A review on potential development of flame retardant kenaf fibers reinforced polymer composites

Kenaf fibers have been extensively explored from the past few decades in polymer composites industries owing to its extensive adaptations, excellent properties together with its comparable mechanical properties to traditional glass fibers polymer composites. The combustibility or lowered flame retardancy hampered the diverse applications of kenaf fibers reinforced polymer composites, as it affects the mechanical strength and stiffness of composites during fire. Current review article intended to be a comprehensive source of published literature involving the flame retardants (FRs), types and applications of FRs and the fabrication of kenaf fibers reinforced polymer composites. This article will also provide a perfect data on the recent development of the FR kenaf fibers polymer composites with different FRs and explored its structural and semi‐structural industrial application for performing further research in this topic. Copyright © 2016 John Wiley & Sons, Ltd.     

Cone calorimeter analysis of flame retardant poly (methyl methacrylate)-silica nanocomposites

Nanocomposite is a promising method to reduce fire hazards of polymers. Specifically due to increased interfacial area between polymer and nanofillers, polymer nanocomposites have an advantage in reducing fire hazards efficiently even when the flame retardant additives are at a concentration of 5 mass% or less. In theory, crosslinking between the polymer chains can create a carbon-dense structure to enhance char formation, which can further promote the flame retardancy. However, little research has been done to explore the flammability of crosslinking polymer nanocomposites with a low concentration of nanosilica particles. In this study, crosslinked and non-crosslinked poly (methyl methacrylate) (PMMA) nanocomposites of a low concentration of nanosilica particles have been prepared via an in situ method. Their fire properties were tested by using the cone calorimeter at the heat flux of 50 kW m^?2. Although silica-containing flame retardants tend to negatively affect the ignitability and soot production especially at a high concentration, through the condensed phase mechanism, the samples of high loading rate of nanosilica particles show better fire retardancy performance in the aspect of flammability, including decreased heat release rate, mass loss rate, and total heat release. Additionally, crosslinking indeed attributes to the less intensive combustion of crosslinked PMMA samples, especially at a low concentration of nanosilica. The combination of nanosilica particles with the modification of the internal structure of the polymer nanocomposites might be a good strategy to improve fire retardancy.     

Fire retardancy effects in single and double layered sol–gel derived TiO2 and SiO2-wood composites

Sol–gel derived TiO₂ and SiO₂-wood inorganic composites are prepared by direct vacuum infiltration of silicon and titanium alkoxide based precursors in pine sapwood in one or two cycles followed by a controlled thermal curing process. The resulting flame retardancy effect is investigated under two different fire scenarios using cone calorimetry and oxygen index (LOI). Heat release rates (HRR) especially the values for the second peak, are reduced moderately for all single layered composites. This effect is more pronounced for double layered composites where HRR was reduced up to 40 % showing flame retardancy potential in developing fires. Beside this, smoke release was lowered up to 72 % indicating that these systems had less fire hazards compared to untreated wood, whereas no meaningful improvement is realized in terms of fire load (total heat evolved) and initial HRR increase. However impressively, the LOI of the composites were increased up to 41 vol% in comparison to 23 vol% for untreated wood displaying a remarkable flame retardancy against reaction to a small flame. An approximate linear interdependence among the fire properties and the material loading as well as fire residue was observed. A residual protection layer mechanism is proposed improving the residue properties for the investigated composites.     

Evaluation of various fire retardants for use in wood flour-polyethylene composites

Wood-plastic composites represent a growing class of materials used by the residential construction industry and the furniture industry. For some applications in these industries, the fire performance of the material must be known, and in some cases improved. However, the fire performance of wood-plastic composites is not well understood, and there is little information regarding the effectiveness of various fire retardants in the public domain. We used oxygen index and cone calorimeter tests to characterize the fire performance of wood flour-polyethylene composites, and compared the results with unfilled polyethylene and solid wood. We then evaluated the effect of five additive-type fire retardants on fire performance. Generally, magnesium hydroxide and ammonium polyphosphate improved the fire performance of WPCs the most while a bromine-based fire retardant and zinc borate improved fire performance the least.     

