Recent Progress in Two-dimensional Nanomaterials Following Graphene for Improving Fire Safety of Polymer (Nano)composites

The high fire safety of polymer nanocomposites is being pursued by research institutions around the world. In addition to intrinsic flame retardancy strategy, the additive-type flame retardants have attracted increasing attention due to low commercial cost and easy fabrication craft. However, traditional additive-type flame retardants usually need high addition amount to achieve a desirable effect, which causes many side-effects on the overall performance of polymer materials, such as deteriorated mechanical property and processability. At present, two-dimensional(2 D) nanomaterials have also been applied to reduce the fire hazards of polymer(nano)composites with the coupling of barrier function and catalysis as well as carbonization effect. Even though most research work mainly focus on graphene-based flame retardants, more emerging two-dimensional nanomaterials are taking away research attention, due to their complementary and unique properties, mainly including hexagonal boron nitride(h-BN), molybdenum disulfide(MoS_2), metal organic frameworks(MOF), carbon nitride(CN),titanium carbide(MXene) and black phosphorene(BP). In this review, except for graphene, the flame retardant mechanism involving different layered nanomaterials are also reviewed. Meanwhile, the functionalization method and flame retardancy effect of different layered nanomaterials are emphatically discussed for offering an effective reference to solve the fire hazards of polymer materials. Moreover, this work objectively evaluates the practical significance of polymer/layered nanomaterials composites for industrial application.     

Synergistic effect of graphene oxide and boron-nitrogen structure on flame retardancy of natural rubber/IFR composites

In this paper, GO-BN(graphene oxide grafted boron nitride) was synthesized from graphene oxide and boron nitride by silane coupling agent KH550. Furthermore, GO-BN and intumescent flame retardant (IFR) were added into natural rubber (NR) simultaneously to improve its flame retardancy. The structure of GO-BN was studied by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The analysis showed that GO-BN was successfully synthesized. The enhanced flame retardancy performance of flame retardant natural rubber (FRNR) was evaluated by limiting oxygen index (LOI) and UL-94 tests. Moreover, the combustion action of FRNR in fire was evaluated by cone calorimetry. Notably, the results showed that the sample with a GO-BN content of 12 phr showed the best flame retardancy performance. The heat release rate (HRR) and total heat release rate (THR) were remarkably decreased by 42.8% and 19.4%, respectively. Carbon residues were analyzed by infrared spectroscopy and scanning electron microscopy, which showed that GO-BN and IFR had a synergistic catalytic effect. The formation of compact thermal stable carbon layer after combustion was the key to protect engineering materials from combustion.     

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.     

Fire reaction properties of polystyrene-based nanocomposites using nanosilica and nanoclay as additives in cone calorimeter test

Using nanofiller additives in the polymer matrix to form nanocomposites is a potential way of reducing the flame spread and enhancing flame retardancy of polymeric materials during fire. To understand the fire reaction properties and the relative performance of flame-retardant additives in polymer during well-developed fire, neat polystyrene, polystyrene–silica and polystyrene–nanoclay (MMT) have been tested in a cone calorimeter. The neat polystyrene and the polystyrene nanocomposites have been prepared via an in situ polymerization method. An external heat flux of 50 kW m^?2 was applied in the test, and parameters such as heat release rate, peak heat release rate, time to ignition, smoke toxicity, CO and CO₂ yield have been investigated. Both neat polystyrene and polystyrene nanocomposites have shown the trend of a thermally thick charring polymer in the heat release rate over time data. The nanocomposites had an overall better flame retardancy than the neat polystyrene in terms of lower peak heat release rate, lower average mass loss rate and enhanced char formation. The nanocomposites had also reduced smoke emission with lower CO and CO₂ yield compared to the neat polystyrene. The overall flame retardancy was enhanced as the nanofiller loading was increased for both the nanosilica and MMT nanocomposites.

     

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.     

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.     

Flame retardancy and smoke suppression of magnesium hydroxide filled polyethylene

In this work, halogen‐free, flame‐retarded polyethylene was investigated to study the effect of inorganic fillers on the improvement of flame retardancy and the suppression of smoke density. Through analyses on the thermal stability and smoke density, it was found that the flame retardancy developed by magnesium hydroxide could effectively be increased by the additional incorporation of zinc borate and talc. Furthermore, a synergistic effect was observed when zinc borate and talc were incorporated together. This result was confirmed by the observation of fire performance with cone calorimetry. A morphological study supported the idea that the improvement in the flame retardancy and the suppression of smoke density was due to hard and compact charred layers formed by the interactions between polymer and inorganic fillers. The charred layers provided a good thermal and flame barrier. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 936–944, 2003     

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.     

