Influence of polymeric flame retardants based on phosphorus‐containing polyesters on morphology and material characteristics of poly(butylene terephthalate)

Flame retarded poly(butylene terephthalate) (PBT) is required for electronic applications and is mostly achieved by low molar mass additives so far. Three phosphorus‐containing polyesters are suggested as halogen‐free and polymeric flame retardants for PBT. Flame retardancy was achieved according to cone calorimeter experiments showing that the peak heat release rate and total heat evolved were reduced because of flame inhibition and condensed‐phase activity. The presented polymers containing derivatives of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide form immiscible blend systems with PBT. Shear‐rheology shows an increase in storage moduli at low frequencies. This is proposed as quantitative measure for the degree of phase interaction. The phase structure of the blends depends on the chemical structure of the phosphorus polyester and was quite different, depending also on the viscosity ratio between matrix and second phase. A lower viscosity ratio leads to two types of phases with spherical and additionally continuous droplets. Addition of the flame retardants showed no influence on the dielectric properties but on the mechanical behavior. The polymeric flame retardants significantly diminish the impact strength because of several reasons: (1) high brittleness of the phosphorus polyesters themselves, (2) thermodynamic immiscibility, and (3) weak phase adhesion. By adding a copolymer consisting of the two base polymers to the blend, an improvement of impact strength was obtained. The copolymer particularly acts as compatibilizer between the phases and therefore leads to a smaller phase size and to a stronger phase adhesion due to the formation of fibrils. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of flame heat flux on thermal response and fire properties of char‐forming composite materials

This study evaluates the effect of flame heat flux on the prediction of thermal response and fire properties of a char‐forming composite material. A simplified two‐layer flame model was developed and incorporated into a heat transfer thermal model to predict the thermal response and fire reaction characteristics of a burning material. A typical char‐forming material, E‐glass reinforced polyester composite, was used in the study. A cone calorimeter was used to measure the fire reaction characteristics of the composite. The flame heat flux in a cone calorimeter test setup was estimated using the simplified flame model. Thermal response and fire property predictions with and without the effect of flame heat flux were compared with experimental data obtained from the cone calorimeter tests. Results showed that the average flame heat flux of the composite in a cone calorimeter was 19.1 ± 6 kW/m² from model predictions. The flame had a significant effect on the thermal response and fire properties of the composite around the first heat release peak but the effect decreased rapidly afterwards. Copyright © 2012 John Wiley & Sons, Ltd.     

Flammability behavior of fiber–fiber hybrid fabrics and composites

The effect of heat flux levels on burning behavior and heat transmission properties of hybrid fabrics and composites has been investigated using cone calorimeter and heat transmission techniques. The hybrid fabric structures woven out of E‐glass (warp) and polyether ether ketone (PEEK) (weft) and E‐glass (warp) and polyester (weft) have been studied at high heat flux levels keeping in view the flame retardant requirements of structural composites. The performance of the glass–PEEK fabric even at high heat flux levels of 75 kW/m² was comparable with the performance of glass–polyester fabric evaluated at 50 kW/m². The results further demonstrate that glass–PEEK hybrid fabrics exhibit low peak heat release rate, low heat release rate, low heat of combustion, suggesting an excellent combination of materials and fall under the low‐risk category and are comparable with the performance of carbon fiber‐epoxy‐based systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Ignition performance of new and used motor vehicle upholstery fabrics

This paper examines the standards for fire safety in transport systems and in particular the test method for the flammability of materials within passenger compartments of motor vehicles. The paper compares data from ignition tests conducted in the cone calorimeter and the FIST apparatus with tests conducted using the FMVSS 302 horizontal flame spread apparatus. Ten materials were selected as representative of those used as seat coverings of private and commercial passenger vehicles. The time to ignition of new and used materials subject to exposure heat fluxes between 20 kW/m² and 40 kW/m² was measured. The results from the ignition tests were analysed using thermally thick and thermally thin theoretical models. The critical heat flux for sustained piloted ignition was determined from the time to ignition data using the thermally thin approach. Derived ignition temperatures from both the thermally thick and thermally thin methods were compared with measurements using a thermocouple attached to the back surface of materials in selected tests. The flame spread rates in the FMVSS 302 apparatus were determined and a comparison was made between the performance of the materials in the flame spread apparatus, the cone calorimeter and the FIST. The results suggests that a critical heat flux criterion could be used to provide an equivalent pass/fail performance requirement to that specified by the horizontal flame spread test although further testing is needed to support this. Copyright © 2004 John Wiley & Sons, Ltd.     

