Direct Measurement of Transformation Zone Strains in Toughened Zirconia

Residual strains responsible for crack tip shielding have been measured within transformation zones surrounding cracks in Mg-PSZ. Two techniques were used for strain measurement: moiré interferometry and high-resolution image matching. Both methods provide maps of differential in-plane displacements within the specimen surface intersected by the crack, the latter method with the higher resolution. The results are compared with finite-element analysis to assess surface relaxation effects, and the measured strains are used to evaluate the crack tip shielding stress intensity factor. Calculations based on the assumption that the unconstrained transformation strain is hydrostatic dilatation yielded results that were significantly smaller than the measured toughness increases.     

Property-composition relationships for diesel and kerosene fuels

A range of 18 diesel fuels and 21 kerosene fuels from mainly Australian petroleum and synthetic fuel sources, including coal, shale and peat, was investigated. Compositional details were defined as the weight per cent abundances of n-alkanes, branched plus cyclic saturates, single-ring aromatics, doublering aromatics and polynuclear aromatics, using both h.p.l.c. and ¹³C n.m.r. techniques. Relationships between fuel composition and a range of fuel properties were sought. Simple linear relationships between property values and compositional data were used. Explicit correlative expressions were derived using multiple linear regression analysis, with the coefficient of multiple determination, R², indicating the quality of the fit between observed and calculated property values. In most cases good correlations were achieved. For diesels the properties investigated, with R² values in parentheses, were: inverse specific gravity (0.99); ¹³C n.m.r. aromaticity (0.99); ¹H n.m.r. aromaticity (0.88); cetane index (0.97); aniline point (0.96); diesel index (0.98); and FIA-measured aromatics content (0.77). For kerosenes the properties, with R² values in parentheses, were: ¹³C n.m.r. aromaticity (0.98); ¹H n.m.r. aromaticity (0.97); smoke point (0.88); and FIA-measured aromatics content (0.94). The results are shown to be of value in assessing the potential and limitations of hydrotreating as a process for upgrading synfuels.     

Some aspects of the analysis of coal by X-ray fluorescence spectroscopy

Bituminous coal samples from 84 distinct sources were analysed by conventional British Standards (BS) methods for phosphorus, sulphur, chlorine, ash and the ash-forming elements (calcium, silicon, aluminium, iron, sodium, magnesium, potassium, titanium and manganese). In most cases four determinations were made per element per source. Samples were crushed to ?212 μm (72 BS mesh) and pressed into aluminium cups at 20 t in^?2 (309 MPa) without binder or backing. Two pellets from each sample were analysed by wave-length dispersive X-ray fluorescence techniques, using a spectrometer equipped with a rhodium rube; the X-ray count took 60 s. The X-ray results were calibrated against the conventional results using multiple regression. The accuracy obtained was comparable with routine ‘wet chemical’ techniques. The X-ray technique is suitable for the routine determination of large numbers of samples.     

Development of high-performance liquid chromatography criteria for determination of grades of commercial olive oils. Part I. The normal ranges for the triacylglycerols

Criteria for authentic olive oils were developed from isocratic high-performance liquid chromatography analyses of 99 olive oils from the major Mediterranean producers in the 1983–1986 crop years. Authentic olive oils include extra virgin, virgin and pure or refined oils, but exclude all reesterified and adulterated oils. The extra virgin through pure grades will have a combined area for the LOO (C_18:2C_18:1C_18:1), LOP (C_18:2C_18:1C_16:0), OOO (C_18:1C_18:1C_18:1), POO (C_16:0C_18:1C_18:1), POP (C_16:0C_18:1C_18:1), and SOO (C_18:0C_18:1C_18:1) peaks between 82.0 and 92.6% of the total area (L, linoleic; O, oleic; P, palmitic; S, stearic). Authentic oils will have ratios of LOO/LOP and OOO/POO that coincide with a line defined by OOO/POO=0.7844(LOO/LOP)+0.0968; correlation coefficient is 0.885. Authentic oils will not have a trilinolein (LLL) peak over 0.5% in area. Neither triolein (OOO) nor any other single peak suffices to characterize an olive oil sample as one of the authentic grades.     