Flame retardant performance of carbonaceous nanomaterials on polyester fabric

Flame retardants (FRs) are applied to select consumer products such as baby clothing, construction materials, electronics and furniture upholstery to slow or prevent fire ignition or growth by physical/chemical mechanisms. The most commonly used FRs have historically been halogenated molecules. However, their bioaccumulation in mammals has been investigated, leading to some of them to be banned. As an alternative FR, this study investigated the potential of carbonaceous nanomaterials (CNMs) such as carbon nanotubes (CNTs) and graphene oxide (GO) coating material on polyester fabric. CNMs mass loadings on fabrics were verified by programmed thermal analysis (PTA) and tested for flame retardancy using a new assessment approach based on National Fire Protection Association (NFPA) method 705. Compared with traditional FRs, select CNMs showed similar flame retardancy at lower mass loadings. The oxygen content of CNMs, as measured by X-ray photoelectron spectroscopy (XPS), emerged as a critical parameter with higher oxygen content resulting in reduced flame retardancy of the coating. Non nano-sized carbonaceous materials such a carbon black did not exhibit the same flame retardant properties as CNMs. Multi-walled carbon nanotubes (MWCNTs) and amine functionalized multi-walled carbon nanotubes (e.g., NH₂-MWCNT) required significantly lower mass loadings to achieve flame retardancy similar to traditional FRs and hence are promising alternatives that warrant further investigation.     

Modified boron nitride as an efficient synergist to flame retardant natural rubber: preparation and properties

A new flame retardant system with organic modified boron nitride (m‐BN) and intumescent flame retardant (IFR) was used in this paper, and the synergistic flame retardancy of m‐BN and IFR on natural rubber (NR) was studied. NR/IFR/m‐BN composites were characterized by X‐ray photoelectron spectroscopy(XPS), Fourier transform infrared spectrometry (FTIR), thermogravimetric analysis, UL‐94, limiting oxygen index (LOI), tensile testing, cone calorimeter testing, and thermal conductivity testing. When 4 wt% m‐BN was added, the flame retardancy and mechanical properties of the composites were improved. The LOI value of NR/IFR/4 phr m‐BN reached 26.8%, and suppressed fire spread in a UL‐94 test. Compared with pure NR, the peak heat release rate (pHRR) was reduced by 52.2%, the total heat release (THR) was reduced by 27.6%, and CO yields were reduced by 51.4%. As a key aspect of fire safety, the ignition time is effectively delayed to 23 seconds due to the increased thermal conductivity of NR/IFR/m‐BN. Since the synergistic effect of m‐BN effectively improves the flame retardancy of NR, it provides a feasible method for improving the fire safety of polymers.     

硅橡胶复合材料阻燃研究进展

将功能填料引进到硅橡胶及其复合材料中可以获得特定功能的硅橡胶复合材料,已经成为近些年研究热点。目前阻燃剂种类繁多,但是性能比较单一,这已经不能满足人们的需要。人们在关注硅橡胶复合材料阻燃性能的同时,也考虑与其它性能兼备以及成本等问题。因此,本文综述了铂化合物、磷系阻燃剂、阻燃涂层、阻燃填料和微胶囊化阻燃剂等阻燃体系下硅橡胶复合材料的阻燃研究现状,总结了不同阻燃剂的阻燃机理,并且给出了其今后的改进方法,最后对硅橡胶复合材料阻燃研究的发展做了展望。     

Flammability of Polymer/Clay Aerogel Composites: An Overview

ABSTRACT

Polymer/clay aerogel composites fabricated using the freeze-drying method and water as solvent has drawn extensive attentions during the past decade. Such aerogels possess layered or network microstructures, low thermal conductivities, and good thermal stabilities; of special interest, they generally have very low flammability, which could be influenced by the composition and microstructure of the aerogel composites. The fire performance of the aerogels can be further improved with flame retardant modifications. Polymer/clay aerogel composites can also serve as effective flame retardant coatings. The mechanisms of the flame retardancy of polymer/clay aerogel composites are also discussed herein. The thorough survey of the current literatures offers useful information to realize potential of polymer/clay aerogels and help guidance to design novel high-performance polymer/clay aerogel composites.     

