Effect of metal chelates on the ignition and early flaming behaviour of intumescent fire-retarded polyethylene systems

Polyethylene (PE) was treated with various formulations containing an intumescent fire retardant, which consists of melamine phosphate (MP), pentaerythritol (PER) and ammonium polyphosphate (APP), and one or none of following metal chelates: CuSAO, CoSAO and NiSAO. The behaviour of this intumescent system can be enhanced significantly by the addition of small amounts (0.2%) of metal chelate (CuSAO, CoSAO and NiSAO). The thermal stabilization, burning behaviour and char formation of the fire retardant PE system have been investigated by TGA, LOI, UL-94 test, SEM and cone calorimetry. All formulations studied provide good fire retardant behaviour, with LOI ≥ 27.4 and UL-94 V-0 rating. TGA results present more complicated thermal decomposition behaviour after the addition of small amounts (0.2%) of metal chelate when compared to that of PE-IFR. Cone calorimetry of PE-IFR–metal chelate (PE-IFR–CuSAO, PE-IFR–CoSAO and PE-IFR–NiSAO) shows a very significant decrease in HRR, PHRR, ML, THR and a very significant improvement of TTI compared to samples without metal chelate. Furthermore, SEM and photographs of the char layer show that the char layer from PE-IFR–metal chelate has a compact and tough char structure compared to the open porous char layer produced by sample without metal chelate.     

高密度聚乙烯/蒙脱土纳米复合材料膨胀阻燃体系的性能

使用以乙烯/醋酸乙烯共聚物(EVA)为相容剂的高密度聚乙烯/蒙脱土(HDPE/OMT)纳米复合材料作为基体,制备了含不同成炭剂的聚磷酸铵(APP)膨胀阻燃体系,对其阻燃性能进行了比较和研究,并分析了蒙脱土与膨胀阻燃剂协效作用的机理。热重分析(TGA)、垂直燃烧(UL-94)、极限氧指数(LOI)、锥形量热计结果表明:APP/季戊四醇(PER)体系熔融过程较短可形成蒙脱土增强炭层;PER/PA/OMT体系中较高的有机物含量有利于蒙脱土迁移和堆积。     

Synthesis of functionalized α-zirconium phosphate modified with intumescent flame retardant and its application in poly(lactic acid)

A novel functionalized α-zirconium phosphate (F-ZrP) modified with intumescent flame retardant was synthesized by co-precipitation method and characterized. Poly (lactic acid) (PLA)/F-ZrP nanocomposites were prepared by melt blending method. The thermal stability and combustion behavior of PLA/F-ZrP nanocomposites were investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), vertical burning test (UL-94), scanning electronic microscopy (SEM), and cone calorimeter test (CCT). The results showed that the addition of flame retardant F-ZrP slightly affect PLA's thermal stability, but significantly improve the flame retardancy of PLA composites. In comparison with neat PLA, the LOI value of PLA/F-ZrP was increased from 19.0 to 26.5, and the UL-94 rating was enhanced to V-0 as the loading of F-ZrP at 10%. SEM results suggested the introduction of F-ZrP in the PLA system can form compact intumescent char layer during burning. All these results showed that the F-ZrP performed good flame retardancy for PLA.     

Preparation and flammability of a novel intumescent flame-retardant poly(ethylene-co-vinyl acetate) system

A phosphorus-containing flame retardant, 4-(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinan-2-yloxymethyl)-2,6,7-trioxa-1-phospha-bicyclo[2.2.2]octane-1-oxide (MOPO), was synthesized successfully and characterized. The flame retardancy and thermal behavior of a new intumescent flame-retardant (IFR) system for EVA, which was made of MOPO and ammonium polyphosphate (APP), were investigated by limiting oxygen index (LOI) test, vertical burning test (UL-94), cone calorimeter, and thermogravimetric analysis (TGA). An LOI value of 28.4 and UL-94 V-0 rating can be achieved when the total loading of MOPO and APP was 30 wt.%. The results from cone calorimeter indicate that both the heat release rate (HRR) and the total heat release (THR) of IFR-EVA decreased significantly compared with those of neat EVA. TG curves showed that the amount of residues increased significantly when intumescent additives were added; it also could be found that the LOI values increased with the increase in char residues. Meanwhile, morphology of the residues obtained from burning IFR-EVA in LOI test was studied through the SEM observations and rich compact char layers could explain the excellent flame retardance.     

