Some aspects of the role of coal thermoplasticity and coke structure in coal gasification. 2. The effects of pressure and heating rate on dilatometric parameters and optical anisotropy development

An examination of the influence of pressure and heating rate on the thermoplastic properties of a weakly coking coal and of coal with various pitch-like additives was carried out using a high pressure dilatometer. Pressure up to 4 MPa markedly increased the swelling properties and increased the plastic range by decreasing the softening temperature, but the effects of pressure were strongly influenced by rate of heating with high heating rates enhancing the effects. Additions of tar or pitch also enhanced swelling at low pressure. The solid carbonization residues from the dilatometer were examined by polarized light microscopy to determine the content and composition of optically anisotropic species. The anisotropic content was increased by increases in pressure and heating rate and pitch additives enhanced the anisotropic content, especially at low pressure, without affecting the composition of the anisotropy. No direct correlations exist between the dilatometric parameters and the optical anisotropy but their dependence on the conditions emphasizes that when considering high pressure gasification of coal, it is necessary to obtain data under appropriate conditions.     

Effect of plasticizers on the thermal decomposition of chlorinated polyvinylchloride

Plasticized samples of chlorinated polyvinylchloride (CPVC) were investigated by using thermogravimetric (TG) analysis and differential scanning calorimetry (DSC). Three different plasticizers were studied, namely, dioctyl phthalate (DOP), alkyldiaryl phosphate ester (Santiciser 2148), and triaryl phosphate ester (Reofos 50). TG experiments in nitrogen showed one major decomposition stage, involving dehydrochlorination, and minor pyrolysis reaction of the hydrocarbon residue. In contrast to the three stages previously reported to occur in the nonplasticized‐stabilized CPVC, TG analyses in air showed two distinctive decomposition stages for the plasticized CPVC samples. The DOP system provided a suggestion of a third stage. The first decomposition stage was due not only to the loss of all the chlorine present, but also to loss of the plasticizer or its decomposition products. The second decomposition stage was mostly due to char oxidation, the char being formed almost exclusively from the DCE and VDC units in CPVC polymer. DSC results showed that in the presence of nitrogen, there was no significant plasticizer effect on the thermal decomposition behavior of CPVC up to about 330°C, while in air the DSC traces also show no significant differences below 400°C. The two phosphate plasticizers showed no significant differences in their effect on the thermal decomposition behavior of CPVC under the same experimental conditions. It is believed that P₂O₅ and polyphosphoric acid are among the main constituents of the residua. These would impart a protective glassy surface to the char. This will facilitate effective flame retardant action. This preliminary conclusion is based on the premise that the more stable the char layers are, the more resilient will be the protective layer, and consequently, the better the flame retardant effect. J. VINYL ADDIT. TECHNOL., 11:21–27, 2005. © 2005 Society of Plastics Engineers     

Structural and magnetic characterization of norbornene-deuterated norbornene dicarboxylic acid diblock copolymers doped with iron oxide nanoparticles

A series of iron oxide doped norbornene (NOR)/deuterated norbornene dicarboxylic acid (NORCOOH) diblock copolymers were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), small angle neutron scattering (SANS) and superconducting quantum interference device (SQUID) experiments. γ-Fe₂O₃ nanoparticles were synthesized within the microdomains of diblock copolymers with volume fractions of NOR/NORCOOH 0.64/0.36, 0.50/0.50 and 0.40/0.60. A spherical nanoparticle morphology was displayed in the polymer with 0.64/0.36 volume fraction. Polymers with 0.50/0.50 and 0.40/0.60 volume fractions exhibited interconnected metal oxide nanostructures. The observed changes in the shape and peak positions of the small-angle neutron scattering profiles of polymers after metal doping were related to the scattering from the metal oxide particles and to the possible deformed morphologies due to the strong interparticle interactions between metal particles, which may influence the polymer microphase separation. The combined scattering from both polymer domains and magnetic particles was depicted in SANS profiles of metal oxide doped polymers. γ-Fe₂O₃ containing block copolymers were superparamagnetic at room temperature. An increase in the blocking temperature (T_b) of interconnected nanoparticles was observed and was related to the interparticle interactions, which depends on the average distance (d) between particles and individual particle diameter (2R). The sample with volume fraction of 0.4/0.6 have the lowest d/(2R) ratio and exhibit the highest T_b at 115 K.     

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.     

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.     

Dewatering behaviour of water treatment sludges associated with contaminated site remediation in Antarctica

Sludge reduction and dewatering is an important aspect of water and waste water treatment. This is especially true in the case of Australia's Antarctic contaminated site remediation program, where the reduction in volume of wastes to be returned to Australia can lead to significant transport and handling cost savings. The dewatering characterisation of water treatment sludges from an Antarctic contaminated site was conducted using a theory of suspension dewatering developed by Buscall, Landman and White. This theory uses fundamental material properties of compressibility and permeability to determine the diffusivity of a suspension. Diffusivity is a useful property that can be used to directly compare the dewaterability of various sludges. In this investigation, several water treatment sludges were collected and characterised in the field to determine the impact of temperature and additives on compressibility, permeability and diffusivity. The Antarctic sludges were found to be less compressible and less permeable than materials such as mineral suspensions and alum water treatment sludges. Compressibility was found to decrease with the addition of powdered coagulation aids such as bentonite and chitosan.     

Objective classification of vehicle seat discomfort

The objective of this study was to identify how physiological measures relate to self-reported vehicle seating discomfort. Twelve subjects of varied anthropometric characteristics were enrolled in the study. Subjects sat in two seats over a 2-h period and were evaluated via three physiological measures (near-infrared spectroscopy, electromyography and pressure mapping) yielding six testing sessions. Subjective discomfort surveys were recorded before and after each session for nine regions of the body. Conditional classification discomfort models were developed through dichotomised physiological responses and anthropometry to predict subjective discomfort in specific body locations. Models revealed that subjects taller than 171 cm with reduced blood oxygenation in the biceps femoris or constant, low-level muscle activity in the trapezius tended to report discomfort in the lower extremities or neck, respectively. Subjects weighing less than 58 kg with reduced blood oxygenation in the biceps femoris or unevenly distributed pressure patterns tended to report discomfort in the buttocks. The sensitivities and specificities of cross-validated models ranged between 0.69 and 1.00.