Flame Retardant and Smoke Suppressant of Fe‐Organophilic Montmorillonite in Polyvinyl Chloride Nanocomposites

Two kinds of polyvinyl chloride (PVC)/organophilic montmorillonite (OMT) nanocomposites are prepared by a melt intercalation method. This study has been designed to determine if the presence of iron and zinc ions in the structure of montmorillonite (MMT) lattice can affect thermal, flame retardant and smoke suppressant properties. The information about the morphological structure of PVC/OMT nanocomposites was obtained using X-ray diffraction and transmission electron microscopy. The thermal and flame retardant properties of the nanocomposites were characterized by thermogravimetric analysis, limiting oxygen index and smoke density. The nanocomposites based on Fe-OMT exhibit better thermal, flame retardant properties and lower degradation degree than those of pure PVC. The degradation mechanism was studied by pyrolysis, gas chromatography and mass spectrometry (Py-GC-MS).     

THERMAL DEGRADATION AND FLAME RETARDANCY OF CALCIUM ALGINATE FIBERS

Calcium alginate fibers were prepared by wet spinning of sodium alginate into a coagulating bath containing calcium chloride.The thermal degradation and flame retardancy of calcium alginate fibers were investigated with thermal gravimetry(TG),X-ray diffraction(XRD),limiting oxygen index(LOI) and cone calorimeter(CONE).The results show that calcium alginate fibers are inherently flame retardant with a LOI value of 34,and the heat release rate(HRR),total heat release(THR),CO and CO_2 concentrations during ...     

Improved flame retardant properties of epoxy resin by fluorinated MMT/MWCNT additives

Flame retardant additives of montmorillonite (MMT) and multi-walled carbon nanotube (MWCNT) were embedded in epoxy resin to improve the resin's flame retardant properties. MMT was fluorinated to exfoliate its layers and enhance its dispersion into the epoxy resin. The MWCNT was also fluorinated to create hydrophobic functional groups for improved dispersion into the epoxy resin. The MWCNT reduced the degradation rate of the epoxy resin and increased the char yield. Limiting oxygen index also increased showing first order against char yield. The exfoliated MMT acted as an energy storage medium to hinder thermal transfer within the epoxy resin. The activation energy increased almost two times by fluorinated MMT/MWCNT additives. The fluorination of the additives, MMT and MWCNT significantly improved the flame retardant properties of the epoxy resin.     

Thermal and burning properties of wood flour-poly(vinyl chloride) composite

The present study deals with the effects of wood flour on thermal and burning properties of wood flour-poly(vinyl chloride) composites (WF-PVC) using thermogravimetric (TG), cone calorimetry (CONE), and pyrolysis?Cgas chromatography/mass spectrometry (Py?CGC/MS). TG tests show that an interaction occurred between wood flour and PVC during the thermal degradation of WF-PVC. Wood flour decreased the temperature of onset of decomposition of PVC. However, the char formation could be increased by adding wood flour to PVC. CONE test indicates that wood flour had positive effects on heat release and smoke emission of PVC. Comparing with PVC, WF-PVC reduced average heat release rate and the peak HRR by about 14 and 28%, respectively; smoke production rate was also decreased. The degradation mechanism was studied by Py?CGC/MS. The results show that the volatile pyrolysis products of WF-PVC are very different from PVC. The yields of HCl and aromatic compounds decreased dramatically, and the aliphatic compounds increased by the incorporation of WF.     

Influence of layered zinc hydroxide nitrate on thermal properties of paraffin/intumescent flame retardant as a phase change material

The thermal properties of paraffin as phase change material (PCM), combined with layered zinc hydroxide nitrate (LZHN) and intumescent flame retardant (IFR), have been studied by thermogravimetric analysis (TG), TG-Fourier transform infrared spectrometry (TG-FTIR), cone calorimeter (CONE),and differential scanning calorimetry (DSC). The TG results indicated that the thermal stabilities of the paraffin and paraffin/IFR composites could be improved when dodecyl sodium sulfate-modified LZHN (ds-LZHN) was incorporated. The TG-FTIR results indicated that ds-LZHN could reduce the release of combustible gases for paraffin and paraffin/IFR. The CONE results showed that the flame-retardant efficiency of IFR could be improved in the paraffin/IFR system owing to ds-LZHN. DSC results presented that the phase change temperatures and latent heats of the composites were determined by the dispersed paraffin with their mass percentage.     