Synergistic effect between a novel hyperbranched charring agent and ammonium polyphosphate on the flame retardant and anti-dripping properties of polylactide

A novel hyperbranched polyamine charring agent (HPCA), a derivative of triazines, was synthesized and well characterized by ¹H NMR and FTIR. HPCA and ammonium polyphosphate (APP) were added into polylactide (PLA) resin as an intumescent flame retardant (IFR) system to impart flame retardancy and dripping resistance to PLA. The flammability and thermal stability of IFR-PLA composites were investigated by limiting oxygen index (LOI), UL-94 vertical burning, cone calorimetry and thermogravometric analysis (TGA) tests. The results showed that the IFR system had both excellent flame retardant and anti-dripping abilities for PLA. The TGA curves suggested that HPCA has good ability of char formation and when combined with APP, would induce synergistic effect which could be clearly observed. This effect greatly promoted the char formation of IFR-PLA composites, hence improved the flame retardant property. Additionally, the structure and morphology of char residues were studied by XPS, FTIR and SEM.     

Synergistic Effect of Novel Synergists–Transition Metal Ion-incorporated Nickel Phosphates with Intumescent Flame Retardants in Polypropylene

The two kinds of transition metal ion-incorporated nickel phosphates (TMIVSB-1) were synthesized by the hydrothermal method. The flame retardancy and thermal behavior of intumescent flame retardants (IFR), with and without TMIVSB-1 for PP, were investigated by LOI, UL-94 test, thermogravimetric analyses (TGA) and cone calorimetry. TMIVSB-1 can obviously improve the flame retardant behavior of IFR systems according to the results of LOI values and UL-94 test. The results of LOI show that 2 wt% TMIVSB-1 can increase the LOI value by 3–5 unit compared with that of PP/IFR composite. The UL-94 test shows that PP with 20% IFR burns and has no rating, but the addition of a small content 2 wt% of TMIVSB-1 with 18 wt% of IFR can reach a UL-94 V-0 rating. TGA results show that the thermal stability of PP/IFR/TMIVSB-1 increases obviously more than that of PP/IFR when the temperature is above 265°C. From cone calorimetry results, it can be observed that the HRR peaks are not obviously decreased, but the burning time of PP/IFR/FeVSB-1 (351s) and PP/IFR/ZnVSB-1 (380s) is obviously prolonged compared with that of PP/IFR (303s). The real time FTIR spectra (RTFTIR) demonstrates that the addition of TMIVSB-1 further staves the decomposition of the PP composites. The scanning electron microscopy (SEM) indicates the quality of char forming of PP/IFR/ TMIVSB-1 is superior to that of PP/IFR.     

Thermal and flame retardant properties of novel intumescent flame retardant polypropylene composites

Novel intumescent flame retardant polypropylene (PP) composites were prepared based on a char forming agent (CFA) and silica-gel microencapsulated ammonium polyphosphate (Si-MCAPP). The thermal and flame retardancy of flame retardant PP composites were investigated by limiting oxygen index, UL-94 test, cone calorimetry, thermogravimetric analysis, scanning electron micrograph, and water resistance test. The results of cone calorimetry show that the flame retardant properties of PP with 30 wt% novel intumescent flame retardants (CFA/Si-MCAPP = 1:3) improve greatly. The peak heat release rate and total heat release decrease, respectively, from 1,140.0 to 156.8 kW m^?2 and from 96.0 to 29.5 MJ m^?2. The PP composite with CFA/Si-MCAPP = 1:3 has the excellent water resistance, and it can still obtain a UL-94 V-0 rating after 168 h soaking in water.     