Enhancement of fire retardancy properties of glass fibre–reinforced polyesters composites

This paper presents the results of an experimental investigation on the fire retardancy properties of glass fibre–reinforced polyester (GFRP) composites with bisphenol‐A vinylester and isophthalic polyester as matrices and low electrical conductivity E‐glass fibres as reinforcement. The fire protection systems tested were alumina trihydrate (ATH), decabromodiphenyl ether (DBDE), and antimony trioxide (Sb₂O₃). A mass loss cone calorimeter was used to obtain the properties of heat release rate (HRR), peak HRR, total heat released, total mass loss, time to ignition, and time of combustion. Moreover, limiting oxygen index (LOI), UL‐94, and glow‐wire tests were also performed. The fire tests were carried out in order to investigate if the combination of ATH and DBDE could have “additive,” “antagonistic,” or “synergistic” effects on the flame retardant properties of the GFRP studied in this work. In addition, the influence of the ATH content variation on flame retardant properties was also evaluated. The results indicate that the sole addition of ATH at 47.7 phr could lead to the complete inhibition of the composites ignition, while the materials containing DBDE exhibit ignition and flame propagation in the cone calorimeter test.     

Burning behaviors of selected chlorosilanes and SiH‐containing siloxanes

Chlorosilanes are silanes containing the Si‐Cl functional group and SiH‐containing siloxanes are siloxanes containing the Si‐H functional group. Some chlorosilanes and SiH‐containing siloxanes present potentially high fire or explosion hazards during handling, storage, transport and process operations. Cone calorimeter tests have been used to study the burning behaviors of selected chlorosilanes and SiH‐containing siloxanes at various incident heat fluxes to simulate pool fire burning. The peak heat release rate of a silicon intermediate obtained from the cone calorimeter at 15 kW/m² incident heat flux was very close to that measured by a relatively large‐scale field test. The flammability of monochlorosilanes was similar to that of organic hydrocarbons having comparable volatility. The flammability of chlorosilanes descends in the order of monochlorosilanes, dichlorosilanes and trichlorosilanes. SiH‐containing siloxanes ignited faster than non‐SiH‐containing siloxanes because of the reactive silicon‐hydrogen linkages. The ignition of SiH‐containing siloxanes was much more violent than the ignition of non‐SiH‐containing siloxanes. The SiH‐containing siloxanes exhibited a lower peak heat release rate, less total heat released and a lower peak smoke extinction coefficient compared with non‐SiH‐containing siloxanes having comparable volatility. Copyright © 2004 John Wiley & Sons, Ltd.     

Novel phosphorus‐containing dicyclopentadiene‐modified phenolic resins for flame‐retardancy applications

2‐[4‐(2‐hydroxyphenyl)tricyclo[5.2.1.0^2,6]dec‐8‐yl]phenol (HPTCDP) were prepared from dicyclopentadiene (DCPD) and phenol via Friedel‐Crafts alkylation. DCPD‐containing phenolic resin (DPR) was also synthesized by incorporating the DCPD‐containing monomer HPTCDP with formaldehyde. DPR was further modified by grafting the phosphate group. The phosphorylation was confirmed by a Fourier transform infrared, ³¹P‐NMR spectroscopy, and an element analysis. The phosphorus content in the DPR could be successfully tailored to give values of 3.46 to 7.79 wt % by varying the feeding ratios of the phosphorus group. The thermal stabilities of the phosphorus‐containing polymers were identified by differential scanning calorimeter and thermogravimetric analysis. The glass transition temperature values were decreased as the content of phosphorus increased. High char yield 39–47 wt % in thermogravimetric analysis evaluation and limiting oxygen index values of 27 to 34 were found for all the phosphorylated phenolic resins. Such properties make these polymers highly promising for flame‐retardant applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 342–349, 2001     

Phosphorus‐containing silica gel‐coated ammonium polyphosphate: Preparation,characterization, and its effect on the flame retardancy of rigid polyurethane foam

A phosphorus‐containing silica gel was synthesized via a reaction between phenyl dichlorophosphate, poly(ether polyol), and γ‐aminopropyltriethoxysilane. Ammonium polyphosphate (APP) was modified by the synthesized phosphorus‐containing silica gel (MAPP) and then incorporated into the rigid polyurethane foam (PU). Results showed that APP had a smaller particle size, lower initial decomposition temperature, better heat resistance at high temperature, and better compatibility with PU matrix after the modification. The cone calorimeter test results showed that the incorporation of MAPP obviously reduced the values including peak of heat release rate, total heat release, average effective heat of combustion, and total smoke release, and increased the char yield of PU composite comparing with APP. The improved flame retardancy of PU/MAPP composite was attributed to the quenching effect of PO· and PO₂· free radicals released by MAPP in the early stage and the improved thermal stability of phosphorus‐ and silicon‐containing char layer formed in the later stage. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46334.     