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.     

Modified montmorillonite combined with intumescent flame retardants on the flame retardancy and thermal stability properties of unsaturated polyester resins

Modified montmorillonite‐containing phytic acid (PA‐MMT) has been prepared by acid treatment and then introduced into unsaturated polyester resin (UPR) with an intumescent flame retardant (IFRs). The flame retardancy and thermal degradation of UPR/IFRs/PA‐MMT were evaluated by a limiting oxygen index (LOI) test, a vertical burning test (UL‐94), a thermogravimetric analysis (TGA), and a cone calorimeter test (CCT). Besides, the mechanical properties were studied by a universal testing machine. The LOI value of UPR/IFRs/PA‐MMT composites was increased to 29.2%. The CCT results indicated that the incorporation of PA‐MMT and IFRs significantly improved the combustion behavior of UPR. The results of the mechanical properties indicated that 1.5 wt% loading of PA‐MMT in UPR/IFRs showed the highest improvement in flexural strength and tensile strength. The flame‐retardant mechanism of PA‐MMT/IFRs was examined and discussed based on the results of combustion behavior and char analysis.     

Thermal stability and flame retardancy of LDPE/EVA blends filled with synthetic hydromagnesite/aluminium hydroxide/montmorillonite and magnesium hydroxide/aluminium hydroxide/montmorillonite mixtures

The combination of organophillised montmorillonite (MMT), synthetic hydromagnesite and aluminium hydroxide (ATH) as flame retardant system for polyethylene-based materials was studied and compared with a similar system with magnesium hydroxide, ATH and MMT. The thermal stability and the flame retardant properties were evaluated by thermogravimetric analysis (TGA), differential thermal analysis (DTA), limiting oxygen index (LOI) and cone calorimeter tests. The results indicated that the addition of montmorillonite makes it possible to reduce the total filler content to achieve the flame retardant requirements. The thermal stability of filled LDPE/EVA blends increases to a higher extent for the samples containing MMT. In the cone calorimeter tests we observed a reduction of the peak heat release rate for the sample containing montmorillonite in comparison with a sample with higher filler loading without this nanoclay. An increase of the stability of the char formed could be responsible for this favourable behaviour when montmorillonite is added.In addition, mechanical properties significantly improved for the composites containing montmorillonite both for the filler loading reduction and the reinforcement effect of the nanoclay.     

Thermogravimetric investigation ofwastes from electrical and electronic equipment (WEEE)

Two components of electronic wastes (sample A – a mixture of three types of printed circuit boards, sample B – a mixture of electronic junctions with metal wires) were investigated using thermogravimetric analysis (TG). Thermogravimetric and derivative thermogravimetric data (TG and DTG) give information on the thermal stability of A and B samples and allows finding the correct conditions for their degradation using pyrolysis in an experimental system, built on the laboratory scale for utilization of hazardous wastes. X-ray fluorescence measurements prove that brominated flame retardant is present in sample A, whilst chlorinated flame retardant is a probable component of sample B. Preliminary liquid chromatography of oil products obtained as a result of thermal waste degradation shows that the hydrocarbons released during pyrolysis could be used as a fuel.     

Roles of organic intercalation agent with flame retardant groups in montmorillonite (MMT) in properties of polypropylene composites

Three kinds of organic intercalation agent containing flame retardant groups, melamine (MA), triphenylphonium (TPP) chloride, and tetradecyl trihexyl phosphonium (TTP) bromide were intercalated into montmorillonite (MMT) via cation exchange reactions. These modified MMTs are combined with intumescent systems and compounded with PP. The flame retardant and thermal properties of the PP composites are studied. The organic intercalation agents in the layers of MMT play important roles in the char formation and flame retardant properties of PP composites. MA shows a better performance in limiting oxygen index (LOI) value and TPP helps to increase UL‐94 properties, whereas TTP maintains or deteriorates the flame retardancy of polypropylene/intumescent flame retardant (IFR) composites. The LOI and UL‐94 properties increase firstly and then decrease as the content of MMT increases. The MA acts as a blowing agent and emits an inert gas to provide migration impetus, which results in a better intumescent structured and stronger char to endure heat erosion. Although TPP and TTP emit combustible gas that burn, especially for TTP as it has a more flammable aliphatic chain. The synergistic effect between MA‐MMT and IFR is better than that for TPP‐MMT and TTP‐MMT. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Effects of thermal-oxidative aging on the flammability and thermal-oxidative degradation kinetics of tris(tribromophenyl) cyanurate flame retardant PA6/LGF composites

