Flame‐retardant and smoke‐suppressant properties of zinc borate and aluminum trihydrate‐filled rigid PVC

The effects of zinc borate (ZB), aluminum trihydrate (ATH), and their mixture on the flame‐retardant and smoke‐suppressant properties of poly(vinyl chloride) (PVC) as well as their mechanism for flame retardancy and smoke suppression were studied through the limiting oxygen index (LOI) test, smoke density test, TGA, GC–MS, and SEM. The results show that incorporation of a small amount of ZB, ATH, and their mixture can greatly increase the LOI of PVC and reduce the smoke density of PVC during combustion. The mixture of ZB with ATH has a good synergistic effect on the flame retardance and smoke suppression of PVC. TGA and GC–MS analyses results show that incorporation of a small amount of ZB, ATH, and their mixture greatly promotes the char formation of PVC and decreases the amount of hazardous gases such as benzene and toluene released in PVC during combustion. Their mechanism is also proposed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3119–3127, 2000     

电缆用高阻燃耐热软质PVC的制备及性能研究

以软质PVC为基体,选用氢氧化铝-氢氧化镁(ATH/MDH)为复配阻燃剂、硼酸锌(ZB)为阻燃协效剂及钙锌材料为复合热稳定剂(Ca-Zn),通过共混法对PVC进行改性,制备PVC/ATH/MDH、PVC/ATH/MDH/ZB及PVC/ATH/MDH/ZB/Ca-Zn等软质PVC复合电缆料。分析3种电缆料的阻燃性能、拉伸性能及热稳定性。结果表明:相较纯软质PVC,PVC/ATH/MDH与PVC/ATH/MDH/ZB的阻燃性能提高,拉伸性能显著下降,且热稳定性改善不明显。而PVC/ATH/MDH/ZB/Ca-Zn的阻燃性能显著提升,与纯软质PVC相比,其极限氧指数(LOI)增加34.90%,烟密度等级下降29.50%,复合材料的炭层更连续且致密;PVC/ATH/MDH/ZB/Ca-Zn的拉伸强度和断裂伸长率分别提高1.78%和2.48%。Ca-Zn的添加提高软质PVC的残炭率,热稳定性增强。PVC/ATH/MDH/ZB/Ca-Zn的综合性能最佳。     

Halogen‐free flame‐retardant rigid polyurethane foams: Effect of alumina trihydrate and triphenylphosphate on the properties of polyurethane foams

Rigid polyurethane foam (PUF) filled with mixture of alumina trihydrate (ATH) and triphenyl phosphate (TPP) as fire retardant additive was prepared with water as a blowing agent. In this study, the ATH content was varied from 10 to 100 parts per hundred polyol by weight (php), and TPP was used at a higher loading of ATH (75 and 100 php) in a ratio of 1 : 5 to enhance the processing during PUF preparation. The effects of ATH on properties such as density, compressive strength, morphological, thermal conductivity, thermal stability, flame‐retardant (FR) behavior, and smoke characteristics were studied. The density and compressive strength of the ATH‐filled PUF decreased initially and then increased with further increase in ATH content. There was no significant change in the thermal stability with increasing ATH loading. We determined the FR properties of these foam samples by measuring the limiting oxygen index (LOI), smoke density, rate of burning, and char yield. The addition of ATH with TPP to PUF significantly decreased the flame‐spread rate and increased LOI. The addition of TPP resulted in easy processing and also improved FR characteristics of the foam. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structural characterization of LDPE/EVA blends containing nanoclay‐flame retardant combinations

The combination of different types of organo‐modified montmorillonite (MMT) with aluminum hydroxide (aluminum trihydrate—ATH), as a flame retardant system for polyethylene‐ethylene vinyl acetate (LDPE/EVA), blends were studied. Five different types of organically modified montmorillonite clays, each with different modifier, were used. The structural characterization was carried out by X‐ray diffraction (XRD) and scanning electron microscopy in transmission mode (STEM). The mechanical and rheological properties were also evaluated. The XRD analysis showed a clear displacement of the d₀₀₁ signal, which indicates a good degree of intercalation, especially for the MMT‐I28 and MMT‐20, from Nanocor and Southern Clay Products, respectively. The presence of ATH and the compatibilizer did not have any effect on the exfoliation of the studied samples. The thermal stability and flame retardant properties were evaluated by thermogravimetric analysis (TGA), limiting oxygen index (LOI—ASTM D2863), and flammability tests (Underwriters Laboratory—UL‐94). The effect of different compatibilizers on the clay dispersion and exfoliation was studied. The results indicated that the addition of montmorillonite makes it possible to substitute part of the ATH filler content while maintaining the flame retardant requirements. The thermal stability of MMT/ATH‐filled LDPE/EVA blends presented a slight increase over the reference ATH‐filled LDPE/EVA blend. Compositions with higher clay content (10 wt %) showed better physicochemical properties. The increased stability of the higher clay content compositions results from the greater inorganic residual formation; this material has been reported to impart better performance in flammability tests. The mechanical properties and flame retardancy remained similar to those of the reference compound. The reduced ATH content resulted in lower viscosities and densities, facilitating the processing of the polymer/ATH/clay compounds. Extrusion of these compounds produced a lower pressure in the extrusion head and required reduced electrical power consumption. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of irradiation on the mechanical,electrical, and flammability properties of (low‐density polyethylene)/(ethylene‐[vinyl acetate] copolymer) blends containing alumina trihydrate

