Thermal behavior and flame retardancy of flexible poly(vinyl chloride) treated with zinc hydroxystannate and zinc stannate

The flame‐retardant and smoke‐suppressant properties of inorganic tin compounds such as zinc hydroxystannate (ZHS) and zinc stannate (ZS) were studied in comparison with those of alumina trihydrate and magnesium hydroxide through the limiting oxygen index test and a smoke density test. The thermal degradation in air of flexible poly(vinyl chloride) (PVC) treated with the above compounds was studied by thermal analysis from ambient temperature to 800°C. The activation energy was calculated by using the Vyazovkin model‐free kinetic method and the Kissinger method. The results showed that tin compounds such as ZHS and ZS could be used as highly effective flame retardants for flexible PVC; these flame retardants enhanced the stability and the activation energy of the oxidation of the char. J. VINYL ADDIT. TECHNOL, 2008. © 2008 Society of Plastics Engineers     

Recent studies on the use of zinc borate as a flame retardant and smoke suppressant in PVC

By the Oxygen Index test, zinc borate alone is an effective flame retardant in rigid PVC. In flexible PVC formulations containing 50 phr of dioctyl phthalate as the plasticizer, zinc borate in combination with antimony oxide displays a synergistic effect at a total loading of more than 10 phr (1-to-1 ratio). In the presence of 30 phr of alumina trihydrate, this synergism increases significantly at a total loading as low as 5 phr. Zinc borate also shows strong synergism with alumina trihydrate. Zinc borate acts as a smoke suppressant in plasticized PVC. With alumina trihydrate, a strong smoke-reducing synergism is created. Zinc borate in a flexible PVC formulation markedly increases the amount of char formed, whereas the addition of antimony oxide, a vapor phase flame retardant, has little effect on char formation. Zinc borate is a good afterglow suppressant. Volatilized zinc derived from the zinc borate probably contributes to flame retardancy but not to smoke suppression. Zinc compounds can alter the pyrolysis chemistry by catalyzing dehydrohalogenation and promoting crosslinking, resulting in increased char formation and a decrease in both smoke production and flaming combustion.     

Effect of co-additives on the flame/smoke suppression properties of zinc borates

Two zinc borates are useful partial replacements for the antimony oxide flame retardant normally used to flame retard flexible PVC products. The effect of using various co-additives with zinc borates on the flame retardancy and smoke formation of a model flexible PVC cable jacket was evaluated in an attempt to further improve the properties of the formulation. The use of ammonium octamolybdate with the borates yields products with improved properties. Highly flame retarded formulations that yield low levels of smoke can be prepared by using alumina trihydrate or magnesium compounds as replacements for the usual calcium carbonate filler. Replacement of part of the phthalate ester plasticizer with brominated ester, a phosphate ester, or a brominated phosphate ester also results in formulations with oxygen values as high as 39.5 which produce lower levels of smoke.     

Advances in the use of molybdenum compounds as smoke suppressants for PVC

Molybdenum-based compounds are effective smoke suppressants for rigid and flexible polyvinyl chloride formulations, both unfilled and filled with calcium carbonate and alumina trihydrate. These compounds, two of which are new compounds based on zinc molybdate with or without a phosphite synergist, are useful as is or extended onto core materials such as clay or talc. The addition of molybdenum-containing additives to flexible PVCs containing antimony trioxide usually raises the oxygen index and thus improves flame retardancy. Tests indicate that molybdenum acts as a flame and smoke suppressant in the solid phase.     

