The autoignition of polymers

A consistent and relatively simple method is presented for studying the unpiloted ignition of polymeric materials in contact with hot air. The ignition behavior of a particular polymer as determined by its bulk properties may be characterized by the relationship between sample mass and ignition time at constant area for a series of furnace temperatures. Extrapolation of this linear relationship at a given furnace temperature to zero mass results in an intrinsic ignition time which represents the rate of the ignition process when the time required to heat the sample to its decomposition temperature has been eliminated, i.e., the sample is brought to its decomposition temperature instantaneously. The temperature dependence of this intrinsic ignition time shows an Arrhenius relationship with an apparent activation energy of 8–10 kcal/mole for all but one material investigated. This indicates that the mechanism controlling the kinetics of such an ignition process is a physical one, most likely the diffusion of combustible gaseous products into the heated air surrounding the sample.     

Colitis cystica profunda

Colitis cystica profunda is a benign disease of the colon. Its importance lies in differentiating it from mucus-producing adenocarcinoma. It has rarely been described in the surgical literature. A review of records of patients seen at the Mayo Clinic produced 66 clinical cases of localized colitis cystica profunda, and in 21 patients the diagnosis was confirmed histologically. Follow-up, which was available in all patients, ranged from 2 months to 29 years, with a mean follow-up of more than 8 years. The data suggest that local excision is the preferred initial therapy.     

Chemical composition of degrading mangrove leaf litter and changes produced after consumption by mangrove crabNeosarmatium smithi (Crustacea: Decapoda: Sesarmidae)

The leaves of the mangroveCeriops tagal contained 3.2–4.1% (all percentages relate to dry weight) ofd-1-O-methyl-muco-inositol previously unreported in mangroves. They consisted of 37% aqueous acetone-water-soluble material, 18% water-insoluble polysaccharides, and ca. 50% polyphenols, which include soluble and insoluble tannins and lignin. The polysaccharide component sugars were glucose, arabinose, uronic acids, mannose, xylose, galactose, and rhamnose in the proportions 28262210752, respectively. The leaves were pectate rich, and the low level of glucan was presumed to consist mainly of cellulose. After four weeks of biodegradation, ca. 60% of the acetone-water-soluble material was lost from the leaves. Degradation processes greatly altered the polysaccharide components in the leaves. Pectates were rapidly degraded, while other polysaccharides, although reduced proportionately, resisted degradation at about the same level, and all component sugars were found in the 8-week-old leaves. Apparent lignin contents increased from 15 to >30% during biodegradation up to eight weeks. The yields of the major fractions in corresponding fecal material fromNeosarmatium smithi showed a similar trend to the diets. An enrichment of the insoluble residue was noticeable due to the digestion of dialyzable material. The fecal carbohydrate content was greatly reduced (7–11%) and the apparent lignin increased (27–39%) due to its resistance to degradation. All dietary polysaccharide component sugars were found in the fecal residues, including some uronic acids. The leaves also contained a readily water-soluble fraction (15%) which consisted of pectates strongly complexed with proanthocyanidins.     

Thermodynamics of titanium alloys: I. Development of a triple Knudsen cell and its use to study the activity of copper in the Ti−Cu system

A new experimental technique for the determination of thermodynamic activity of alloys has been developed utilizing a triple Knudsen cell with a pure enriched natural isotope as the standard reference state. The alloy for which activity is to be determined is placed in one of the two effusion chambers of the triple cell and the pure isotopic standard in the other. The molecular beams from each chamber effuse into a third upper chamber and through a collimating hole into the ion source of a Bendix time-of-flight mass spectrometer. Since the recorded intensities are proportional to the vapor pressures within the chambers, a simple calculation based upon their ratio gives a direct determination of the activity of the solute in the alloy. The accuracy of the triple cell technique for the experimental determination of activities was checked by the measurement of the copper activity in a Ni?Cu alloy containing 30.6 wt pct Cu. A value ofRT γ_Cu=1778±142 cal per g-atom at 1450°K was obtained, which is in excellent agreement with values in the literature. The activity of copper in the bcc β phase when then determined for four Ti?Cu alloys (X _Cu=0.033 to 0.085), using pure enriched Cu⁶⁵ as the standard reference state. The composition range investigated was limited to alloys belowX _Cu=0.10, the maximum solubility within the experimental temperature range between 1423° and 1573°K, the activity of copper in the bcc β phase can be expressed using pure liquid copper as the standard state by the following equation:RT Ina _Cu=RT InX _Cu+X _Ti ² (1.92±0.30) in kcal per g-atom. The activity of titanium is given byRT Ina _Ti=RT InX _Ti+X _Cu ² (1.92±0.30) in kcal per g-atom.     