Comparison of cone and OSU calorimetric techniques to assess the flammability behaviour of fabrics used for aircraft interiors

Two test methods for measuring the heat release rate, HRR have been compared on fabric composites used for aircraft interior materials as side‐wall panels. These methods are based on the principles of direct measurement of the convective and radiant heat by thermopiles using an Ohio State University (OSU) calorimeter, and oxygen consumption using a cone calorimeter. It has been observed when tested by standard procedures, cone results at 35 kW/m² incident heat flux do not correlate with OSU results at the same heat flux. This is because in the cone calorimeter, the sample is mounted horizontally whereas the OSU calorimetric method requires vertical sampling with exposure to a vertical radiant panel. A further difference between the two techniques is the ignition source—in the cone it is spark ignition, whereas in the OSU it is flame ignition; hence, samples in the OSU calorimeter ignite more easily compared to those in the cone under the same incident heat fluxes. However, in this paper we demonstrate that cone calorimetric exposure at 50 kW/m² heat flux gives similar peak heat release results as the 35 kW/m² heat flux of OSU calorimeter, but significantly different average and total heat release values over a 2 min period. The performance differences associated with these two techniques are also discussed. Moreover, the effects of structure, i.e. type of fibres used in warp/weft direction and design of fabric are also analysed with respect to heat release behaviour and their correlation discussed. Copyright © 2005 John Wiley & Sons, Ltd.     

Thermal behaviors and flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives

The thermal behaviors and the flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives were studied. The combustion was measured by the Underwriter laboratory (UL) test and cone calorimeter test and thermogravimetric analysis and program‐mass spectroscopy were applied to analyze the thermal behaviors. The blend with halogen additives showed the best result in the UL test. However, the blend with red‐phosphorous was the best in the cone calorimeter test. As the styrene sequence in the copolymer tended to degradate at a lower temperature, the major scission products spouted out from the polymer surface originated from polystyrene. The shorter the ignition times of the blends with red‐phosphorous were, the lower the peak heat release rates were. It was an interesting phenomenon because it suggested that the chemical structure of the residue changed to more stable polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 156–161, 2007     

Poly(methyl methacrylate)/montmorillonite nanocomposites prepared with a novel reactive phosphorus–nitrogen‐containing monomer of N‐(2‐(5,5‐dimethyl‐1,3,2‐dioxaphosphinyl‐2‐ylamino)ethyl)‐ acrylamide and its thermal and flame retardant properties

A novel reactive phosphorus–nitrogen‐containing monomer, N‐(2‐(5,5‐dimethyl‐1,3,2‐dioxaphosphinyl‐2‐ylamino)ethyl)‐acrylamide (DPEAA), was synthesize and characterized. Flame retardant poly(methyl methacrylate)/organic‐modified montmorillonite (PMMA‐DPEAA/OMMT) nanocomposites were prepared by in situ polymerization by incorporating methyl methacrylate, DPEAA, and OMMT. The results from X‐ray diffraction and transmission electron microscopy (TEM) showed that exfoliated PMMA‐DPEAA/OMMT nanocomposites were formed. Thermal stability and flammability properties were investigated by thermogravimetric analysis, cone calorimeter, and limiting oxygen index (LOI) tests. The synergistic effect of DPEAA and montmorillonite improved thermal stability and reduced significantly the flammability [including peak heat release rates (PHRR), total heat release, average mass loss rate, etc.]. The PHRR of PMMA‐DPEAA/OMMT was reduced by about 40% compared with pure PMMA. The LOI value of PMMA‐DPEAA/OMMT reached 27.3%. The morphology and composition of residues generated after cone calorimeter tests were investigated by scanning electronic microscopy (SEM), TEM, and energy dispersive X‐ray (EDX). The SEM and TEM images showed that a compact, dense, and uniform intumescent char was formed for PMMA‐DPEAA/OMMT nanocomposites after combustion. The results of EDX confirmed that the carbon content of the char for PMMA‐DPEAA/OMMT nanocomposites increased obviously by the synergistic effect of DPEAA and montmorillonite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Cone calorimeter analysis of UL‐94 V‐rated plastics

