Flame retardancy and thermal stability of polyhedral oligomeric silsesquioxane nanocomposites

The flame retardancy and thermal stability of polyhedral oligomeric silsesquioxane (POSS) nanocomposites are reviewed. Results are summarized and compared on the basis of structure–property relationships. Because of the variability of groups attached on POSS, they exhibit different performance in polymer nanocomposites: metal‐containing POSS show good catalytic charring ability; vinyl‐containing and phenyl‐containing POSS promote the strength of char. Improvements in the cone calorimeter (such as reduced peak heat release rate) are advantages of POSS as preceramics for fire retardancy compared with traditional flame retardants, and it will pave the way to the design of inorganic–organic hybrid polymer nanocomposites with enhanced flame retardancy and thermal stability. Copyright © 2011 John Wiley & Sons, Ltd.     

Flame retardancy and thermomechanical properties of the poly‐(glycidyloxypropyl) phenyl silsesquioxane/layered titanate nanocomposites

Poly‐(glycidyloxypropyl) phenyl silsesquioxane (PGPSQ) was combined with an organo‐layered titanate filler. The phase structure of the obtained composite was evaluated by XRD and TEM observations. Moreover, a burning test was carried out according to the UL‐94 test method. The extinguishing time of the nanocomposites was classified V‐0 even for the 1 wt % layered titanate content. Based on the results, it was clarified that the frame retardancy of the PGPSQ/organo‐layered titanate system was superior to the poly‐(glycidyloxypropyl) silsesquioxane (PGSQ)/organo‐layered titanate system, which was reported in a previous paper. In addition, the layered titanate as a filler also improved the ductility of the PGPSQ. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

PP/纳米蒙脱土复合材料炭层结构对阻燃性能的影响

采用熔融插层法制备了不同纳米蒙脱土含量的聚丙烯(PP)/有机蒙脱土(OMMT)和PP/无机蒙脱土(MMT)复合材料,且评价了复合材料的阻燃性能:采用数码相机、扫描电子显微镜观察了燃烧残余物结构.加入OMMT可显著提高PP/OM MT的阻燃性能:纯PP的热释放速率(HRR)峰值为1 337.59 kW/m2;w(OMMT...     

New developments in flame retardancy of glass‐reinforced epoxy composites

This work involves the development of novel glass fiber–reinforced composite materials containing a commercially available epoxy resin, a phosphate‐based intumescent, and inherently flame‐retardant cellulosic (Visil, Sateri) and phenol–formaldehyde (Kynol) fibers. The intumescent and flame‐retardant fiber components were added both as additives in pulverized form and fiber interdispersed with the intumescent as a fabric scrim for partial replacement of glass fiber. Thermal stability, char formation, and flammability properties of these novel structures were studied by thermal analysis, limiting oxygen index, and cone calorimetry. The results are discussed in terms of effect of individual additive component on thermal degradation/burning behavior of neat resin. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2511–2521, 2003     

Influence of morphology and ammonium polyphosphate dispersion on the flame retardancy of polystyrene/nylon‐6 blends

The influences of the distribution of ammonium polyphosphate (APP) in polystyrene/nylon‐6 [PS/polyamide‐6 (PA6)] blends and the continuity of the (PA6 + APP) phase on flame retardancy were investigated. The flame retardant properties were evaluated by limiting oxygen index (LOI), vertical flammability test and cone calorimeter tests. The results showed that APP is exclusively dispersed in the PA6 phase, and (PA6 + APP) phase formed a continuous state when the content of PA6 in PS/PA6 blends was higher than 32% (w/w). For blends with a continuous (PA6 + APP) phase, the decrease of PA6 content caused an increase in LOI values from 26% to 33% and a reduction of peak heat release rate. The improvement of flame retardancy was attributed to the increase of APP concentration in the PA6 phase, which benefited the fast formation of a continuous intumescent charred layer. The transformation of (PA6 + APP) phase morphology from a continuous state to a discontinuous state at a PA6 content of below 32% (w/w) caused a decrease in LOI. Results of thermo‐gravimetric and cone calorimeter tests indicated that the discontinuous intumescent charred layer thus formed could be responsible for the deterioration of flame retardant properties, which was also confirmed by scanning electron microscopy. Copyright © 2013 John Wiley & Sons, Ltd.     