Influences of coupling agent on thermal properties, flammability and mechanical properties of polypropylene/thermoplastic polyurethanes composites filled with expanded graphite

In this study, polypropylene (PP)/thermoplastic polyurethanes (TPU) filled with inorganic intumescent flame retardant expanded graphite (EG) was prepared by melt blending in a twin-screw extruder. The thermal stability, fire retardancy, mechanical properties, and fracture morphology of PP/TPU composites with treated and untreated EG were investigated by thermogravimetric analysis, cone calorimeter, and scanning electron microscope. The results showed that both untreated and treated EG can greatly enhance the thermal stability and fire resistance of polymer matrix materials. Compared with untreated EG, treated EG can further improve the flame retardancy of the composites. For example, treated EG can further reduce the heat release rate, total heat release, and CO emissions of the composites in the combustion. Surface treatment of EG could significantly improve elongation at break and impact strength of PP/TPU/EG composites due to its enhanced interfacial adhesion and the good dispersion of EG particles in the polymer matrix.     

Thermal and Mechanical Properties of Zeolite Filled Ethylene Vinyl Acetate Composites

Ethylene vinyl acetate (EVA) composites filled with zeolite (25 vol.%) were prepared using an internal mixer followed by compression molding machine. In order to enhance the thermal properties and fire retardancy of the composites, an intumescent flame retardant consisting of ammonium polyphosphate (APP)/pentaerythritol (PER) was incorporated into the composites. Two kinds of flame retardants were used which are untreated APP (APP1) and silane treated APP (APP2), where their effectiveness was evaluated by means of differential scanning calorimetry (DSC) and also thermogravimetric analysis (TGA). The results showed that both types of flame retardants have the ability to enhance the thermal stability of EVA/zeolite composites by producing charred layer which protects the underlying composites from the action of flame. Moreover, the incorporation of APP1 and APP2 has a significant effect on the composites degree of crystallinity. Meanwhile the results of tensile testing showed that the composites with APP2/PER exhibit better tensile properties compared to that with APP1/PER. This is expected since the application of silane-treated APP (APP2) could improve the dispersion of APP particles within EVA matrix.     

A facile strategy to fabricate intumescent fire-retardant and smoke suppression protective coatings for natural rubber

As flammable natural rubber (NR) becomes more ubiquitous in industrial fields, there is a growing need for safe and effective flame retardant treatments through efficient techniques. Remarkably, our developed highly efficient natural tannic acid (TA)-based intumescent flame-retardant system (AGT) has the unique function in the rubber flame retardant aspect. Meanwhile, the developed coating method through polyurethane elastomer (PU) both as adhesive medium and a carbonforming agent can not only minimize the influence of flame retardant on the desirable intrinsic properties of base polymer and also maximize the efficiency of flame retardant. The flame-retardant coating (AGT/PU) exhibits highly efficient flame retardant performances reflected by a 31.9% reduction in peak heat release rate and a 27.3% reduction in total heat release and a 26.2% reduction in total smoke production with 50 wt% loading in 1 mm thick coating due to synergistic flame retardant effects. More importantly, the excellent flame retardancy performance are obtained by the PU@AGT10, as reflected in flame retardancy index (FRI) value of 11.88 makes it as excellent flame retardancy performance. While many physically mixed flame retardants are usually seriously detrimental to mechanical properties of NR, the influence of AGT/PU coating on mechanical properties of NR decreases obviously because fire retardant just directly impacts on PU adhesive layer rather than NR matrix, and the reinforcement function of graphene is also much significant. Moreover, the coating method requires just less flame retardant to achieve high flame retardant effect for NR. These findings suggest that significant opportunities for flame retardant polymer materials in industry.     