Cone calorimeter analysis was conducted on 18 thermoplastics with different UL‐94 vertical burn test (V) ratings. Ratings varied from V‐0 to no rating (NR), and the types of thermoplastics included were polycarbonate (PC), acrylonitrile–butadiene–styrene (ABS), PC/ABS blends, high‐impact polystyrene (HIPS), polypropylene (PP), and poly(vinyl chloride) (PVC). Our analysis of the cone calorimeter data found that there were correlations between UL‐94 V rating and some cone calorimeter measurements (peak heat release rate (HRR) average and HRR at 60 s) and no relationship for other measurements (time to ignition and total heat release). However, no precise correlation was found due to significant differences in flame retardant mechanism and polymer fuel energy values. In this paper, we seek to explain further why a broad quantitative relationship between UL‐94 V and cone calorimeter remains elusive, and also to show how the cone calorimeter can be used to understand why a material passes or fails a particular UL‐94 V rating. Copyright © 2006 John Wiley & Sons, Ltd.     

Modeling and experimental studies of thermal degradation of glass fiber reinforced polymer composites

This study developed a numerical model that simulated the degradation rate and temperature profiles of a glass fiber reinforced polyester resin composite exposed to a constant heat flux in a cone calorimeter. By considering the thermal properties of the composite structure consisting of alternating layers of pure polymer and polymer‐infused glass fiber mat, the numerical model seeks to reproduce the experimental data from the cone calorimeter test. The final results are achieved through adding a simulated heat flux from the pilot ignition of the degraded gas of the polyester resin. The good agreement between the predicted and experimental results suggests that such models are cost‐saving tools over the process of designing and manufacturing of composites for meeting fire safety requirements, without having to fabricate many samples for testing and final selection. Copyright © 2013 John Wiley & Sons, Ltd.     

阻燃型PETMF/WPU复合材料的制备与性能研究

用聚酯/碱溶性聚酯（PET/COPET）海岛纤维无纺布含浸含磷自阻燃的水性聚氨酯（WPU）浆料，通过干法凝固、碱减量和后整理等工艺制备阻燃型聚酯超细纤维/水性聚氨酯（PETMF/WPU）复合材料。分析并探讨不同固含量含磷自阻燃的WPU浆料对PETMF/WPU复合材料的阻燃性能和力学性能的影响。采用锥形量热仪、极限氧指数和垂直燃烧对其阻燃性能进行表征；采用电子扫描显微镜对其微观结构进行表征；采用TGA对其热稳定性进行表征。结果表明：当固含量达到35wt%时，PETMF/WPU复合材料的LOI值达到31.7%，垂直燃烧达到V-0级，在燃烧过程中能够自熄且无熔滴产生，力学性能仍能满足行业标准，使用含磷自阻燃原料减少了燃烧过程中有害气体的释放。     

Flammability of GRP for use in ship superstructures

The burning characteristics of glass-reinforced panels with an isophthalic polyester resin, the same resin with an inorganic flame retardant, two differing vinylester resins or a resole phenolic as the matrix were tested at a range of incident heat flux values using a cone calorimeter. The phenolic composite was superior at all levels showing a longer ignition time, reduced heat output, less contribution to a low-level sustained fire (25 kWm^?2) and lower smoke yield.     

Synthesis of aluminum ethylphenylphosphinate flame retardant and its application in epoxy resin

A novel flame retardant additive, aluminum ethylphenylphosphinate (AEPP), was synthesized from diethyl phenylphosphonite and aluminum chloride hexahydrate, and characterized by FTIR, ¹H NMR, and ³¹P NMR. AEPP was added into diglycidyl ether of bisphenol A epoxy resin (EP) cured by bisphenol A‐formaldehyde novolac resin. The flame retardancy of the cured EP was investigated by limited oxygen index, UL 94 test, and cone calorimeter test. The results revealed that the EP composite containing 15% AEPP had a limited oxygen index value of 28.2% with a UL 94 V‐0 rating. The incorporation of AEPP effectively decreased the peak heat release rate and the total heat release in cone calorimeter test analysis. Scanning electron microscopy results showed that the introduction of AEPP benefited to the formation of a smooth and continuous char layer during combustion of the flame retarded EP. The thermogravimetric analysis results indicated that the incorporation of AEPP promoted the initial decomposition of EP matrix, but AEPP/EP composites had a higher char yield at high temperatures. Moreover, the flexural properties of the flame retarded EP composites were studied.     