Combustion properties and thermal degradation behavior of polylactide with an effective intumescent flame retardant

An intumescent flame retardant spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine (SPDPM) has been synthesized and its structure was characterized by Fourier transformed infrared spectrometry (FTIR), ¹H and ³¹P nuclear magnetic resonances (NMR). A series of polylactide (PLA)-based flame retardant composites containing SPDPM were prepared by melt blending method. The combustion properties of PLA/SPDPM composites were evaluated through UL-94, limiting oxygen index (LOI) tests and microscale combustion calorimetry (MCC) experiments. It is found that SPDPM integrating acid, char and gas sources significantly improved the flame retardancy and anti-dripping performance of PLA. When 25 wt% flame retardant was added, the composites achieved UL-94 V0, and the LOI value was increased to 38. Thermogravimetric analysis (TGA) showed that the weight loss rate of PLA was decreased by introduction of SPDPM. In addition, the thermal degradation process and possible flame retardant mechanism of PLA composites with SPDPM were analyzed by in situ FTIR.     

Self-extinguishing polypropylene with a mass fraction of 9% intumescent additive II – Influence of highly oriented fibres

Recently, noticeably enhanced flame retardancy of multilayered self-reinforced composites, flame retarded with common ammonium polyphosphate based intumescent system, was described. In this paper the observed novel flame retardant synergism between intumescent additive system and highly oriented polymer fibres is further studied. The ignitability and combustion behaviour of flame retarded multilayer self-reinforced composites were compared to flame retardant compounds, prepared by simple melt compounding, of identical low additive contents, both when the heat was applied parallel (UL-94 tests) and perpendicular (cone calorimetric tests) with the direction of the embedded oriented tapes in self-reinforced composites. SEM and EDS analyses supported the different foaming process of the two types of samples to be understood, while the structure and character of the finally (after combustion) obtained charred layers were examined by compression tests. Considering the results of all the applied testing methods, the complex picture of the mechanism behind the enhanced flame retardant efficiency of flame retarded self-reinforced composites could be clarified.     

An efficient halogen-free flame retardant for glass-fibre-reinforced poly(butylene terephthalate)

Compared with poly(butylene terephthalate) (PBT), glass-fibre-reinforced poly(butylene terephthalate) (GF-PBT) is difficult to flame retard with halogen-free flame retardants. In the present study, the aluminium salt of hypophosphorous acid (AP) was used as a flame retardant for GF-PBT. A series of flame-retardant GF-PBT composites was prepared via melt compounding. The flame retardance and combustion behaviour of the composites were studied by limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimetric test. Thermal behaviours and thermal decomposition kinetics were investigated by thermogravimetric analysis (TGA) under N₂ atmosphere. The addition of AP to the composites could result in an increased LOI value, a UL-94 V-0 (1.6 mm) classification and a better fire performance in cone calorimetric tests. The char morphology observation after flame-retardant tests, calculation of decomposition kinetics, X-ray photoelectron spectroscopy (XPS) and infra-red spectral analysis of the char residue confirmed the condensed-phase flame-retardant mechanism. Furthermore, the mechanical properties of the flame-retardant composites were not deteriorated, retaining an acceptable level.     

磷杂菲类阻燃剂的合成及其与聚磷酸铵复合膨胀体系对环氧树脂的阻燃性能研究

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、五硫化二磷(P2S5)为原料合成9,10-二氢-9-氧杂-10-磷杂菲-10-硫化物(DOPS),并将DOPS与聚磷酸铵(APP)组成复合阻燃剂,用于环氧树脂(EP)的阻燃改性.通过氧指数(LOI)、垂直燃烧(UL-94)、热失重(TGA)、锥形量热(CONE)和扫描电镜(SEM)等方法对改性后的环氧树脂的阻燃性能和阻燃机理进行了测试和分析.实验结果表明,DOPS/APP阻燃体系对EP具有很好的阻燃性能,且复配阻燃剂的阻燃效果比单一的阻燃剂阻燃效果好;其中,当阻燃剂的总添加量达到30%时即W_(DOPS)=10%、W_(APP)=20%时,阻燃EP复合材料的LOI值可达到29.2%,垂直燃烧等级达到UL-94 V-0级,残炭量可达49.3%.     