The study of mechanical behavior and flame retardancy of castor oil phosphate-based rigid polyurethane foam composites containing expanded graphite and triethyl phosphate

The goal of this work was the synthesis of novel flame-retarded polyurethane rigid foam with a high percentage of castor oil phosphate flame-retarded polyol (COFPL) derived from renewable castor oil. Rigid flame-retarded polyurethane foams (PUFs) filled with expandable graphite (EG) and diethyl phosphate (TEP) were fabricated by cast molding. Castor oil phosphate flame-retarded polyol was derived by glycerolysis castor oil (GCO), H₂O₂, diethyl phosphate and catalyst via a three-step synthesis. Mechanical property, morphological characterization, limiting oxygen index (LOI) and thermostability analysis of PUFs were assessed by universal tester, scanning electron microscopy (SEM), oxygen index testing apparatus, cone calorimeter and thermogravimetric analysis (TGA). It has been shown that although the content of P element is only about 3%, the fire retardant incorporated in the castor oil molecule chain increased thermal stability and LOI value of polyurethane foam can reach to 24.3% without any other flame retardant. An increase in flame retardant was accompanied by an increase in EG, TEP and the cooperation of the two. Polyurethane foams synthesized from castor oil phosphate flame-retarded polyol showed higher flame retardancy than that synthesized from GCO. The EG, in addition to the castor oil phosphate, provided excellent flame retardancy. This castor oil phosphate flame-retarded polyol with diethyl phosphate as plasticizer avoided foam destroy by EG, thus improving the mechanical properties. The flame retardancy determined with two different flame-retarded systems COFPL/EG and EG/COFPL/TEP flame-retarded systems revealed increased flame retardancy in polyurethane foams, indicating EG/COFPL or EG/COFPL/TEP systems have a synergistic effect as a common flame retardant in castor oil-based PUFs. This EG/COFPL PUF exhibited a large reduction of peak of heat release rate (PHRR) compared to EG/GCO PUF. The SEM results showed that the incorporation of COFPL and EG allowed the formation of a cohesive and dense char layer, which inhibited the transfer of heat and combustible gas and thus increased the thermal stability of PUF. The enhancement in flame retardancy will expand the application range of COFPL-based polyurethane foam materials.     

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.     

A novel flame-retardant composite material based on calcium alginate/poly (vinyl alcohol)/graphite hydrogel: thermal kinetics,combustion behavior and thermal insulation performance

Cellulose - Design and development of fire-resistant composite materials with improved flame retardancy are critically needed for firefighters in fire protection fields. Herein, a novel...     

Phosphorus polyester versus aluminium phosphinate in poly(butylene terephthalate) (PBT): Flame retardancy performance and mechanisms

Pyrolysis and fire behaviour of a phosphorus polyester (PET-P-DOPO) have been investigated. The glycol ether of the hydroquinone derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was used as a reactive halogen-free flame retardant in PET-P-DOPO. PET-P-DOPO is proposed as an alternative to poly(butylene terephthalate) (PBT) with established halogen-free additives. It exhibits a high LOI (39.3%) and achieves V-0 classification in the UL 94 test. Three different mechanisms (flame inhibition, charring and a protection effect by the intumescent char) contribute to the flame retardancy in PET-P-DOPO and were quantified with respect to different fire risks. The fire load was reduced by 66% of the PBT characteristic. The reduction is the superposition of the relative reduction due to flame inhibition (factor 0.625) and charring (factor 0.545). The peak of heat release rate (pHRR) was reduced by 83% due to flame inhibition, charring and the protection properties of the char (factor 0.486). The strength of all three mechanisms is in the same order of magnitude. The intumescent multicellular structure enables the char to act as an efficient protection layer. PBT flame-retarded with aluminium diethylphosphinate was used as a benchmark to assess the performance of PET-P-DOPO absolutely, as well as versus the phosphorus content. PET-P-DOPO exhibits superior fire retardancy, in particular due to the additional prolongation of the time to ignition and increase in char yield. PET-P-DOPO is a promising alternative material for creating halogen-free flame-retarded polyesters.     

A liquid phosphorous flame retardant combined with expandable graphite or melamine in flexible polyurethane foam

A systematic series of flexible polyurethane foams (FPUF) with different concentrations of flame retardants, bis([dimethoxyphosphoryl]methyl) phenyl phosphate (BDMPP), and melamine (MA) or expandable graphite (EG) was prepared. The mechanical properties of the FPUFs were evaluated by a universal testing machine. The pyrolysis behaviors and the evolved gas analysis were done by thermogravimetric analysis (TGA) and TGA coupled with Fourier-transform infrared (TG-FTIR), respectively. The fire behaviors were studied by limiting oxygen index (LOI), UL 94 test for horizontal burning of cellular materials (UL 94 HBF), and cone calorimeter measurement. Scanning electronic microscopy (SEM) was used to examine the cellular structure's morphology and the postfire char residue of the FPUFs. LOI and UL 94 HBF tests of all the flame retarded samples show improved flame retardancy. BDMPP plays an essential role in the gas phase because it significantly reduces the effective heat of combustion (EHC). This study highlights the synergistic effect caused by the combination of BDMPP and EG. The measured char yield from TGA is greater than the sum of individual effects. No dripping phenomenon occurs during burning for FPUF-BDMPP-EGs, as demonstrated by the result of the UL 94 HBF test. EG performs excellently on smoke suppression during burning, as evident in the result of the cone calorimeter test. MA reduces the peak heat release rate (pHRR) significantly. The synergistic effect of the combination of BDMPP and EG as well as MA offers an approach to enhance flame retardancy and smoke suppression.     

