Phosphorus‐containing polyaryloxydiphenylsilanes with high flame retardance arising from a phosphorus–silicon synergistic effect

Polyaryloxydiphenylsilanes were prepared from phosphorus‐containing diols and diphenydichlorolsilane through solution polymerization. With a stoichiometric imbalance in feed monomers, the resulting polymers exhibited moderate melting points and good processing properties. The polymers prepared showed initial decomposition temperatures above 340 °C, excellent thermal stability, high char yields at 850 °C and very high limited oxygen index values of 56–59. The polymers' char yields and their (P + Si) contents showed linear relationships. © 2003 Society of Chemical Industry     

A new monitoring system for piping systems in fossil fired power plants

A CEC-funded project has been performed to tackle the problem of producing an advanced Life Monitoring System (LMS) which would calculate the creep and fatigue damage experienced by high temperature pipework components. Four areas were identified where existing Life Monitoring System technology could be improved:

1. 1. the inclusion of creep relaxation

2. 2. the inclusion of external loads on components

3. 3. a more accurate method of calculating thermal stresses due to temperature transients

4. 4. the inclusion of high cycle fatigue terms.

The creep relaxation problem was solved using stress reduction factors in an analytical in-elastic stress calculation. The stress reduction factors were produced for a number of common geometries and materials by means of non-linear finite element analysis. External loads were catered for by producing influence coefficients from in-elastic analysis of the particular piping system and using them to calculate bending moments at critical positions on the pipework from load and displacement measurements made at the convenient points at the pipework. The thermal stress problem was solved by producing a completely new solution based on Green's Function and Fast Fourier transforms. This allowed the thermal stress in a complex component to be calculated from simple non-intrusive thermocouple measurements made on the outside of the component. The high-cycle fatigue problem was dealt with precalculating the fatigue damage associated with standard transients and adding this damage to cumulative total when a transient occurred.

The site testing provided good practical experience and showed up problems which would not otherwise have been detected.     

Energy use in controlled temperature marine aquaculture

Temperature control offers benefits in land‐based marine aquaculture: stock growth rates may be enhanced by heating in winter; mortality rates in summer may be reduced by cooling. However, if the plant is not well designed, temperature control may create very large energy demands. This paper describes the application of temperature control in abalone aquaculture in New Zealand, with a focus on energy considerations in plant design. An abalone farm using a semi‐closed water conditioning system is used as a case study for which an energy model, based on a heat pump system, is developed. The model is used to determine the impact of plant design and tank conditions on the economics of the operation. Copyright © 2002 John Wiley & Sons, Ltd.     

NO emission characteristics in counterflow diffusion flame of blended fuel of H2/CO2/Ar

Flame structure and NO emission characteristics in counterflow diffusion flame of blended fuel of H₂/CO₂/Ar have been numerically simulated with detailed chemistry. The combination of H₂, CO₂ and Ar as fuel is selected to clearly display the contribution of hydrocarbon products to flame structure and NO emission characteristics due to the breakdown of CO₂. A radiative heat loss term is involved to correctly describe the flame dynamics especially at low strain rates. The detailed chemistry adopts the reaction mechanism of GRI 2.11, which consists of 49 species and 279 elementary reactions. All mechanisms including thermal, NO₂, N₂O and Fenimore are taken into account to separately evaluate the effects of CO₂ addition on NO emission characteristics. The increase of added CO₂ quantity causes flame temperature to fall since at high strain rates a diluent effect is prevailing and at low strain rates the breakdown of CO₂ produces relatively populous hydrocarbon products and thus the existence of hydrocarbon products inhibits chain branching. It is also found that the contribution of NO production by N₂O and NO₂ mechanisms are negligible and that thermal mechanism is concentrated on only the reaction zone. As strain rate and CO₂ quantity increase, NO production is remarkably augmented. Copyright © 2002 John Wiley & Sons, Ltd.     