环三磷腈类阻燃剂的合成及应用研究进展

简要介绍了制备环三磷腈类阻燃剂所需起始原料六氯环三磷腈的合成方法、合成及取代反应机理;介绍了环三磷腈阻燃剂的阻燃机理;着重阐述了近20年间反应型的羟基/氨基环三磷腈、环氧基环三磷腈、含不饱和双键的环三磷腈、羧基环三磷腈阻燃剂,以及添加型烷氧基环三磷腈、芳氧基环三磷腈的合成及阻燃应用,同时综述了其应用材料的热稳定性能和阻燃性能,并对其发展趋势作了总结和展望。     

Phosphorylated cellulose/Fe3+ complex: A novel flame retardant for epoxy resins

A novel flame retardant containing cellulose, phosphorus and ferrum complex (Cell‐P‐Fe) was successfully synthesized and then it was used as flame retardants in epoxy resins (EP). Due to the present of acid sources and carbon sources, the Cell‐P‐Fe exhibits improved thermal stability and flame retardant properties. The EP/Cell‐P‐Fe composites with 10 wt% of Cell‐P‐Fe show remarkably improved LOI and UL‐94 values compared with the flame retardants without ferrum. At the loading of 10.0 wt% flame retardants, the char yield for EP/Cell‐P‐Fe composites increased to 29.1 wt%, indicating the improved thermal stability at high temperature. Moreover, thermogravimetric analysis, morphology of char residues and FTIR results demonstrate that stable char layers are formed on the surface of the composites during the combustion, attributing to the catalytic carbonization effect of Fe and phosphorus and the present of cellulose as carbon source. The stable char layers, which can protect the underlying materials from heat and oxygen, play an important role in the flame retardancy enhancement.     

Development of additives possessing both solid-phase and gas-phase flame retardant activities

Effective additives are required to impart a measure of fire retardancy to polymeric materials used in a variety of applications. Traditionally, these have been gas-phase active additives, most commonly organohalogen compounds or solid-phase active agents, often organophosphorus compounds. Organosphosphorus flame retardants are often very effective but may suffer from a cost disadvantage when compared with their organobromine counterparts. Organohalogen flame retardants are usually quite effective but their use is a subject to several environmental concerns. The development of additives that could simultaneously promote both types of fire retardant action could make available flame retardants that are both more cost effective and more environmentally friendly than those currently in use. Several sets of compounds with the potential to display both solid-phase and gas-phase flame retardant activities have been prepared and evaluated.     

Vanillin‐derived phosphorus‐containing compounds and ammonium polyphosphate as green fire‐resistant systems for epoxy resins with balanced properties

Flame retardants from vanillin when utilized together with ammonium polyphosphate (APP) yield excellent synergistic flame retardancy toward epoxy resins. Bisphenol A epoxy resins have been widely used due to their excellent mechanical properties, chemical resistance, electrical properties, adhesion, etc., while they are flammable. Environment‐friendly and bio‐based flame retardants have captured increasing attention due to their ecological necessity. In this paper, 3 bio‐based flame retardants were synthesized from abundant and more importantly renewable vanillin, and their chemical structures were determined by ¹H NMR and ¹³C NMR. They were used together with APP (an environment‐friendly commercial flame retardant) to improve the fire resistance of bisphenol A epoxy resin. With the addition APP content of 15 phr, the modified bisphenol A epoxy resin could reach UL‐94V0 rating during vertical burning test and limit oxygen index values of above 35%, but reducing APP content to 10 phr, the flame retardancy became very poor. With the total addition content of 10 phr, the epoxy resins modified by 7 to 9 phr APP and 1 to 3 phr bio‐based flame retardants with epoxy groups or more benzene rings showed excellent flame retardancy with UL‐94V0 rating and limit oxygen index values of around 29%. The T_gs of the epoxy resins could be remained or even increased after introducing bio‐based flame retardants, as the control; those of APP alone‐modified epoxy resins compromised a lot. The green synergistic flame‐retardant systems have a great potential to be used in high‐performance materials.     

Thermal properties of compounds possessing both solid-phase and gas-phase flame retardant potential

Effective additives are required to impart a measure of fire retardancy to polymeric materials used in a variety of applications. Traditionally, these have been gas-phase active additives, most commonly organohalogen compounds, or solid-phase active agents, often organophosphorus compounds. Organosphosphorus flame retardants are often very effective but may suffer from a cost disadvantage when compared with their organobromine counterparts. Organohalogen flame retardants are usually quite effective but their use is subject to several environmental concerns. The development of additives that could simultaneously promote both types of fire retardant action could make available flame retardants that are both more cost effective and more environmentally friendly than those currently in use. Several sets of compounds including bromoanilino triazine derivatives and bromoaryl phosphates with the potential to display both solid-phase and gas-phase flame retardant activity have been prepared and evaluated by a variety of thermal methods.     