Intumescent flame retardant–montmorillonite synergism in polypropylene‐layered silicate nanocomposites

Polypropylene/clay nanocomposites have been prepared starting from pristine mont morillonite (MMT) and reactive compatibilizer hexadecyltrimethylammonium bromide (C16). The nanocomposite structure is evidenced by the X‐ray diffraction and high resolution electronic microscopy. Intumescent flame retardant has been added to polypropylene/clay hybrids. Their flammability behaviours have been evaluated using cone calorimetry. Synergy was observed between the nanocomposites and intumescent flame retardant. Copyright © 2003 Society of Chemical Industry     

Flame retardancy,antifungal efficacies,and physical–mechanical properties for wood/polymer composites containing zinc borate

This work aimed to examine flame retardancy, antifungal performance and physical–mechanical properties for silane‐treated wood–polymer composites (WPCs) containing zinc borate (ZnB). ZnB with content from 0.0 to 7.0 wt% was added to WPCs, and silane‐treated wood contents were varied. The polymers used were poly(vinyl chloride) (PVC) and high‐density polyethylene (HDPE). The decay test was performed according to the European standard EN 113. Loweporus sp., a white‐rot fungus, was used for antifungal performance evaluation. Antifungal performance was observed to decrease with wood content. Incorporation of ZnB at 1.0 wt% significantly increased the antifungal performance of WPCs. ZnB content of greater than 1.0 wt% lowered the antifungal properties of WPCs. The results suggested that the wood/PVC composite exhibited better antifungal performance than the wood/HDPE composite. The addition of wood flour to PVC and HDPE decreased flame retardancy, whereas the incorporation of ZnB retained the flame retardancy. ZnB was found to be more appropriate for wood/PVC than wood/HDPE as a result of hydrogen chloride generated from the dehydrochlorination reaction of PVC. The results indicated that the addition of ZnB did not affect the physical‐mechanical properties of neat polymers and the composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and characterization of resol‐layered silicate nanocomposites

Resol‐layered silicate nanocomposites were synthesized by intercalative polymerization of phenol and formaldehyde using layered clays such as an aminoacid‐modified montmorillonite (MMT) and a commercial modified MMT (Cloisite 30B). The composites were prepared by a sequential process in which one of the reactives of the phenolic resin was reacted with the organosilicate and subsequently cured with triethylamine. The nanocomposites were studied by means of X‐ray diffraction, atomic force microscopy, and thermogravimetric analysis. Results show a strong clay composition dependence on the intercalation state. The composite of resol with 2 wt % aminoacid‐modified MMT content has the best dispersion of clay layers. Thermal stability of nanocomposites was slightly increased in comparison with the neat resol. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

无卤阻燃聚乙烯的阻燃性能及热裂解分析

通过极限氧指数(LOI)和锥形量热法(Cone),考察了添加质量分数30%磷系阻燃剂1,2,3-三(5,5-二甲基-1,3-二氧杂己内磷酰氧基)苯(FR)的PE(阻燃PE)的阻燃性能。借助裂解-气相色谱质谱(PY-GC/MS)联用技术研究了纯PE及阻燃PE的热裂解产物结构以探讨其阻燃机理。结果表明:阻燃PE的LOI达到25.8%,平均热释放速率相对纯PE降低55.4%,呈现出良好的阻燃性能;PY-GC/MS分析表明,FR的加入没有改变PE热分解反应的机理,但FR的添加对PE的热裂解及燃烧反应具有较强的抑制作用。     

Structure and crystallization behaviour of syndiotactic polystyrene/layered double hydroxide nanocomposites

Syndiotactic polystyrene (sPS) based polymer nanocomposites have been prepared using surfactant‐free layered double hydroxides (SF‐LDHs) by a modified solvent mixing method with different loadings of 1, 2.5, 5 and 10 wt%. The nanocomposite preparation process involves a wash treatment of as‐prepared SF‐LDHs in an appropriate organic solvent followed by gel formation in a non‐polar solvent. The gel was directly used to make highly dispersed polymer nanocomposites. The influence of highly dispersed SF‐LDH platelets on the crystallization, polymorphism, thermal stability and flame retardancy of sPS was examined. It was shown that SF‐LDHs significantly enhance the crystallization rate of sPS and favour the formation of the thermodynamically stable β form along with the α form of sPS. Moreover, highly dispersed SF‐LDHs decrease the heat release rate and total heat release of sPS indicating the enhancement of flame‐retardant properties of sPS. In this way, it was found that the dispersed SF‐LDH platelets act as a multifunctional nanofiller for sPS. © 2015 Society of Chemical Industry     

Structure and thermal property of intumescent char produced by flame‐retardant high‐impact polystyrene/expandable graphite/microencapsulated red phosphorus composite

This paper is aimed to illustrate the structure and thermal property of intumescent char produced by flame‐retardant polymers containing expandable graphite (EG). For this purpose, high‐impact polystyrene (HIPS) flame retarded by EG individually or in combination with microencapsulated red phosphorus (MRP) was prepared. The results indicate that the intumescent char from HIPS/EG/MRP composite, which contains a small amount of phosphorus element and more oxygen element, is much more compact and continuous than that from HIPS/EG composite with identical loading of flame retardant due to binding effect of phosphoric acid and its derivatives. The intumescent char produced by HIPS/EG/MRP composite exhibits much enhanced thermal and thermo‐oxidative stability as well as thermal‐insulating effect, which can withstand destruction of heat and oxygen effectively and thus provide a good fire‐proof barrier. The temperature beneath this intumescent char is decreased significantly in case of action by flame. By comparison, the porous and loose intumescent char generated by HIPS/EG composite has poor thermo‐oxidative endurance, and most of it can be consumed in air at high temperature without effective protection for the polymer. This has resulted in remarkable increase in flame retardancy of the HIPS/EG/MRP composite.     