Role of Copper Oxide on Epoxy Coatings with New Intumescent Polymer-Based Fire Retardant

Epoxy resins (EP) have been used as a thermos-setting material in the field of coating, casting, bonding agent, and laminating. However, a major drawback associated with its use is the lack of good flaming properties, and it is responsible for heavy smoke along with hazardous gases considerably limiting its uses in various fields. In this study, N-ethanolamine triazine-piperizine, a melamine polymer (ETPMP), was established as a new charring-foaming agent and was successfully synthesized with ethanolamine, piperizine, cyanuric chloride, and melamine as precursor molecules via the nucleophilic substitution reaction method. Elemental analysis and Fourier transform infrared (FTIR) spectroscopy analysis were applied to approve the synthesis of ETPMP and confirmation of its structure and characterization. The epoxy coating of intumescent flame retardant (IFR) was equipped by introducing ETPMP, ammonium polyphosphate (APP), and copper oxide (CuO) in multiple composition ratios. CuO was loaded at various amounts into the IFR-coating system as a synergistic agent. The synergistic action of CuO on IFR coatings was scientifically examined by using different analytical tests such as vertical burning test (UL-94V), limited oxygen index (LOI), thermal gravimetric analysis (TGA), cone calorimeter, and scanning electron microscope (SEM). The results showed that small changes in the amount of CuO expressively amplified the LOI results and enhanced the V-0 ratings in the UL-94V test. The TGA data clearly demonstrate that the inclusion of CuO can transform the thermal deprivation behavior of coatings with a growing char slag proportion with elevated temperatures. Information from cone calorimeter data affirmed that CuO can decrease the burning factors by total heat release (THR) together with peak heat release rate (PHRR). The SEM images indicated that CuO can enrich the power and compression of the intumescent char that restricts the movement of heat and oxygen. Our results demonstrate a positive influence of CuO on the epoxy-headed intumescent flame retardant coatings.     

An efficiently halogen-free flame-retardant long-glass-fiber-reinforced polypropylene system

In order to solve the “candlewick effect” caused by glass fibers, which results in the decrease of flame retardancy of flame-retardant long-glass-fiber-reinforced polypropylene (LGFPP) systems, and the deterioration of mechanical properties caused by adding an additional amount of flame retardants compared with flame-retardant non-glass-fiber-reinforced polypropylene systems so as to keep a same flame retardancy, a novel intumescent flame retardant (IFR) system, which is composed of a charring agent (CA), ammonium polyphosphate (APP) and organically-modified montmorillonite (OMMT), was used to flame retard LGFPP. The thermal stability, combustion behavior, char formation, flame retardant mechanism and mechanical properties of the IFR-LGFPP samples were investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), UL-94 test, cone calorimeter test, scanning electronic microscopy, and mechanical property tests. When the content of IFR is 20 wt%, the LOI value of IFR-LGFPP reaches 31.3, and the vertical burning test reaches UL-94 V-0 rating, solving the “candlewick effect” caused by long glass fiber without additional amount of the IFR. All the relevant cone calorimeter parameters also show that IFR-LGFPP has much better flame-retardant behaviors than LGFPP. Furthermore, the mechanical properties of IFR-LGFPP almost remain unchanged in comparison with those of LGFPP containing no IFR. The flame retardant mechanism was also discussed.     