The influence of thermal-oxidative aging on the flame retardancy of the flame retardant long-glass-fiber reinforced polyamide 6 composites (FR/PA6/LGF) with different thermal-oxidative exposure times at 160 °C were studied in this work. The flammability and flame-retardant properties of FR/PA6/LGF were investigated by means of the limiting oxygen index (LOI), vertical burning test (UL-94), cone calorimeter test (CONE), and scanning electronic microscopy (SEM), before and after thermal-oxidative aging. The thermal-oxidative stability and degradation kinetics of the unaged and aged composites were studied by thermogravimetric analysis (TGA) with the methods of Kissinger and Ozawa in dynamic measurements (10 °C/min–40 °C/min). The results indicated that the flammability properties mirrored the degradation behaviors of these FR/PA6/LGF composites whatever their forms (aged or not). The Ozawa method showed that the causes of the first peak in the heat release rate change by CONE measurement corresponded to the apparent activation energies of the first stage degradation of aged FR/PA6/LGF composites, and the same conclusion with respect to the other heat release rate peak. Moreover, this aging slightly enhanced the solid phase flame-retardant mechanism by a char-promotion function, but had no effect on the gaseous flame-retardant mechanism and the decrease of harmful gas release rates. The existence of a surface migration effect on the flame retardant would endow FR/PA6/LGF composites with better LOI values, a more protective char layer structure, and excellent UL-94 ratings.     

Flammability and thermal degradation of epoxy acrylate modified with phosphorus‐containing compounds

A series of UV‐curable flame retardant resins was obtained using epoxy acrylate (EA) modified with 1‐oxo‐4‐hydroxymethyl‐2,6,7‐trioxa‐1‐phosphabicyclo[2.2.2]octane (PEPA). The flammability was characterized by limiting the oxygen index (LOI), UL 94 and cone calorimeter, and the thermal degradation of the flame retardant resins was studied using thermogravimetric analysis (TGA) and real time Fourier transform infrared (RTFTIR). The results indicated that the flame retardant efficiency increases and the heat release rate (HRR) decreases greatly with the content of PEPA. The TG data showed that the modified epoxy acrylates (MEAs) have lower initial decomposition temperatures and higher char residues than pure EA. The RTFTIR study indicates that the MEAs have lower thermal oxidative stability than the pure EA. Copyright © 2009 John Wiley & Sons, Ltd.     

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%.     

Boron/nitrogen flame retardant additives cross‐linked cellulose nanofibril/montmorillonite aerogels toward super‐low flammability and improved mechanical properties

Low‐flammability freeze‐dried cellulose nanofibril (CNF)/sodium montmorillonite (MMT) aerogels with improved mechanical properties were fabricated via a facile cross‐linking of boric acid (BA) and melamine‐formaldehyde (MF) resins. Scanning electron microscopy analysis showed that BA cross‐linking reduced the interspacing of layered CNF/MMT aerogels whereas introduction of MF formed polymeric fibrils that connected the layers. These changes on microstructures resulted in the improvement on compressive mechanical properties of the cross‐linked aerogels. Moreover, the boron (B)/nitrogen (N) containing flame retardant cross‐linkers greatly increased the limiting oxygen index values that could reach 85% and leveled the UL‐94 rating from no rating to V‐0. Cone calorimetric results suggested that BA and MF induced a synergistic effect on the flame retardant properties of the CNF/MMT aerogels. However, the thermal conductivity was little affected because pore structure and size was not substantially modified. This simple approach fabricated highly flame‐resistant and mechanically strong CNF‐based aerogels that could be used in various engineering fields.     

