixtures of [(Me₃Si)_0.80((CH₂=CH)MeSi)_1.0(MeHSi)_0.35] _n (VPS) or [MeHSiCH₂] _n (MPCS) with [R₂AlNH₂]₃, where R=Et, i -Bu or simply by slow pyrolysis of the precursor mixture in the case of [Et₂AlNH₂]₃. In contrast, slow pyrolysis of mixtures of VPS or MPCS with [ i -Bu₂AlNH₂]₃ yields a composite of 2 H -AlN and 3 C -SiC at 1600°C, which transforms into a single 2 H -SiC/AlN solid solution on heating to 2000°C. The influences of the nature of the precursor and processing conditions on the structure, composition, and purity of the SiC/AlN materials are discussed.     

Binding of heavy metal ions by formaldehyde-polymerized peanut skins

Peanut skin, when treated with formaldehyde to polymerize tannins, is a highly efficient substrate for removal of many heavy metal ions from aqueous waste solutions. The ions Ag¹⁺, Cd²⁺, Cr⁶⁺, Cu²⁺, Hg²⁺, Ni²⁺, Pb²⁺, Zn²⁺, as well as Ca²⁺ and Mg²⁺, were contacted with formaldehyde-treated peanut skin. Quantitative removal could be achieved with Ag¹⁺, Cd²⁺, Cu²⁺, Hg²⁺, Pb²⁺, and Zn²⁺. Capacity of the substrate for ions was promising for Pb²⁺ (2.1 meq/g substrate), Cu²⁺ (3.0 meq/g), and Cd²⁺ (1.3 meq/g). Sorption from a solution containing Cd²⁺, Cu²⁺, Hg²⁺, Ni²⁺, Pb²⁺, Zn²⁺, on a packed column of formaldehyde-treated peanut skin indicated that Hg²⁺, Pb²⁺, and Cu²⁺ were rapidly and completely bound to the packing, while Cd²⁺, Ni²⁺, and Zn²⁺ were poorly bound until the preferred ions had been removed from solution.     

Partial oxidation of methane to methanol-comparison of heterogeneous catalyst and homogeneous gas phase reactions

Potential catalysts for the partial oxidation of methane to methanol have been synthesised and tested in high pressure annular reactors. Uranium oxide and molybdenum oxide catalysts and iron sodalite catalyst have been tested under the conditions reported in the patents and under conditions which allow comparison with reactions carried out in the gas phase. None of the catalysts tested showed an improvement on the gas phase results. It was found that the oxidative nature of the metal oxide catalysts is an inherent feature which reduces the selectivity to methanol.     

Studies on modeling and control of spouted bed reactors—II: Control

Control and operability characteristics of an adiabatic spouted bed reactor with a first order reaction are investigated. The reactor transient response to changing operating conditions is analyzed and the generic control problems are formulated. Reduced-order state space models suitable for process control studies are constructed by utilizing the methods of orthogonal collocation and singular perturbation.Based on modern control and estimation techniques a hierarchy of different control systems is systematically generated. The assessment of alternative d     

Dose and enantiospecific responses of white pine cone beetles,Conophthorus coniperda,to alpha-Pinene in an eastern white pine seed orchard

The white pine cone beetle, Conophthorus coniperda, exhibited dose and enantiospecific responses to -pinene in stands of mature eastern white pine, Pinus strobus, in a seed orchard near Murphy, North Carolina, USA. (–)--Pinene significantly increased catches of cone beetles to traps baited with (± )-trans-pityol. (+)--Pinene did not increase catches of beetles to pityol-baited traps and interrupted the response of beetles to traps baited with (±)-trans-pityol and (–)--pinene. Maximal attraction of cone beetles to pityol-baited traps was obtained with lures releasing (–)--pinene at a rate of 103 mg/day at 23^°C. Lures releasing (–)--pinene at rates lower or higher than 103 mg/day resulted in reduced catches to traps baited with (±)-trans-pityol. The sex ratio in all catches was heavily male biased. Attraction of the clerid predator, Thanasimus dubius, to traps baited with (±)-trans-pityol increased significantly with the presence of -pinene, irrespective of enantiomeric composition. Maximal attraction of T. dubius to pityol-baited traps occurred with devices releasing (–)--pinene at the highest rate tested, 579 mg/d at 23^°C, a sub optimal rate for cone beetles.     

The fatty acids of wax esters and sterol esters from vernix caseosa and from human skin surface lipid

Separation of sterol esters from wax esters in the lipids of vernix caseosa and adult human skin surface was accomplished by column chromatography on MgO. The fatty acids of the sterol esters and wax esters of both samples were separated into saturates and monoenes, and examined in detail by gas liquid chromatography (GLC). The saturated fatty acids of the wax esters of vernix caseosa and of adult human skin surface were remarkably similar. They ranged in chain length from at least C₁₁ to C₃₀, six skeletal types being present: straight even, straight odd, iso, anteiso, other monomethyl branched and dimethyl branched. A large number of patterns of monoenes were observed, each pattern consisting of desaturation of a specific chain at Δ6 or Δ9 plus its extension or degradation products. The mole per cent of the total Δ6 and Δ9 patterns of wax ester fatty acid monoenes of vernix caseosa were 87% and 12%, respectively, and 98% and 1%, respectively, for adult human skin surface lipid. The sterol ester fatty acids of vernix caseosa were much different from those of adult human skin surface: vernix caseosa saturates were largely branched and of lengths greater than C₁₈, whereas the saturates of adult human surface lipid resembled the wax ester fatty acids. Of the vernix caseosa monoene patterns, the mole per cent was 30% Δ6 and 70% Δ9, whereas of the adult human skin surface sterol ester fatty acids 89% were Δ6 and 11% Δ9. Chain extension was particularly pronounced in the sterol ester fatty acid monoenes of vernix caseosa amounting to 7–8 C₂ units in some cases. The fatty acids of the sterol esters of both vernix caseosa and adult human skin surface appear to be derived from the sebaceous gland and from the keratinizing epidermis, but those of the wax esters are from the sebaceous glands only.