Surface mass transport of alumina

The kinetics of thermal grooving at the intersection of rhombohedral twin boundaries with the \((10\bar 10)\) plane in aluminium oxide were measured from 1773 to 2273 K. Analysis of the data using the model of Mullins showed that surface diffusion was the dominant mechanism for mass transport. The results were compared with other similar published work on alumina, and the following equation for surface diffusion was determined: $$D_s (cm^2 sec^{ - 1} ) = 4.05 x 10^5 exp - (452kJ mol^{ - 1} /RT).$$      

Mechanisms of antioxidant action: The role of nitroxyl radicals in the stabilization of PVC

Hindered amines and their derived oxidation products, the hindered nitroxyls and hydroxylamines are processing stabilizers and photoantioxidants for poly(vinyl chloride). The evidence suggests that oxidation of the amines occurs very rapidly and completely during mechanooxidation and that the resulting redox couple operates by a catalytic mechanism as described previously for hydrocarbon polymers.     

Comparative reactivities of coal asphaltenes during hydropyrolysis

Comparisons have been drawn in the relative reactivities of three coal asphaltenes during hydropyrolysis. All were derived from hydrogen donor-solvent extracts of bituminous coal, but had different hydrotreatment histories and different carbon contents (87.1, 91.9 and 90.8 wt% for asphaltenes 1, 2 and 3, respectively). The hydropyrolyses were carried out in the presence of CoO–MoO₃ catalyst and gaseous hydrogen at 8.7 MPa. For two of the asphaltenes (1 and 2) systematic comparisons were made for different reaction times at 425°C; for all three asphaltenes comparisons were made for l h of hydropyrolysis at 425°C. The general pattern of asphaltenes conversion indicated that more pentane-soluble product was produced from asphaltene isolated from straight coal extract (asphaltene 1). For the asphaltenes isolated from hydrotreated extracts, the extent of conversion to liquids was limited when the carbon content was high (asphaltene 2) although the pattern of conversion was similar in the other hydrotreated asphaltene (asphaltene 3). The aliphatic content of the liquid products formed was low, and the distribution of hydrogenated species in the highly aromatic liquid products indicated that complete hydrogenation of the polyaromatics produced in pyrolysis is difficult. Altogether the aliphatics made up ≈ 10 wt% of the asphaltene 1 hydropyrolysate. Aromatic hydrocarbons made up 90% of the liquid product. Phenanthrene, pyrene and anthracene were prominent, and the largest component in the mixture was phenanthrene which, together with other polyaromatics such as fluoroanthene, dominated the liquid product.     

Autocatalytic reactions in the isothermal,continuous stirred tank reactor: Isolas and other forms of multistability

Autocatalytic reactions are often complicated, and analyses of their behaviour in open systems can seem too particular to permit useful generalisation. We study here the simplest of circumstances (uniform temperatures and concentrations in the isothermal CSTR) and the simplest of reaction schemes: (i) quadratic autocatalysis (A + B→2B); and (ii) cubic autocatalysis (A + 2B→3B). The catalyst B may be stable or have a finite lifetime (B→ inert products). Allowing for this finite lifetime adds another dimension to the interest.The phenomena encountered include multistability, hysteresis, critical extinctions, critical ignitions, and anomalous relaxation times (though infinite values do not arise). Patterns of stationary states as function of residence time can show isolas and mushrooms. All these aspects yield to simple algebraic analysis. The presence of the catalyst B in the inflow can make qualitative differences of a kind parallelled by an additional, non-catalytic reaction of the same stoichiometry (e.g. A→B). Invoking the reversibility of the reactions neither increases nor diminishes their variety, and thermodynamic considerations have little to do with the many different patterns of reactivity displayed.The local stability of the various stationary states has also been characterized. Quadratic autocatalysis shows limited variety (stable node, stable focus); cubic autocatalysis generates all the kinds of stationary state possible in a two-variable system. Again all the algebra is straightforward if not always simple. Sustained oscillatory behavior (limit cycles) also occur.All these remarks relate to isothermal systems, but there are the most striking parallels between isothermal autocatalysis and the exothermic, first-order reaction in the CSTR. Behaviour with an autocatalyst of complete stability corresponds to perfect heat insulation (adiabatic operation) in the non-isothermal, exothermic system.     

Mechanisms of antioxidant action: The effect of spin traps during the processing and photooxidation of PVC

It is demonstrated by the use of spin traps that during the early stages of thermal processing of PVC considerable concentrations (> 3 × 10^?6 mol g^?1) of free radicals are produced which are primarily responsible for the initial products (hydroperoxides, unsaturation, and hydrogen chloride) previously shown to be formed in the polymer. From a semiquantitative analysis of these products, it is estimated that more than 50% of the radicals are formed from hydroperoxides and the rest by mechanoscission of the polymer chain. The spin traps are effective processing stabilizers in combination with a tin maleate HC1 scavenger. One of them (2-methyl-2-nitroso propane, MNP) has also been shown to be a photoantioxidant.     

Olfactory aposematism

Visual and acoustic cues may serve as aposematic signals that warn predators of poisonous foods. Olfactory aposematism, the use of innocuous odors as warning signals for toxic foods, is another possible means of alerting an animal that a potential food item is unpalatable. Although it has been suggested that olfactory aposematism might be the principle mode of warning utilized by plants in their defense against herbivores, experimental evidence is lacking. This study demonstrates that the opossum,Didelphis virginiana, can utilize an innocuous volatile compound found naturally in a mushroom as a warning signal for a delayed illness caused by mushroom toxin. This supports the contention that characteristic odors of toxic plants may serve a warning function, protecting herbivores from being poisoned and plants from being consumed.     

Effect of nutrient seed coating on the emergence of wheat and oats

A series of experiments was conducted under controlled soil moisture and temperature conditions in a growth chamber to examine the effect of a range of nutrient seed coatings on the emergence to wheat (Triticum aestivum L. cv. Kite) and oats (Avena sativa L. cv. Blackbutt) sown in a coarse sandy loam soil. Final emergence of oats was not reduced by a coating containing 10 kg P ha^–1 (as monocalcium phosphate [MCP]) whereas the same coating reduced wheat emergence by 15%. The emergence of both wheat and oats was severely reduced by urea coatings (supplying 10 kg N ha^–1) to 33 and 13% respectively; this injury was lessened markedly by the inclusion of phenyl phosphorodiamidate (PPD) in the urea coatings at 1% (w/w) (emergence increased to 66 and 56% respectively).Low soil moisture (67% of field capacity [FC]) resulted in almost no emergence of wheat coated with urea (± bentonites of different pH). In soil at FC, the addition of bentonite of pH 5 (B5) to urea coatings permitted greater emergence (54%) than when bentonite of pH 9 (B9) was added (32%) which, in turn, permitted greater emergence than urea coating alone (10%). When PPD and bentonite (B5 or B9) were combined either singly or together with urea in seed coatings, PPD was more effective than either of the bentonites in reducing injury and masked the slight positive effect of B5.Coatings containing various combinations of N and P sources (at 3.6 and at 8 kg ha^–1 respectively) all reduced the emergence of wheat compared to raw seed (91% emergence). When applied alone, MCP was least damaging (74%); the combination of MCP with ammonium sulfate (AS) caused somewhat more injury (68%) whilst combination with calcium nitrate (CN) caused most injury (29%). In contrast, CN alone caused relatively little damage (73%) whilst AS alone was more damaging (50%). There was no significant regression found between percentage emergence and either the calculated partial salt index or the pH of the nutrient coatings. Further work is needed to examine the mechanisms of injury due to nutrient seed coatings so that safe but effective formulations can be developed.