Mechanical,acoustical and flammability properties of SBR and SBR-PU foam layered structure

In this work a layer structure from styrene butadiene rubber (SBR) composites and PU foam with improved flame retardancy property and high sound absorption coefficient at frequency range (200–500 Hz). Different types of flame retardants; iron (acrylic-co-acrylamide) as metal chelate (MC), magnesium hydroxide (MOH) and sodium tripolyphosphate (STP) were blended with SBR. The type and loading level of flame retardant had a great effect on filler dispersion and consequently on mechanical properties of SBR. MOH exhibited the best dispersion as indicated from scanning electron microscope (SEM), and SBR/MOH samples had almost the highest crosslink density (16.04*10⁻⁵ g⁻¹ mol) and the best mechanical properties where the tensile strength was improved by 32.7% at 40 phr MOH. Horizontal burning rate of SBR composites indicated that MC and MOH reduced the rate of burning of SBR at all loading levels. TGA data presented that the addition of flame retardants to SBR increased the maximum decomposition temperature in all composites. A double and triple layer structures of SBR composite and PU foam was designed. The effect of 2.5 cm air cavity on the sound absorption coefficient of SBR-PU foam layered structure was studied. The presence of air cavity behind the layered structure improved the sound absorption in the range of (200–500 Hz) better than the existence of it between the layers. The triple-layer structure gave higher sound absorption coefficient at lower frequencies than that obtained with the double-layer structure where it reached to ≥0.98 at 315 Hz.     

Synergistic effect of flame retardants and graphitic carbon nitride on flame retardancy of polylactide composites

In order to improve the flame retardant of polylactide (PLA), the synergistic effect of graphitic carbon nitride (g‐C₃N₄) with commercial‐available flame retardants melamine pyrophosphate (MPP) and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) was investigated. The PLA composites containing 5 wt% g‐C₃N₄ and 10 wt% DOPO had a highest limited oxygen index (LOI) value of 29.5% and reached the V‐0 rating of UL‐94 test. The cone calorimeter tests exhibited that DOPO had a better synergistic effect with g‐C₃N₄ than MPP to improve flame retardancy of PLA. The peak heat release rate (pHRR) and total heat release (THR) of PLA composites containing 10 wt% DOPO could be reduced by 25.2% and 23.6%, respectively, as compared with those of pure PLA. The presence of rich phosphorus element and aromatic groups in DOPO contributed to obtain continuous compact char layer and increase the graphitization level of char residues, thereby, resulting in improving the flame retardancy of PLA together with g‐C₃N₄. In addition, the incorporation of DOPO can serve as a plasticizer to reduce the complex viscosity, improving the processability of PLA composites.     

A review on flame retardant technology in China. Part II: flame retardant polymeric nanocomposites and coatings

The progress of flame retarded polymer nanocomposites and coatings in China over the past decades are described in this review. Emphasis on flammability performance of polymer nanocomposites containing nanofillers, mainly layered inorganic compounds, nanofibers and nanoparticles, combined with conventional flame retardant additives are addressed based on the open literature. Polymeric coatings with improved flame retardancy prepared using a wide variety of additives and UV‐curing technology are also introduced. Derived from this research, the combination of multiple methods and technologies including catalyst and nanotechnology, is predicted to have a high probability to enhance char formation and improve the flame retardancy of polymeric materials. Copyright © 2011 John Wiley & Sons, Ltd.     

纳米阻燃高分子材料:现状、问题及展望

纳米阻燃体系是一种新型的聚合物阻燃体系,被誉为阻燃技术的革命.极少量(≤5wt%)纳米阻燃剂的加入即能显著降低高分子材料燃烧时的热释放速率(HRR)和烟密度(SEA),延缓其燃烧过程,还能不同程度地提高材料的力学性能.本文总结了近年来国内外纳米阻燃领域的进展,介绍了本课题组在纳米阻燃方面所做的工作,探讨了纳米阻燃研究中存在的问题,并对其未来的发展进行了展望.