A novel phosphazene cyclomatrix network polymer: Design, synthesis and application in flame retardant polylactide

A novel phosphazene cyclomatrix network polymer poly(cyclotriphosphazene-co- pentaerythritol) (PCPP) was synthesized and characterized based on an attempt to look for a high efficient and green intumescent flame retardant. A series of flame retardant polylactide (FR-PLA) composites containing PCPP were prepared by melt blending method. Thermal degradation behavior and combustion properties of FR-PLA composites were evaluated through thermogravimetric analysis, UL-94 experiments, limiting oxygen index and cone calorimeter tests. It is found that the weight of residues for FR-PLA composites improved greatly with the addition of PCPP. Additionally, PCPP show a high flame retardant efficiency for PLA, UL-94 V-0 could be passed only containing 5 wt% PCPP. Fourier transform infrared spectra and scanning electronic microscopy investigations reveal that the residual chars are compact and foaming containing P-O-C structure, which restrains the development of fire and increases the flame retardant properties.     

Thermal and flame retardant properties of novel intumescent flame retardant low-density polyethylene (LDPE) composites

A char-forming agent (CFA) and silica-gel-microencapsulated ammonium polyphosphate (MCAPP) were selected to form novel intumescent flame retardant system (IFRs), and then the influence of this novel IFRs on the thermal and flame retardant properties of low-density polyethylene (LDPE) were studied. The results of cone calorimetry show that the flame retardant properties of LDPE with 30?wt% novel IFR (CFA/MCAPP?=?1:3) improve remarkably. The heat release rate peak, total heat release (THR) decreases, respectively, from 1479.6 to 273.5?kW?m^?2 and from 108.0 to 80.5?MJ?m^?2. The LDPE composite with CFA/MCAPP?=?1:3 has the excellent water resistance, and it can still obtain a UL-94?V-0 rating after treated with water at 70?°C for 168?h.     

聚苯氧基磷酸联苯二酚酯/聚磷酸铵膨胀阻燃剂对环氧树脂阻燃性能影响研究

以聚苯氧基磷酸联苯二酚酯(PBPP)与聚磷酸铵(APP)组成复合阻燃剂,对环氧树脂(EP)进行阻燃改性.通过氧指数(LOI)、垂直燃烧(UL-94)、热失重(TGA)、锥形量热(CONE)和扫描电镜(SEM)等方法研究改性环氧树脂的阻燃性能和阻燃机理.结果表明,PBPP/APP体系对EP具有较好的阻燃性能,阻燃剂添加量为10%时能使环氧树脂的氧指数提高到29.6%,垂直燃烧等级达到UL94 V-0级,残炭量大大增加;平均热释放速率下降45.7%,热释放速率峰值下降51.0%,有效燃烧热平均值下降21.1%;TGA、CONE、SEM等综合分析显示了PBPP/APP改性后的环氧树脂比纯环氧树脂具有更高的热稳定性,燃烧后能够形成连续、致密、封闭、坚硬的焦化炭层,在聚合物表面产生有效覆盖、隔绝了氧气,改善了环氧树脂的燃烧性能.     

Synergistic effect of red phosphorus, novolac and melamine ternary combination on flame retardancy of poly(oxymethylene)

New flame retardant system for poly(oxymethylene) (POM) has been studied. The combination of red phosphorus with novolac and melamine was found to act as an effective flame retardant of POM. The base POM exhibited very low limiting oxygen index (LOI) value of 15.3, while the flame retarded POM gave remarkably high LOI value of 37.5 and UL94 V-1 ranking without dripping at 0.8 mm thickness. The results of cone calorimetry, thermogravimetry and FTIR analysis suggested that the flame retarding mechanism is the intumescent char formation in the condensed phase. Novolac having a phenolic hydroxyl group is miscible with POM, and in the flaming process, red phosphorus yields phosphine and its acidic product such as phosphoric acid due to hydrolysis and oxidation reactions. In addition, all of novolac, melamine and phosphine are able to readily react with formaldehyde generated from POM during burning to give the reinforced and cross-linked char network through the polyaddition and polycondensation reactions. Therefore, the red phosphorus/novolac/melamine ternary combination system could synergistically promote the high flame retardancy of POM without the flaming drips.     

