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     

The flame retardant mechanism of polyolefins modified with chalk and silicone elastomer

This paper presents the current understanding of the flame retardant mechanism of Casico?. The study includes the flame retardant effect of each individual component: ethylene–acrylate copolymer, chalk and silicone elastomer, as well as the formation of an intumescent structure during heating. The flame retardant properties were investigated by cone calorimetry and oxygen index tests. To obtain insight into the flame retardant mechanism, heat treatment under different conditions has also been performed. The results indicate that the flame retardant mechanism of Casico is complex and is related to a number of reactions, e.g. ester pyrolysis of acrylate groups, formation of carbon dioxide by reaction between carboxylic acid and chalk, ionomer formation and formation of an intumescent structure stabilized by a protecting char. Special emphasis is given to the formation of the intumescent structure and its molecular structure as evaluated from ¹³C MAS‐NMR and ²⁹Si MAS‐NMR, ESCA and XRD analysis. After treatment at 500°C the intumescent structure consists mainly of silicon oxides and calcium carbonate and after treatment at 1000°C the intumescent structure consists of calcium silicate, calcium oxide and calcium hydroxide. Copyright © 2003 John Wiley & Sons, Ltd.     

Geometric features of the flame propagation process for an SI engine having dual‐ignition system

Flame front surface area and enflamed volume (the volume enclosed with flame front) is theoretically analysed for a spark‐ignition engine, having cylindrical disc‐shaped combustion chamber with two spark plugs located axisymmetrically on cylinder head, between cylinder axis and cylinder wall. Spherical flame front assumption is used. A computer code is developed based on purely geometric consideration of the flame development process in combustion chamber, and is used to investigate the effects of variations of spark plugs' locations on geometric features of the flame front. A comparison has also been made with a spark‐ignition engine having one spark plug at the same location. Copyright © 2002 John Wiley & Sons, Ltd.     

磷氮阻燃腈纶结构性能及阻燃机理研究

研究了含磷酸二氢铵和脲复合阻燃剂的共混阻燃腈纶的结构和性能。研究表明，在纤维成形加工过程中，部分阻燃剂聚合生成聚磷酸铵和聚脲，阻燃剂以微粒状均匀分散并包埋在纤维内部；阻燃剂的加入使纤维高序区大分子间等距离排列的规整性和片状结构单元等距离平行排列的程度降低，热稳定性亦略有下降；但纤维的宏形态结构及物理机械性能没有明显变化；磷氮阻燃腈纶具有良好的阻燃性和阻燃耐久性，经碱洗２０次、水洗３０次后，阻燃剂的磷和氮的保留率分别高达８２．９％和８９．５％，纤维的ＬＯＩ值仍在２６％以上。     

Synthesis,characterization, and thermal properties of phosphorus‐containing,wholly aromatic thermotropic copolyesters

A series of phosphorus‐containing, wholly aromatic thermotropic copolyesters from acetylated 2‐(6‐oxide‐6H‐dibenz〈c,e〉〈1,2〉oxa phosphorin‐6‐yl)‐1,4‐dihydroxy phenylene, p‐acetoxybenzoic acid, terephthalic acid, and isophthalic acid were prepared by melting polycondensation. The structure and basic properties of the polymers, such as the glass‐transition temperature (T_g), melting temperature (T_m), thermal stability, crystallinity, and liquid crystallinity, were investigated with Fourier transform infrared, elemental analysis, differential scanning calorimetry (DSC), thermogravimetric analysis, wide‐angle X‐ray diffraction, and hot‐stage polarizing optical microscopy. The copolyesters had relatively high T_g values ranging from 183 to 192°C. The T_m values obtained from DSC curves for samples P‐20 and P‐25 were 290 and 287°C, respectively (where the number in the sample name indicates the molar fraction of the phosphorus‐containing monomer in the reactants). The initial flow temperatures of other samples observed with hot‐stage polarizing microscopy were 271–290°C. The 5% degradation temperatures in nitrogen ranged from 431 to 462°C, and the char yields at 640°C were 41–52%. All the copolyesters, except P‐40, were thermotropic and nematic. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1278–1284, 2002     