Synthesis of a novel curing agent containing organophosphorus and its application in flame‐retarded epoxy resins

A novel amine‐terminated and organophosphorus‐containing compound m‐aminophenylene phenyl phosphine oxide oligomer (APPPOO) was synthesized and used as curing and flame‐retarding agent for epoxy resins. Its chemical structure was characterized by Fourier transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance (¹H NMR), ¹³C nuclear magnetic resonance, and ³¹P nuclear magnetic resonance. The flame‐retardant properties, combusting performances, and thermal degradation behaviors of the cured epoxy resins were investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter test, and thermogravimetric analysis. The EPO/APPPOO thermosets passed V‐1 rating with the thickness of 3.0 mm and the LOI value reached 34.8%. The thermosets could pass V‐2 rating when the thickness of the samples was 1.6 mm. The cone calorimeter test demonstrated that the parameters of EPO/APPPOO thermosets including heat release rate and total heat release significantly decreased compared with EPO/PDA thermosets. Scanning electron microscopy revealed that the incorporation of APPPOO into epoxy resins obviously accelerated the formation of the compact and stronger char layer to improve flame‐retardant properties of the cured epoxy resins during combustion. The mechanical properties and water resistance of the cured epoxy resins were also measured. After the water‐resistance test, EPO/APPPOO thermosets still remained excellent flame retardant and the water uptake was only 0.4%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41159.     

Synthesis and characterization of a novel aliphatic polyester based on itaconic acid

A novel potentially biobased aliphatic polyester poly (butylene 2‐methylsuccinate) (PBMS) was synthesized from 1,4‐butanediol (BDO) and 2‐methylsuccinate acid (MSA) via direct esterification and polycondensation route using tetrabutyl titanate (TBT) as catalyst. The reaction conditions were investigated in detail. The proper molar ratio (1.08:1) of BDO to MSA was determined through balancing the reaction efficiency and costs of reactants. TBT was found to be an effective catalyst, and its content (0.1 mol% of MSA) was optimized based on the esterification ratio and intrinsic viscosity. The molecular weight of PBMS polymers was governed by the polycondensation time. The weight average molecular (M_w) characterized by gel permeation chromatography (GPC) ranged from 5,800 to 8,700 g/mol. The polyester was also characterized by nuclear magnetic resonance spectroscopy (¹H NMR), differential scanning calorimeter and thermogravimetric analysis. The results showed that the glass transition temperature continuously increased with molecular weight. The polyester had excellent thermal stability, and its decomposition temperature increased with the molecular weight. As new potentially biobased polyester plasticizer, desirable mechanical properties were achieved at the weight ratio of PBMS was 80/100 and 50/100. In addition, the PBMS/poly(vinyl chloride) (PVC) blends had superior migration‐resistant property to the low‐molecular weight plasticizer dioctyl phthalate for PVC. POLYM. ENG. SCI., 54:2515–2521, 2014. © 2013 Society of Plastics Engineers     

Fire performance and post‐fire mechanical properties of polymer composites coated with hybrid carbon nanofiber paper

In this study, glass fiber reinforced polyester composites were coated with carbon nanofiber/clay/ammonium polyphosphate (CCA) paper and carbon nanofiber/exfoliated graphite nanoplatelets/ammonium polyphosphate (CXA) paper. The composites were exposed to a heat flux of 35 kW/m² during the cone calorimeter testing. The testing results showed a significant reduction in both heat release rates and mass loss rates. The peak heat release rate (PHRR) of CCA and CXA composite samples in the major decomposition period are 23 and 34% lower than the control sample, respectively. The time to reach the PHRR for the CCA and CXA composite samples are ～ 125% longer than the control sample. After the composite samples were exposed to heat for different time periods, their post‐fire mechanical properties were determined by three‐point bending testing. The three‐point bending testing results show that the composite samples coated with such hybrid papers exhibit more than 20% improvement in mechanical resistance at early stages of combustion. The mechanism of hybrid carbon nanofiber paper protecting the underlying laminated composites is discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.