Studies on the properties of polypropylene with a new silicon‐containing intumescent flame retardant

A new intumescent flame retardant (PSiNII), which contains silicon, phosphorus, and nitrogen elements, has been synthesized and incorporated into polypropylene (PP). Its effect on the properties of PP is investigated based on flame retardancy, thermal properties, mechanical properties, and morphologies. The flame retardancy is evaluated by the limiting oxygen index value. The thermal properties (oxidative behaviors and thermal stability) are investigated by thermogravimetric analysis under nitrogen and air atmosphere. The mechanical properties are researched based on the maximum tensile stress and relative strain at break. The morphologies of PP/PSiNII are studied by the scanning electron micrograph. Their flame retardancy and thermal stability are improved by introducing PSiNII. PP/PSiNII blends can achieve high fire performance and keep high mechanical property at the same time. During a fire, the melt‐dripping behaviors of PP‐containing PSiNII are improved. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2548–2556, 2005     

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.     

Weathering resistance of halogen-free flame retardance in thermoplastics

The influence of weathering on the fire retardancy of polymers is investigated by means of a cone calorimeter test, before and after artificial weathering. The surface degradation was monitored using different techniques (ATR-FTIR, microscopy, colour measurement). Different kinds of polymeric materials were chosen, all as they are used in practice: polycarbonate (PC) blends, polyamide (PA) and polypropylene (PP) flame-retarded with arylphosphate, melamine cyanurate (MC) and intumescent formulation based on ammonium polyphosphate (APP), respectively.All samples show material degradation at the surface due to weathering. No significant weathering influence occurs on the flame retardancy when it is a bulk property, as was observed for aryl phosphates in PC blends and MC in PA. When the fire retardancy is dominated by a surface mechanism, dependence on the duration of weathering is detected: for intumescent formulations based on ammonium APP in PP, a worsening in the formation of the intumescent network was observed.     

A way to halogenfree,flame-retardant laminates for electronic applications

Due to legal specifications and standards flame retardant polymers are used as insulating materials for electrical cable and wire, as casing and constructive materials in electrical engineering, as encapsulation materials for electronic components and in laminates for printed circuit boards. The most effective way to achieve flame retardancy is by using halogenated organic materials. Because of ecological reasons a major trend is the development of halogenfree non-corrosive flame retardant polymer materials. On the laminate side Siemens R&D developed a way to halogenfree laminates meeting the UL 94V-O specification.     

Effect of fillers on fire retardancy of intumescent polypropylene blends

Addition of Ammonium Polyphosphate/Polyamide-6 system is known to provide flame retardancy in many polymers blends via an intumescent process. Particulate fillers (talc and calcium carbonate) are used in large quantities in PP. Combination of fillers in PP can modify the properties of the polymeric matrix. This study investigates the effect of fillers (talc and calcium carbonate) on the fire performance of the Polypropylene/Ammonium polyphosphate/Polyamide-6 blend. It is shown that the fire performance strongly depends on the nature of the filler used. Talc increases and calcium carbonate decreases in the fire performance of the blend.     

Synergistic fire retardancy of colemanite, a natural hydrated calcium borate, in high-impact polystyrene containing brominated epoxy and antimony oxide

This study explores for the first time the synergistic fire retardant action of natural hydrated calcium borate, namely the mineral colemanite, which partially replaces antimony oxide in brominated flame retardant high-impact polystyrene compounds. Various antimony oxide to hydrated calcium borate ratios were employed keeping the brominated flame retardant additive at a constant loading level. With partial colemanite substitution for antimony oxide, lower heat release rate, total heat evolved and fire growth index was obtained under forced flaming fire conditions. Synergism was also seen in limiting oxygen index along with maintained V-0 classification in UL-94 tests. Regarding fire behaviour and flammability ratings, a large antimony oxide to calcium borate ratio provided ultimate fire retardant performance whereas magnitudes of synergism in average heat release rate and total heat evolved tend to be higher towards a smaller ratio. Effective heats of combustion and structural/morphological characterization of fire residues ascribed the underlying mechanism demonstrated by hydrated calcium borate to the formation of a consolidated residue that co-operates with the dominant gas phase fire retardancy originating from bromine-antimony synergism. It is thus proposed that coupling is achieved between gas phase and condensed phase modes of action increasing the overall fire retardant effectiveness. Along with enhanced fire retardancy, thermal stability and mechanical properties were satisfactorily maintained with the use of hydrated calcium borate at a variety of loading levels in compounds.