Flame retardancy and thermal degradation mechanism of calcium alginate/CaCO<Subscript>3</Subscript> composites prepared via in situ method

The calcium alginate/CaCO₃ composites were prepared via in situ method, and their flame retardancy and thermal degradation mechanism were investigated. The composites as-prepared were analyzed by the scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, thermogravimetric analysis (TG), vertical burning (UL-94), cone calorimeter (CONE) and X-ray diffraction (XRD). The SEM demonstrated that the inorganic calcium salt in the composites had great influence on the morphology of materials. The TG results indicated the thermal stability of the composites was remarkably improved by 70 °C, compared with that of the calcium alginate. The combustion behaviors of the materials were assessed by CONE. In comparison with those of the calcium alginate, the peak heat release rate and total heat release of the composites decreased by 40.42 and 62.59%, respectively. The different degradation mechanisms of the calcium alginate and the composites were first proposed in detail based on the TG, XRD and SEM results. The composites exhibited excellent thermal stability and flame retardancy, which is promising to be developed for the application as flame-retardant materials in the future.     

Thermal degradation of wood treated with flame retardants

Wood, one of the most flammable materials, was treated with various compounds containing nitrogen, phosphorus, halogens, and boron. For a study of flame retardance from the standpoint of thermal degradation, the samples were subjected to thermogravimetry (TG), differential thermal analysis (DTA) and differential thermogravimetry (DTG) in nitrogen to determine if there were any characteristic correlations between thermal degradation behaviors and the level of flame retardance. From the resulting data, kinetic parameters for different stages of thermal degradation are obtained using the method of Broido. The energies of activation for the decomposition of samples are found to be from 72 to 109 kJ mol^–1. For wood and modified wood, the char yields are found to increase from 10.2 to 30.2%, LOI from 18 to 36.5, which indicates that the flame retardance of wood treated with compounds is improved. The flame retardant mechanism of different compounds has also been proposed.     

聚乙烯/石墨层间化合物热降解过程的TG-FTIR研究

将含磷化合物插层石墨层间化合物(GIC)用于聚乙烯(PE)的阻燃,采用氧指数(LOI)方法评价了PE/GIC的阻燃性能,并采用热分析-红外光谱联用技术(TG-FTIR)研究了PE/GIC的热降解过程,探讨了GIC的阻燃机理。研究表明,不同含磷化合物插层GIC阻燃聚乙烯的氧指数有显著差别,其中以多聚磷酸铵-GIC的阻燃效果较好,氧指数较高。TG-FTIR研究结果表明,GIC并未显著影响PE的热降解方式,但由于GIC体积膨胀所发生的氧化还原反应导致部分PE热降解提前并发生热氧化降解,促进了后期成炭的石墨化过程。     

Development of novel flame‐retardant thermosets based on boron‐modified phenol–formaldehyde resins

Boron‐containing novolac resins were prepared through the modification of a commercial novolac resin with different contents of bis(benzo‐1,3,2‐dioxaborolanyl) oxide. Their thermal and flame‐retardant properties were measured. Then, they were crosslinked with hexamethylenetetramine, and their thermal, thermodynamomechanical, and flame‐retardant properties were evaluated. Their modification degree was related to the segmental motion of the materials. The crosslinking of the boron‐modified novolac resins with hexamethylenetetramine was slower and not as extensive as that of commercial novolac resins because the nitrogen from intermediate species coordinated with boron. The thermal degradation of the boron‐containing novolac resins generated boric acid at high temperatures and gave an intumescent char that slowed the degradation and prevented it from being complete. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3503–3512, 2006     

Fire Retardancy of Aluminum Hydroxide Reinforced Flame Retardant Modified Epoxy Resin Composite

A novel phosphorous containing flame retardant epoxy resin is synthesized by modifying the epoxy resin initially with phosphoric acid and further with aluminum hydroxide (ATH) to enhance the fire retardancy of the modified epoxy resin. The several phosphorous modified epoxy resin to ATH mass ratios were used to study the effect of ATH addition on epoxy. Thermal and mechanical properties. The structure of the modified flame retardant epoxy resin was characterized using Fourier-transform infrared spectroscopy (FTIR) while thermal degradation behavior and flame retardant properties were examined using thermo-gravimetric analysis (TGA) and UL-94 testing. Furthermore, ultimate tensile strength and young modulus were analyzed to study the effect of ATH addition on mechanical properties. The findings indicated that fire retardancy of ATH reinforced modified ep oxy resin is higher than virgin and phosphorous modified epoxy resin and depicted eminent flame retardant properties with suitable mechanical properties.