Friction and wear studies on nylon‐6/SiO2 nanocomposites

Composites of nanometer‐sized silica (SiO₂) filler incorporated in nylon‐6 polymer were prepared by compression molding. Their friction and wear properties were investigated on a pin on disk tribometer by running a flat pin of steel against a composite disc. The morphologies of the composites as well as of the wear track were observed by scanning electron microscopy (SEM). The addition of 2 wt % SiO₂ resulted in a friction reduction (μ) from 0.5 to 0.18 when compared with neat nylon‐6. This low silica loading led to a reduction in wear rate by a factor of 140, whereas the influence of higher silica loadings was less pronounced. The smooth morphology obtained after the wear test indicated the negligible contribution to friction of the pin to the nanocomposite. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1855–1862, 2004     

Essential fracture work of nylon 6‐silicate nanocomposites

In a fracture experiment of polymers, the total fracture work usually consists of an essential part associated with the plastic deformation at the crack tip and a nonessential part related to the viscous relaxation in the background. In this article, the essential fracture work in nylon 6‐silicate nanocomposites is measured through a series of double‐notched‐sample (DNS) tests. The samples are of different silicate contents and crystallization conditions. As the cooling rate rises, the essential work is nearly constant while the total fracture work increases considerably, which should be attributed to the change in effective viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 815–819, 2005     

Reduced copper diffusion in layered silicate/fluorinated polyimide (6FDA‐ODA) nanocomposites

The copper diffusion barrier properties of layered silicate/fluorinated polyimide nanocomposites were analyzed by transmission electron microscopy (TEM) and secondary ion mass spectrometry (SIMS). It was found that the particles of copper are effectively retarded from penetrating into the polyimide matrix by layered silicates. The diffusion coefficients of layered silicate/polyimide nanocomposites are lower than that of the pure polyimide. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1422–1425, 2004     

Effect of trace chloride on the char formation and flame retardancy of the LLDPE filled with NiAl‐layered double hydroxides

Layered double hydroxides (LDHs) have received intensive attentions for the potential as flame retardants of polyolefin. In the work, trace amounts of chloride were investigated for their synergistic effects on the char formation and flame retardancy of the linear low‐density polyethylene (LLDPE) filled with NiAl‐LDHs. Results showed that 0.5 wt% of NH₄Cl incorporation enabled the char yield of 20%LDH/LLDPE (20 wt% of NiAl‐LDH) increase from 10.4% to 49.6%. Other chlorides likewise offered significant increase in the char yield of 20%LDH/LLDPE. With the flame‐retardant measurements of cone calorimeter and limiting oxygen index device, it is revealed that the flame retardancy of LLDPE filled with NiAl‐LDHs could be greatly improved when trace amounts of NH₄Cl were further introduced. Thermal stability analysis illustrated that the presence of NiAl‐LDHs or NH₄Cl all had positive effects on the thermal stability of LLDPE, in which the chlorides influenced the LLDPE thermal stability via direct participation in the degradation of LLDPE. The synergetic mechanism analysis reveals that the introduction of chloride enabled the LLDPE decomposed products have more tendency to grow carbon nanotubes with the presence of NiAl‐LDH catalysts. Finally, the mechanical properties of LLDPE filled with NiAl‐LDHs and NH₄Cl were also investigated.     

Flame retardancy and mechanical properties of pet‐based composites containing phosphorus and boron‐based additives

Flame retardancy of poly(ethylene terephthalate), PET, was improved using different flame retardant additives such as triphenylphosphate, triphenylphosphine oxide, zinc borate, and boron phosphate (BP). Composites were prepared using a twin screw extruder and subsequently injection molded for characterization purposes. The flame retardancy of the composites was determined by the limiting oxygen index (LOI) test. Smoke emission during fire was also evaluated in terms of percent light transmittance. Thermal stability and tensile properties of PET‐based composites were compared with PET through TGA and tensile test, respectively. The LOI of the flame retardant composites increased from 21% of neat PET, up to 36% with the addition of 5% BP and 5% triphenyl phosphate to the matrix. Regarding the smoke density analysis, BP was determined as an effective smoke suppressant for PET. Enhanced tensile properties were obtained for the flame retardant PET‐based composites with respect to PET. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42016.     

