Compound types and properties of Utah and Athabasca tar sand bitumens

Properties and compound types were examined in detail for tar-sand bitumens representative of four major deposits in Utah and Alberta. Methods for bitumen extraction, separation, and compound type (functional group) analysis are presented. Results of the analyses are compared with each other and with results in the literature for tar-sand bitumens and petroleum. Comparison of the results of Utah bitumens with the Athabasca bitumen provides a basis for evaluation of the Utah bitumens because considerable information about the processing characteristics of the Athabasca bitumen has been reported. Simulated distillation and Chromatographic separation data indicate that, in general, the tarsand bitumens most closely resemble Wilmington petroleum with respect to hydrocarbon/non-hydrocarbon distribution, especially in the non-distilling portion (the distillable portions, mainly hydrocarbons, are similar for all samples). Tar-sand bitumens were also shown to differ significantly from one another, principally in the amounts and kinds of heteroatomic compound types present. This information is important because of the effects that composition has on recovery and refining processes. Analyses of the chemical functionalities also provide a basis for developing correlations between bitumen composition and the recovery and processing characteristics of the bitumen.     

On the mechanism of kerogen pyrolysis

Aromaticities determined by ¹³C n.m.r. are reported for five shale oil samples (Green River formation) prepared under widely different pyrolysis conditions. In the absence of high-pressure hydrogen, the total amount of aromatic carbon in the products is nearly twice that in the raw shale. This is true for a wide range of pyrolysis conditions, although the distribution of aromatic carbon between the oil and carbonaceous residue changes. High-pressure hydrogen appears to inhibit both the formation of additional aromatic carbon during pyrolysis and the coking of aromatic oil. An improved kerogen decomposition mechanism is reported that accounts for these effects and provides for changes in the aromaticity of the liquid product with pyrolysis conditions. Further work is necessary to make it quantitative and account for gas formation.     

In-Plane Cracking Behavior and Ultimate Strength for 2D Woven and Braided Melt-Infiltrated SiC/SiC Composites Tensile Loaded in Off-Axis Fiber Directions

The tensile mechanical properties of ceramic matrix composites (CMC) in directions off the primary axes of the reinforcing fibers are important for the architectural design of CMC components that are subjected to multiaxial stress states. In this study, two-dimensional (2D)-woven melt-infiltrated (MI) SiC/SiC composite panels with balanced fiber content in the 0° and 90° directions were tensile loaded in-plane in the 0° direction and at 45° to this direction. In addition, a 2D triaxially braided MI SiC/SiC composite panel with a higher fiber content in the ±67° bias directions compared with the axial direction was tensile loaded perpendicular to the axial direction tows (i.e., 23° from the bias fibers). Stress–strain behavior, acoustic emission, and optical microscopy were used to quantify stress-dependent matrix cracking and ultimate strength in the panels. It was observed that both off-axis-loaded panels displayed higher composite onset stresses for through-thickness matrix cracking than the 2D-woven 0/90 panels loaded in the primary 0° direction. These improvements for off-axis cracking strength can in part be attributed to higher effective fiber fractions in the loading direction, which in turn reduces internal stresses on weak regions in the architecture, e.g., minicomposite tows oriented normal to the loading direction and/or critical flaws in the matrix for a given composite stress. Both off-axis-oriented panels also showed relatively good ultimate tensile strength when compared with other off-axis-oriented composites in the literature, both on an absolute strength basis as well as when normalized by the average fiber strength within the composites. Initial implications are discussed for constituent and architecture design to improve the directional cracking of SiC/SiC CMC components with MI matrices.     

Chemistry of organosulphur compound types occurring in heavy oil sands: 3. Reaction of thiophene and tetrahydrothiophene with vanadyl and nickel salts

As part of a study of the chemistry of the steam-stimulated recovery of heavy oils, the hydrolysis and subsequent desulphurization of tetrahydrothiophene and thiophene by aqueous solutions of vanadyl and nickel salts was investigated. Vanadyl sulphate and vanadyl chloride were shown to behave very differently, emphasizing that these salts have different molecular species in aqueous solutions.     