Effect of hydrated fillers and red phosphorus on the limiting oxygen index of poly(ethylene‐co‐vinyl actate)‐poly(vinyl butyral) and low density polyethylene‐poly(ethylene‐co‐vinyl alcohol) blends

The limiting oxygen index (LOI) values of EVA‐PVB and low density polyethylene (LDPE)‐poly(ethylene‐co‐vinyl alcohol) (EVOH) polymer blends containing hydrated filler‐type flame retardants and red phosphorus were measured. When used as the sole flame retardant, magnesium hydroxide [Mg(OH)₂] and alumina trihydrate (ATH) performed best in EVA and PVB, respectively. Magnesium hydroxide addition had a limited effect on the LOI of plasticized PVB, and addition of red phosphorus made little difference. This result is attributed to a mismatch between the decomposition temperature of Mg(OH)₂ and the temperature at which the PVB plasticizer vaporizes. Otherwise, low‐level addition of red phosphorus significantly improved LOI values. The presence of hydroxyl groups on the polymer backbone had a beneficial effect with respect to LOI values in ATH‐filled blends. An LOI value of 30 was achieved in EVOH with as little as 32% of ATH and 3% of red phosphorus. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers     

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     

高填充三元乙丙橡胶电性能的研究

研究了三水合氧化铝、增塑剂及偶联剂用量对三元乙丙橡胶电性能的影响，结果表明，三水合氧化铝能有效提高三元乙丙橡胶的抗漏电起痕性能及抗腐蚀性能，但同时引起介电常数及损耗因子增大，电阻率下降；增塑剂及偶联剂用量增均使电性能降低，其用量应限定在一定范围内。     

Flame retardancy of some ethylene–vinyl acetate copolymer‐based formulations

The combustion behaviour and thermal decomposition of ethylene–vinyl acetate copolymer (EVA) (26 wt% vinyl acetate content) formulations containing alumina trihydrate, ammonium polyphosphate, melamine, pentaerythritol and their co‐mixtures, were studied using cone calorimetry and thermogravimetric analysis. Formulations containing ammonium polyphosphate burned with the formation of intumescent carbonaceous chars, with EVA acting as a carbonization agent. EVA materials containing ammonium polyphosphate (20 wt%), with a sufficient amount of alumina trihydrate or melamine, were superior to the non‐intumescent alumina trihydrate and melamine containing formulations in terms of the heat release rate, mass loss rate and smoke production. Melamine showed some smoke suppressant effect and significant CO reducing properties. However, the melamine–EVA and melamine–alumina trihydrate–EVA showed a very high heat release rate. Thermogravimetric studies showed that oxygen played a favourable role in enhancing the char formation by encouraging active participation of the polymer matrix in the interaction with polyphosphoric acid. Copyright © 2000 John Wiley & Sons Ltd.     

Effects of montmorillonite on the electron beam irradiated alumina trihydrate added polyethylene and ethylene vinyl acetate nanocomposite

This study aims at investigating the effects of montmorillonite (MMT) nanocomposite on the electron beam irradiated alumina trihydrate flame retardant added polyethylene and ethylene vinyl acetate blends (FRLE). The addition of MMT into FRLE blends has increased the limiting oxygen index (LOI%), which corresponds the improvement of flame resistivity, whereas increasing amount of MMT and irradiation dosage were found moderately influenced LOI% of the blends. However, incorporation of MMT has shown reinforcing effect to the FRLE, where the tensile strength for the samples subjected to 150 and 250 kGy irradiation have increased for 10.7 and 27%, respectively. In addition, increasing loading level of MMT and irradiation dosage caused inferior effects to the surface and volume resistivity of FRLE as high as four folds. This is due to the enhancement of transportability of MMT ionic in polymer matrix that caused the reduction of resistivity of FRLE. POLYM. COMPOS., 33:1883–1892, 2012. © 2012 Society of Plastics Engineers     

Synergistic effects between red phosphorus and alumina trihydrate in flame retardant silicone rubber composites

Abstract

The synergistic flame retardant effects between red phosphorus (RP) and alumina trihydrate (ATH) in silicone rubber (SR) composites were evaluated using limiting oxygen index, UL 94 rating, cone calorimeter, thermogravimetric analysis and digital photographs. It has been found that the SR composite containing only ATH does not show good flame retardancy at 39·0 wt-% loading. The cone calorimeter results showed that the heat release rate, mass loss rate, mass and total heat release of SR/ATH/RP composites decrease greatly in comparison with the SR/ATH composites. The digital photographs demonstrated that 1·0 wt-%RP could promote the formation of the homogenous and compact char layer. Thus, a suitable amount of RP has a synergistic effect with ATH in the flame retardant SR composite system.     