Synergistic effects of aluminum hypophosphite on intumescent flame retardant polypropylene system

The effects of aluminum hypophosphite(AHP) as a synergistic agent on the flame retardancy and thermal degradation behavior of intumescent flame retardant polypropylene composites(PP/IFR) containing ammonium polyphosphate(APP) and triazine charring-foaming agent(CFA) were investigated by limiting oxygen index(LOI), UL-94 measurement, thermogravimetric analysis(TGA), cone calorimeter test(CONE), scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS). It was found that the combination of IFR with AHP exhibited an evident synergistic effect and enhanced the flame retardant efficiency for PP matrix. The specimens with the thickness of 0.8 mm can pass UL-94 V-0 rating and the LOI value reaches 33.5% based on the total loading of flame retardant of 24 wt%, and the optimum mass fraction of AHP/IFR is 1:6. The TGA data revealed that AHP could change the degradation behavior of IFR and PP/IFR system, enhance the thermal stability of the IFR and PP/IFR systems at high temperatures and promote the char residue formation. The CONE results revealed that IFR/AHP blends can efficiently reduce the combustion parameters of PP, such as heat release rate(HRR), total heat release(THR), smoke production rate(SPR) and so on. The morphological structures of char residue demonstrated that AHP is of benefit to the formation of a more compact and homogeneous char layer on the materials surface during burning. The analysis of XPS indicates that AHP may promote the formation of sufficient char on the materials surface and improve the flame retardant properties.     

Intrinsically flame retardant epoxy resin - Fire performance and background - Part I

The flame retardant effect of newly synthesized phosphorus-containing reactive amine, which can be used both as crosslinking agent in epoxy resins and as a flame retardant, was investigated. The effect of montmorillonite and sepiolite additives on the fire induced degradation was compared to pristine epoxy resin. The effect of combining the organophosphorous amine with clay minerals was also studied. It could be concluded that the synthesized phosphorus-containing amine, TEDAP can substitute the traditional epoxy resin curing agents providing additionally excellent flame retardancy: the epoxy resins flame retarded this way reach 960 °C GWFI value, 33 LOI value and V-0 UL-94 rating - compared to the 550 °C GWFI value, 21 LOI value and “no rate” UL-94 classification of the reference epoxy resin. The peak of heat release was reduced to 1/10 compared to non-flame retarded resin, furthermore a shift in time was observed, which increases the time to escape in case of fire. The flame retardant performance can be further improved by incorporating clay additives: the LOI and the HRR results showed that the optimum of flame retardant effect of clay additives is around 1 mass% filler level in AH-16-TEDAP system. Applying a complex method for mechanical and structural characterization of the intumescent char it was determined that the flame retarded system forms significantly more and stronger char of better uniformity with smaller average bubble size. Incorporation of clay additives (owing to their bubble nucleating activity) results in further decrease in average bubble diameter.     

A novel efficient halogen-free flame retardant system for polycarbonate

A novel silicon- and phosphorus-containing flame retardant, poly (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide siloxane), P(DOPO-VTES) was synthesized from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) and vinyltriethoxy silane(VTES). Its chemical structure was confirmed by FTIR. The thermal gravimetrical analysis (TGA) showed that P(DOPO-VTES) had good thermal stability and a high of char yield (86.31%) at 700 °C in nitrogen atmosphere. Its XRD patterns showed that this compound had a certain ordered structure. P(DOPO-VTES) was blended with polycarbonate (PC) together with montmorillonite(MMT) to prepare a series of organic-inorganic hybrids of flame retardant (PC)/P(DOPO-VTES)/MMT via melt blending. The thermal degradation behavior and flame retardancy of those hybrids were investigated with TGA, limiting oxygen index (LOI), vertical burning test (UL-94), and cone calorimeter. The LOI value of the flame-retardant PC systems could reach a maximal value of 32.8 when the content of P(DOPO-VTES) was 5 wt%. When 2 wt% MMT was added into the PC/5%P(DOPO-VTES) system, the UL-94 rating reached V-0. The possible flame retardant mode of MMT was studied via the dynamic rheological properties of the systems and the morphology of the chars remaining after the LOI test and the cone calorimeter test.