A vibrational study of the activation sequence of C–H and C–C bonds of isobutene and 1-butene on Mo(110) and (4 × 4)-C/Mo(110) surfaces

The thermal decomposition pathways of isobutene and 1-butene on both Mo(110) and 4 × 4-C/Mo(110) surfaces have been studied using high-resolution electron energy loss spectroscopy (HREELS) in order to highlight the substantially different activities of these two surfaces towards the cleavage of C–H and C–C bonds. On clean Mo(110), the CH₂ group of isobutene decomposes upon heating to 150 K, producing either a /-bonded isobutenylidene [(CH₃)₂CCH] species or a 1,1-di-/-bonded isobutenyl [(CH₃)₂CC] species. Upon further heating, extensive C–H bond scission occurs to form hydrocarbon fragments which do not contain CH₃ or CH₂ groups, but appear to have largely intact carbon skeletons. By contrast, isobutene is molecularly adsorbed on the carbide-modified surface at 150 K. Further heating produces isobutylidyne [(CH₃)₂HCC] by 300 K, which subsequently decomposes via C–C bond scission to generate surface methyl groups. The different activation sequence of the C–H and C–C bonds of isobutene on clean and carbide-modified Mo(110) surfaces is also qualitatively confirmed by comparative studies of 1-butene on the two surfaces.     

Synthesis of rigid rod polymers

Summary Rigid rod polymers containing long rigid side chains have been prepared. The initial approach to this class of materials involved the synthesis of a poly (p-phenyleneterephthalamide) (PPT) backbone with diphenylthiazolothiazole pendant groups. The synthesis and preliminary characterization of the monomer and polymer are reported.     

Diffusion of organic penetrants through low density polyethylene (LDPE) films: Effect of size and shape of the penetrant molecules

The diffusion coefficient at zero penetrant concentration D₀ of dichloromethane, chloroform, carbon tetrachloride, cyclohexane, benzene, o-xylene, m-xylene, and p-xylene, and n-hexane in LDPE were measured at 25°C, using the desorption method. The D₀ values obtained in this way are correlated with the size, shape, and chemical nature of the penetrant molecules. The temperature dependence of the diffusion coefficients of toluene and n-hexane in LDPE are also reported in the limited temperature range of 25–45°C. It indicates that, in spite of a size larger than that of toluene, n-hexane has a lower activation energy of diffusion.     

Permeation and diffusion of environmental pollutants through flexible polymers

Permeation and diffusion characteristics of high density polyethylene (HDPE), elasticized polyolefin, and polychloroprene membranes have been determined for various organic pollutants at 22 and 50°C. A standard ASTM permeation cell method was used to measure the permeation rate while an immersion/weight gain method was used to obtain the diffusion coefficient. Thickness-dependent permeation rates were determined for HDPE membranes. An equimolar mixture of various permeants was also used to see the possibility of synergistic effects by combination of permeants. The experimental results are discussed in relation to the suitability of HDPE membranes in severe environments.     

The development of porosity in heat-treated polymer carbons upon activation by carbon dioxide

A series of microporous carbons was prepared from cellulose triacetate by heat-treatment in the range 1230–2275°K and a parallel series of carbons was prepared by activation of members of the heat-treated series to 30% burn-off by reaction with carbon dioxide. The changes in porosity with heat-treatment temperature (HTT) were investigated by adsorption of carbon dioxide in the range 195–248°K and by measurement of mercury densities. By comparing porosity in unactivated and activated carbons the extents to which closed porosity can be recovered and open porosity developed by activation were investigated as a function of HTT. The predominant effect of heat-treatment was found to be conversion of open micropores to closed micropores with little change in total pore volume. Activation of 1230 and 1475°K carbons is confined almost entirely to development of micropores. With increasing HTT (meso- + macro-) pore development increases on activation while development of open micropores and opening of closed micropores become less significant.     

Effect of the Matrix and Matrix Bonding on the Creep Behavior of a Unidirectional Carbon–Carbon Composite

Creep tests were performed on single-bundle carbon–carbon specimens at high temperatures (>2310°C) and at high stress levels (>770 MPa). It was found that the creep was very strongly dependent on the filament–matrix interfacial bond. When the bond was good, the typical creep was 3.6% after 5.9 h with the primary creep a high percentage of the total deformation. When the bond was absent (dry bundle), rupture with strain was approximately 140%, and it occurred after only 0.39 h. The marked improvement in creep resistance is attributed to the ability of the matrix to distribute loads evenly and to produce a plastic flow inhibiting triaxial stress state among the filaments.