Flame retardancy of polycarbonate–polydimethylsiloxane block copolymer/silica nanocomposites

This report describes the flame retardancy and the thermal degradation behavior of polycarbonate–polydimethylsiloxane (PC–PDMS) block copolymer/silica nanocomposites. PC–PDMS block copolymer with dimethylsiloxane (DMS) block size 40 units increased the dispersibility of nanosized amorphous silica. Addition of the slight nanosized silica caused the increment of flame retardancy of PC–PDMS block copolymer, and the PC–PDMS block copolymer with 1.0 wt % PDMS had the highest limiting oxygen index value when the nanosized silica was added 0.5 wt %. The maximum rate temperature of the PC–PDMS block copolymer increased with the addition of silica and the maximum loss rate was the lowest when silica content is 0.5 wt %. The monodisperse nanosized silica had an effect that enhances the flame retardant mechanism of PDMS for PC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3862–3868, 2006     

A facile method for preparation of PGS@ZB‐N and gas‐sol alternating synergistic effect for fire resistance of EVA

Through the simple precipitation of palygorskite (PGS) by zinc borate (ZB) (to make PGS@ZB) and the decoration of PGS@ZB by dodecylamine (N), a novel organic‐inorganic@inorganic hybrid flame retardant of PGS@ZB‐N was prepared and was incorporated with ethylene vinyl acetate copolymer (EVA) to improve its flame retardance. The structure and morphology of PGS@ZB‐N were characterized by Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), and scanning electron microscopy (SEM), and it was confirmed that the PGS@ZB‐N hybrid had been successfully prepared. The flame retardancy and burning behavior of EVA/PGS@ZB‐N/EG (EG = expandable graphite) composite were studied through thermogravimetric analysis (TGA), limiting oxygen index (LOI), UL‐94 (by the vertical burning test), and cone calorimeter test (CCT) characterizations. The prepared EVA/PGS@ZB‐N/EG composite obtained an LOI value of 41.2% with the addition of 30 wt% PGS@ZB‐N/EG. It was found that EVA/PGS@ZB‐N/EG was protected through a gas phase and condensed phase alternating synergistic effect mechanism.     

Flame retarded epoxy resins by adding layered silicate in combination with the conventional protection‐layer‐building flame retardants melamine borate and ammonium polyphosphate

The pyrolysis and flammability of phosphonium‐modified layered silicate epoxy resin nanocomposites (EP/LS) were evaluated when LS was combined with two flame retardants, melamine borate (MB) and ammonium polyphosphate (APP), that also act via a surface protection layer. Thermogravimetry (TG), TG coupled with Fourier Transform Spectroscopy (TG‐FTIR), oxygen index (LOI), UL 94 burning chamber (UL 94) and cone calorimeter were used. The glassy coating because of 10 wt % MB during combustion showed effects in the cone calorimeter test similar to nanodispersed LS, and somewhat better flame retardancy in flammability tests, such as LOI and UL 94. Adding APP to EP resulted in intumescent systems. The fire retardancy was particularly convincing when 15 wt % APP was used, especially for low external heat flux, and thus, also in flammability tests like LOI and UL 94. V0 classification is achieved when 15 wt % APP is used in EP. The flame retardancy efficiency of the protection layers formed does not increase linearly with the MB and APP concentrations used. The combination of LS with MB or APP shows antagonism; thus the performance of the combination of LS with MB or APP, respectively, was disappointing. No optimization of the carbonaceous‐inorganic surface layer occurred for LS‐MB. Combining LS with APP inhibited the intumescence, most probably through an increase in viscosity clearly above the value needed for intumescent behavior. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Flame retardancy and rearrangement reaction of polyphenylene-ether/polystyrene alloy

The flame retardancy and the rearrangement reaction of polyphenylene-ether [poly-(oxy-2,6-dimethyl-1,4-phenylene), PPE] and polyphenylene-ether/polystyrene (PS) alloys have been studied. The flame retardancy of PPE blended with phosphates was proportional to PPE content as well as to the phosphates. The surface temperatures of PPE during a combustion was higher than that of PS, whereas PPE is more flammable than PS. The element analysis of the polymer surface showed that carbon was richer compared with the content of the newly synthesized PPE. Four monomeric and eight dimeric scission products were recovered by thermogravimetric-mass (TGA-MASS) analysis at high temperature in inert atmosphere. These structures of the scission products suggested that the rearrangement reaction occurred in combustion at high temperature. Namely, the formation of carbonaceous materials on the surface followed the rearrangement reaction and dehydration which was accelerated by the addition of aromatic phosphates. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1175–1183, 1997