Polyether-metal salt complexes: 1. The elevation of the glass transition temperature of polyethers by metal salts

Various metal halides have been dispersed in high and low molecular weight, amorphous poly(propylene oxide), by solution blending techniques, to give single phase polymeric complexes which remained thermoplastic even at very high salt loadings. These complexes were amorphous and showed a single well-defined glass transition temperature (T_g) by differential thermal analysis with the T_g of the complex up to 140°C greater than the T_g of the parent polymer. The T_g elevation depended upon both the amount and the type of salt added and for a given salt the elevation followed a sigmoidal curve which levelled out at high salt concentrations. The T_g data have been interpreted in terms of a chelate ring model involving the co-ordination of two adjacent ether oxygen atoms in the polymer backbone to the salt. Using this model it was possible to consider the complex as a random copolymer consisting of complexed and uncomplexed monomer units. The contribution of crosslinking by metal salts to the elevation of T_g was assessed by studying poly(tetramethylene glycol)-zinc chloride complexes in which chelate formation is entropically unfavourable. Mechanical data are reported for ZnCl₂ complexes with high molecular weight poly(propylene oxide). The results indicate that ZnCl₂ increased the rubbery modulus and this has been interpreted in terms of ZnCl₂ forming a few, weak intermolecular crosslinks.     

Hydrolysis of fish oils containing polymers of triacylglycerols by pancreatic lipasein vitro

Fish oils containing different levels of polymers of triacylglycerols formed during autoxidation were incubated with pancreatic lipase to establish whether these polymers are substrates for lipase hydrolysis. With oils containing low amounts (less than 4%) of triacylglycerol polymers as substrates, both triacylglycerols and polymers of triacylglycerols were almost completely hydrolyzed, and fatty acid monomers and monoacylglycerols were the major lipid products. Under the same incubation conditions, some triacylglycerols remained intact when highly oxidized oils containing 20 or 30% triacylglycerol polymers were the substrate. The fatty acid composition of these residual triacylglycerols was almost identical to that of triacylglycerols present at the start of the assay. When fish oil containing 30% triacylglycerol polymers was incubated with the lipase, the component triacylglycerols and polymers of triacylglycerols were hydrolyzed at similar rates, and fatty acid dimers were detected as a product. It is concluded that the high molecular weight polymers of triacylglycerols present in oxidized fish oils can be hydrolyzed by pancreatic lipasein vitro.     

Synthesis and characterization of polyacrylonitrile grafted with poly(2,6-dimethyl-1,4-phenylene oxide)

Summary Free radical copolymerization of acrylonitrile (AN, M₁) with poly(2,6-dimethyl-1,4-phenylene oxide)--vinylbenzyl ether (PPO-VBE, M₂, _n + 4200g/mol, _w/ _n + 1.04) was performed at 60°C in either a mixture of N,N-dimethylformamide/toluene or tetrahydrofuran, using 2,2-azoisobutyronitrile (AIBN) as initiator. The characterization of the resulting polyacrylonitrile grafted with poly(2,6-dimethyl-1,4-phenylene oxide) (PAN-g-PPO) was performed by 200 MHz ¹H-NMR spectroscopy and solubility.     

Automatic and Efficient Human Pose Estimation for Sign Language Videos

We present a fully automatic arm and hand tracker that detects joint positions over continuous sign language video sequences of more than an hour in length. To achieve this, we make contributions in four areas: (i) we show that the overlaid signer can be separated from the background TV broadcast using co-segmentation over all frames with a layered model; (ii) we show that joint positions (shoulders, elbows, wrists) can be predicted per-frame using a random forest regressor given only this segmentation and a colour model; (iii) we show that the random forest can be trained from an existing semi-automatic, but computationally expensive, tracker; and, (iv) introduce an evaluator to assess whether the predicted joint positions are correct for each frame. The method is applied to 20 signing footage videos with changing background, challenging imaging conditions, and for different signers. Our framework outperforms the state-of-the-art long term tracker by Buehler et al. (International Journal of Computer Vision 95:180–197, 2011), does not require the manual annotation of that work, and, after automatic initialisation, performs tracking in real-time. We also achieve superior joint localisation results to those obtained using the pose estimation method of Yang and Ramanan  (Proceedings of the IEEE conference on computer vision and pattern recognition, 2011).     

Methods for the determination of cyclopropenoid fatty acids. VII. The dilution-HBr-titration technique as a general method

The stepwise HBr titration method for the cyclopropenoid analysis of cottonseed oils is subject to serious inaccuracies when applied to samples containing higher cyclopropenoid concentrations, particularly if they contain appreciable amounts of alumina-adsorbable materials. A modification of the method is described which eliminates these sources of error. Its validity has been established by the analysis of a wide range of synthetic compositions including compositions containing massive amounts of interfering HBr-reactive substances and other alumina-adsorbable materials. The method with further modification can be used to analyze glycerides with the same high degree of accuracy. Presented at the AOCS Meeting in Houston, April 1965. So. Utiliz. Res. Dev. Div., ARS, USDA.