Effects of water content on the properties of starch/poly(ethylene–vinyl alcohol) blends

The physical properties of unmodified starch, poly(ethylene vinyl alcohol), glycerol, and water mixtures are reported. Thermal and melt-flow properties of the preprocessed, physically mixed materials were determined along with the tensile properties and morphology of injection-molded microtensile samples. Melt-flow properties were measured by a capillary rheometer, and the water content was varied from 4 to 18%. The morphology, rheology, and tensile properties are all highly related to the percentage of water present. A transition in the tensile properties and morphology of the blends was observed at approximately 11% moisture content. © 1994 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

The Role of Alumina Trihydrate Filler on semiflexible unsaturated polyester resin-4 and inhibition of double-base rocket propellants

The use of unsaturated polyesters for inhibition of double-base rocket propellants has become popular in recent years. A direct bonding inhibition system termed as semiflexible unsaturated polyester resin-4 has been recently developed and reported by us. It has been reported in literature that the use of some fillers such as antimony trioxide, titanium dioxide, lithophone, alumina trihydrate etc. impart better mechanical and heat resistance properties. The effect of 10% to 60% of alumina trihydrate (Al₂O₃ · 3 H₂O) on semiflexible unsaturated polyester resin-4 in respect of gel time, exotherm peak temperature, tensile strength, %-elongation, nitroglycerin absorption, water absorption, heat resistance and flame retardance has been studied and the result obtained have been discussed. It is observed that 30% of alumina trihydrate imparts desirable properties. The 108 mm and 148 mm-diameter propellant sustainers inhibited with resin-4 containing 30% alumina trihydrate and conditioned at ambient, sub-zero temperature (−40°C for 18 hr) and high temperature (+50°C for 18 hr) were statically evaluated. The pressure-time profiles at all temperatures have been found to be flat and neutral which infer that the inhibition system works satisfactorily.     

Synthesis and application of a novel cardanol‐based plasticizer as secondary or main plasticizer for poly(vinyl chloride)

A novel plasticizer based on cardanol, hydrogenated cardanol glycidyl ether acetic ester containing phosphaphenanthrene group (HCGEP), was prepared and incorporated into poly(vinyl chloride) (PVC) for the first time. The molecular structure was characterized with Fourier transform infrared and ¹H NMR spectroscopies. The thermal degradation behavior and flame retardant performance of PVC films with HCGEP as secondary or main plasticizer were investigated using thermogravimetric analysis, combustion tests, limiting oxygen index tests and morphological analysis of residues. Furthermore, the mechanical properties of PVC films were examined based on the results of tensile testing. The results were compared to those of the petroleum‐based plasticizer dioctyl phthalate. With the substitution of dioctyl phthalate with HCGEP, PVC films exhibited high thermal stability and better flame retardant performance. The tensile test results showed that the addition of HCGEP could endow PVC resin with well‐balanced properties of flexibility, strength and hardness. © 2017 Society of Chemical Industry     

Skin and layer formation in films prepared from carbohydrates,poly(ethylene-co-acrylic acid), and polyethylene

Cornstarch, a canary dextrin, and a maltodextrin were compared in films blown from carbohydrates compounded with poly(ethylene-co-acrylic acid) (EAA), low-density polyethylene (LDPE), and aqueous ammonium hydroxide plasticizer. Dextrins or maltodextrins having dextrose equivalent values of one and greater caused dark-colored films with caramel odors, probably due to Maillard reactions. Blown films with hydrophobic skins and water sensitive cores were produced with the dextrinized carbohydrates, but not from natural cornstarch. Water sensitivity of films containing the dextrinized carbohydrate was reduced by recycling the films through the blown film die. A mechanism for development of the skins is proposed, as is a method for preparing thin semipermeable membranes. © 1993 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

     