Physico-chemical properties of ceramic pigments for high-temperature application

Heat resistant coatings are required primarily for stacks, exhaust pipes, reactors, space crafts and similar equipments that are permanently or occasionally exposed to elevated temperatures. High-temperature coatings are generally based on silicone resin with ceramic and metallic pigments. In this study, iron oxide, cobalt oxide (thermo chromic compound) and aluminum oxide are used for the preparation of four new types of coloured pigments. The thermal resistant characteristics of these ceramic pigments were studied by differential thermal analysis, thermo gravimetric analysis and differential scanning calorimetric analysis. These ceramic pigments are found to be thermally stable up to 400 °C.     

Synthesis and characterization of new thermally stable poly(ester‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic dihydroxy compounds

A series of new alternating aromatic poly(ester‐imide)s were prepared by the polycondensation of the preformed imide ring‐containing diacids, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A model compound (3) was also prepared by the reaction of 2b with phenol, its synthesis permitting an optimization of polymerization conditions. Poly(ester‐imides) were fully characterized by FTIR, UV‐vis and NMR spectroscopy. Both biphenylene‐ and binaphthylene‐based poly(ester‐imide)s exhibited excellent solubility in common organic solvents such as tetrahydrofuran, m‐cresol, pyridine and dichloromethane. However, binaphthylene‐based poly(ester‐imide)s were more soluble than those of biphenylene‐based polymers in highly polar organic solvents, including N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 261 and 315 °C. Thermal behaviour of the polymers obtained was characterized by thermogravimetric analysis, and the 10 % weight loss temperatures of the poly(ester‐imide)s was in the range 449–491 °C in nitrogen. Furthermore, crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resultant poly(ester‐imide)s exhibited nearly an amorphous nature, except poly(ester‐imide)s derived from hydroquinone and 4,4′‐dihydroxybiphenyl. In general, polymers containing binaphthyl units showed higher thermal stability but lower crystallinity than polymers containing biphenyl units. Copyright © 2005 Society of Chemical Industry     

The impact of roasting on the ochratoxin A content of coffee

Roasting coffee led to a drop in the ochratoxin A (OTA) concentration, as measured by the reference method, especially for dark type roasts. The way the beverage was prepared also affected the OTA content, which could paradoxically be higher than that of the initial roasted coffee. Assays on the thermal stability of pure OTA showed that it ought to be found in larger quantities in roasted coffee. This suggested that OTA was masked by reactions with the substrate during roasting. The absence of OTA in green coffee is therefore the best guarantee of safety.     

Heat resistance of Escherichia coli O157:H7 in cook‐in‐bag ground beef as affected by pH and acidulant†

Summary The heat resistance of a four‐strain mixture of Escherichia coli O157:H7 was tested. The temperature range was 55–62.5 °C and the substrate was beef at pH 4.5 or 5.5, adjusted with either acetic or lactic acid. Inoculated meat, packaged in bags, was completely immersed in a circulating water bath and cooked to an internal temperature of 55, 58, 60, or 62.5 °C in 1 h, and then held for pre‐determined lengths of time. The surviving cell population was enumerated by spiral plating meat samples on tryptic soy agar overlaid with Sorbitol MacConkey agar. Regardless of the acidulant used to modify the pH, the D ‐values at all temperatures were significantly lower (P < 0.05) in ground beef at pH 4.5 as compared with the beef at pH 5.5. At the same pH levels, acetic acid rendered E. coli O157:H7 more sensitive to the lethal effect of heat. The analysis of covariance showed evidence of a significant acidulant and pH interaction on the slopes of the survivor curves at 55 °C. Based on the thermal‐death–time values, contaminated ground beef (pH 5.5/lactic acid) should be heated to an internal temperature of 55 °C for at least 116.3 min and beef (pH 4.5/acetic acid) for 64.8 min to achieve a 4‐log reduction of the pathogen. The heating time at 62.5 °C, to achieve the same level of reduction, was 4.4 and 2.6 min, respectively. Thermal‐death–time values from this study will assist the retail food processors in designing acceptance limits on critical control points that ensure safety of beef originally contaminated with E. coli O157:H7.