Ignition and Combustion of Dust-Gas Suspensions

The ignition and combustion of dust-gas suspensions are considered. It is shown that the ability of these systems to accumulate heat is determined not only by their kinetic and thermal properties but also by the relation between their reaction surface and the heat-removal surface (f). Experimental information on flame temperatures, ignition delays, and flame propagation over gas suspensions is processed using the parameter f, and the postulate on the stimulating role of the developed reaction surface in activating these processes is validated. It is shown that during overall burning, diffusion combustion of particles occurs only for rather small values of f. The ambiguous effect of the parameter f on the ignition and combustion processes leads to the necessity of optimizing the fuel size distribution and concentration for the effective operation of the power devices. The role of the macroparameters of two-phase flames of refractory metals in the synthesis of combustion nanoproducts is analyzed. __________ Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 6, pp. 3–14, November–December, 2005.     

热处理前后丙烯腈／溴乙烯共聚纤维的热性能和阻燃性能研究

分析了热处理前后丙烯腈／溴乙烯共聚纤维的热性能与溴乙烯含量、升温速率或热处理时间的关系，并对纤维的阻燃性与溴含量或热处理时间关系进行了研究。结果表明，溴含量的增加或热处理时间的延长对热稳定性和阻燃性的提高有较大影响，而且经热处理后纤维的阻燃性与溴无关。     

Zinc hydroxystannate and zinc stannate as flame‐retardant agents for flexible poly(vinyl chloride)

The flame‐retardant and smoke‐suppressant properties of inorganic tin compounds such as zinc hydroxystannate (ZHS) and zinc stannate (ZS) were investigated in a comparison with alumina trihydrate, magnesium hydroxide, and Sb₂O₃ through the limiting oxygen index test and smoke density test. The flame‐retardant mechanisms were studied through the char yield test, SEM, quantitative analysis, thermogravimetry and differential thermal analysis. The thermal degradation in air of flexible PVC treated with the above compounds was studied by thermal analysis from ambient temperature to 800°C. The results showed that tin compounds such as ZHS and ZS could be used as a highly effective flame retardant for flexible PVC, and it appears that the tin compound may exert its action in both the condensed and vapor phases, but mainly in condensed phases as a Lewis acid. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1469–1475, 2005     

A computational fluid dynamic analysis of gas and particle flow in flame spraying

The flame spraying process, which is a common industrial thermal spraying application, has been analyzed by means of three-dimensional computational fluid dynamics (CFD) simulations. The process used at the Volvo Aero Corporation for the coating of fan and compressor housings has been modeled. The process uses the Metco 6P torch (Metco, Westbury, NY), which ejects a mixture of acetylene and oxygen at high speed through a ring of 16 orifices to form the flame. A stream of argon gas flowing through an orifice in the center of the ring carries a powder of nickel-covered bentonite through the flame to the spray substrate. The torch is cooled by a flow of air through an outer ring of 9 orifices. The simulation emulated reality closely by including the individual inlets for fuel, cooling air, and injected particles. The gas combustion was simulated as a turbulent, multicomponent chemically reacting flow. The standard, two-equation k-ε turbulence model was used. The chemical reaction rates appeared as source terms in the species transport equations. They were computed from the contributions of the Arrhenius rate expressions and the Magnussen and Hjertager eddy dissipation model. The first simulations included several intermediate chemical substances whose predicted concentration agreed favorably with measurements. Later, more simplified simulations incorporated only the global chemical reaction involving the initial and the final products, with corrections to the thermal properties being made to account for the missing intermediaries. The gas velocity and temperature fields predicted by the later simulations compared satisfactorily to those predicted by the earlier, more elaborate, ones. Therefore, the final simulations, which incorporated injected particles, were conducted employing the simplified model with only the global reaction. An in-house finite difference code was developed to calculate particle properties. Allowance was made for elliptical shapes, phase changes, and internal heat transfer with regard to the composite material. The particle velocities and temperatures predicted by the final simulations compared fairly well with experimental results obtained with the optical DPV2000 system.     

阻燃剂的现状与发展趋势

通过对无机燃剂和有机燃剂的现状的分析，指出了阻燃剂的无卤化和无机阻燃剂的开发及改性已成为阻燃剂最主要的发展趋势。