Glass fiber-reinforced epoxy composites

Glass fiber-reinforced epoxy composites were prepared from the matrix resins tetraglycidyl diaminodiphenylmethane

1 Systematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-diaminodiphenylmethane.

(TGDDM) and tetraglycidyl bis(o-toluidino)-methane

2 Systematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-bis(o-toluidino)methane.

(TGMBT) using various amines like 4,4′-diaminodiphenylmethane (DDM), 4,4′-diaminodiphenylsulfone (DDS) and diethylene triamine (DETA) as curing agents. The fabricated laminates were evaluated for their mechanical and dielectrical properties and chemical resistance. The composites prepared using an epoxy fortifier (20 phr) showed significant improvement in the mechanical properties.     

The mass burning rate of flame-retarded polypropylene in an oxygen-enriched atmosphere

Polypropylene containing a bromophosphorous flame-retardant exhibits a higher mass burning rate—in the atmosphere containing more than 30 vol % of oxygen — than nonretarded resin. These prodegradative reactions in combustion can be eliminated only by using a high concentration (ca. 40 phr) of inorganic alumina trihydrate. A method for distinguishing the physical and chemical effects of flame retardants is described.     

Solid-state polymerization in poly(butylene terephthalate): The Equilibrium constant

Poly(butylene terephthalate)

1 PBT or Poly-1, 4-butanediyl 1, 4-diearboxylate.

polycondenses readily in the presence of small amounts of organo-titanium compounds to form progressively higher molecular weight polymers, The reaction is reversible in the presence of the condensation byproduct, 1,4-butanediol. Usually this reaction is carried out in the melt phase, but the viscosity is soon limiting. In the current work the polymerization is carried out in the solid phase just below the melting point of 227°C. The equilibrium constant for this reaction is measured by subjecting the polymer to a nitrogen stream saturated with a controlled quantity of butanediol. The reaction is followed by measuring the change in the number of alcoholic end-groups by infrared spectroscopy. At about 220°C the equilibrium constant is 0.31 (σ = 0.08).     

高导热阻燃有机硅灌封胶的制备

以乙烯基硅油、含氢硅油为基础胶料,十六烷基三甲氧基硅烷改性氧化铝为导热填料,二乙基次膦酸铝(ADP)为阻燃剂,制得导热阻燃绝缘有机硅电子灌封胶。研究了改性氧化铝用量对灌封胶黏度、导热性、阻燃性的影响,观察了燃烧残余物的形貌。结果表明,这种改性氧化铝有低吸油值,填充量对灌封胶黏度影响小,所制备的灌封胶具有良好导热性能;而ADP不仅展现出对灌封胶良好的阻燃性,而且还能与改性氧化铝产生协效阻燃性和抑烟作用,同时灌封胶也具有良好的流动性、力学性能和电绝缘性能。当ADP用量50份、改性氧化铝用量600份时,灌封胶的黏度为8 500 mPa·s,硫化后胶条的热导率达2.12 W/m·K,垂直燃烧达到FV-0级,拉伸强度1.72 MPa,拉断伸长率62%,体积电阻率3.9×1012Ω·cm。     

Some aspects of flame retardancy in high density polyethylene

The influence of the flame retardant agents, antimony trioxide and a chlorinated hydrocarbon, on the mechanical and flammability properties of high density polyethylene has been studied. Flammability was assessed by means of the limiting oxygen index test, whilst mechanical properties were measured in the tensile mode on compression moulded samples. An optimum in terms of flame resistance was found at a Sb:Cl mole ratio of 1:3 which tends to confirm that the actual flame retardant is the volatile antimony trichloride. The modulus, yield and drawing behaviour, and ultimate properties of the unoriented samples did not show significant change (< 10%) until the combined level of additive exceeded 25% by wt. Above this level it was found that the samples could not be oriented and that the elongation to break decreased markedly. Alumina trihydrate was studied as an alternative flame retardant but was found to be unsuitable for use in HDPE, since to obtain an adequate level of fire retardancy a high concentration (40%) of additive was required, which resulted in a significant deterioration in the mechanical properties.