A/B-Ratio and Transport Properties of (La0.85Sr0.15)sCoO3−δ Perovskites

The perovskites (La_0.85Sr_0.15)_0.98CoO_{3 –} and (La_0.85Sr_0.15)_1.00CoO_{3 –} have been investigated using x-ray diffraction (XRD), scanning electron microscopy (SEM) and electrical conductivity relaxation (ECR). This system was chosen in order to investigate the influence of cation vacancies on the transport properties in the materials. From ECR-measurements it is concluded that no difference in the chemical diffusion coefficient for oxide ions between the two samples can be found. The activation energy for the chemical diffusion coefficient has been found to be 107 ± 5 kJ mol^{– 1}. However, the surface exchange coefficient differs between the two samples. The Co-rich sample has a significantly higher surface exchange coefficient than the A/B-stoichiometric sample. For both samples the surface exchange coefficient was almost independent of the temperature. At all temperatures the Co-rich sample had a significantly higher electrical conductivity. The difference in electrical conductivity between the two samples diminished when going to higher temperatures. Both materials can be assigned to a single phase hexagonal perovskite. An annealed sample of (La_0.85Sr_0.15)_0.98CoO_{3 –} did however contain an unidentified secondary phase on the surface.     

Composition of Chemical Attractants Affects Trap Catches of the Australian Sheep Blowfly, Lucilia cuprina, and Other Blowflies

Numbers of Lucilia cuprina (Australian sheep blowfly), Chrysomya spp., and Calliphora spp. blowflies caught on sticky traps baited with various synthetic attractants or a standard liver/sodium sulfide attractant in western Queensland were recorded. Numbers of each genus collected were influenced by the composition of the chemical attractants. Attractant mixtures based on 2-mercaptoethanol, indole, butanoic/pentanoic acid, and a sodium sulfide solution gave 5- to 20-fold higher L. cuprina catches than the liver standard. These blends attracted similar numbers of Chrysomya spp. (0.85-2.7x) and fewer Calliphora spp. (0.02-0.2x) compared to the liver standard. These synthetic attractants were more effective and selective for L. cuprina than the standard liver/sodium sulfide attractant, and they can be packaged in controlled-release dispensers to generate constant, prolonged release of the attractant.     

Fungal aerobic reductive dechlorination of ethyl 2-chloroacetoacetate by Saccharomyces cerevisiae: mechanism of a novel type of microbial dehalogenation

Saccharomyces cerevisiae reduces the beta-keto ester ethyl 2-chloroacetoacetate to the respective chiral cis- and trans-beta-hydroxy esters. In the course of chiral reduction, competing dehalogenation of the xenobiotic substrate to ethyl acetoacetate occurs, in a reaction mediated by cytosolic glutathione (GSH). Mechanistically, the dechlorination is a novel type of glutathione-dependent dehalogenation catalysed by an as yet unidentified glutathione-dependent dehalogenase. The first step consists of a nucleophilic replacement of the chloride substituent by glutathione. In the subsequent enzyme-catalysed step, a second glutathione molecule liberates the dehalogenation product by thiolytic attack at the thioether bridge, resulting in a net transfer of two electrons to the substrate and in the formation of glutathione disulfide (GSSG). Being effective under aerobic conditions and catalysed by a fungus, this reductive dechlorination of an aliphatic substrate is an outstanding example of a novel, glutathione-mediated microbial dehalogenation.