Alumina trihydrate (ATH) was added to (low‐density polyethylene)/(ethylene‐[vinyl acetate] copolymer) blends (LPEs) to enhance their flame resistance. The addition of substantial amounts of ATH has been known to have deleterious effects on the mechanical properties of such blends. Hence, electron beam irradiation was used to improve the mechanical properties of our ATH‐filled LPE specimens. The specimens were irradiated at 50 to 150 kGy before being cut into specified shapes for analysis. The increase in the irradiation dosage increased the gel content as a result of the formation of crosslinked networks. Also, the flame resistance of the LPE blends was enhanced by increasing both the loading level of ATH and the irradiation dosage. However, a high ATH loading level reduced tensile strength and elongation at break. Nevertheless, the electron beam irradiation maintained the tensile strength and elongation of the ATH‐filled blends. In addition, a higher content of ATH in the LPE blends showed reactive interaction with irradiation effects. A higher amount of ATH reduced the electrical resistivity of the blends, but analysis of their surface and volume resistivity showed that the electrical resistance of the ATH‐filled LPE blends could be improved by electron beam irradiation in the range of 50 to 150 kGy. J. VINYL ADDIT. TECHNOL., 20:91–98, 2014. © 2014 Society of Plastics Engineers     

Influence of incorporation methods of ATH on microstructure,elastomeric properties,flammability, and thermal decomposition of dynamically vulcanized NR/PP blends

Flame‐retardant thermoplastic vulcanizates (TPVs) of natural rubber (NR)/polypropylene (PP) (60/40 wt %) blends filled with alumina trihydrate (ATH) were prepared with an internal mixer. To increase the properties of flame‐retardant NR/PP TPV, the new mixing method, stepwise masterbatch mixing (SMB) method was adopted. The effects of SMB method along with different ATH loadings on microstructure and properties of NR/PP TPVs were investigated. Conventional one‐step mixing (CV) method was also studied for comparison. Transmission electron microscopy analysis showed that different processes led to a variation in microstructural homogeneity, which imposed various effects on blend properties. The mechanical properties of TPVs changed with ATH loading, and the strength of the samples obtained from SMB method was higher than those of CV method. LOI and cone calorimetry tests revealed that the flame retardancy of NR/PP blends dramatically increased at higher ATH loading. Furthermore, the increment level of flame retardancy was accelerated in the blends produced particularly through SMB method, resulting from homogeneity of local ATH distribution in NR/PP blend. Greater combustion resistance of blends prepared from SMB route were confirmed by thermogravimetry and pyrolysis‐gas chromatography–mass spectrometry techniques. Finally, a burning mechanism between filler structure and flammability of NR/PP TPVs obtained from CV and SMB methods was discussed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46231.     

Preparation and characterization of microcapsulated red phosphorus and its flame‐retardant mechanism in halogen‐free flame retardant polyolefins

Microcapsulated red phosphorus (MRP), with a melamine–formaldehyde resin coating layer, was prepared by two‐step coating processes. The physical and chemical properties of MRP were characterized by Fourier‐transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) and other measurements. The flame retardant action and mechanism of MRP in the halogen‐free flame retardant (HFFR) polyolefins (PO) blends have been studied using cone calorimeter, limiting oxygen index (LOI), thermogravimetric analysis (TGA) and dynamic FTIR spectroscopy. The results show that the MRP, which is coated with melamine–formaldehyde resin, has a higher ignition point, a considerably lower amount of phosphine evolution and of water absorption compared with red phosphorus (RP) itself. The data observed by cone calorimeter, LOI and TGA measurements from the PO/HFFR blends demonstrated that the MRP can decrease the heat release rate and effective heat of combustion, and increase the thermostability and LOI values of PO materials. The dynamic FTIR results revealed the flame‐retardant mechanism that RP can promote the formation of charred layers with the P–O and P–C complexes in the condensed phase during burning of polymer materials. Copyright © 2003 Society of Chemical Industry     

Flame retardant flexible poly(vinyl chloride) compound for cable application

ZnO/MgO, ZnO/CaO, and ZnO/CaO/MgO can form solid solutions. The solid solution for we as flame retardant (SSFR) was obtained by annealing at 1023 K for 4.5 h in a muffle furnace. Flexible poly (vinyl chloride) (PVC) filled with SSFR and Sb₂O₃ was investigated by differential thermal analysis thermogravimetry. Limiting oxygen index (LOI), mechanical properties, and electrical properties were studied. The surface of the char formed after combusting of the PVC compounds was observed through scanning electron microscopy and the effect of the surface area to the LOI was also studied. The data suggested that a small amount of SSFR and Sb₂O₃ have good synergy and can greatly increase the LOI and the char yield, and that the thermal degradation temperature and the activation energy decreased. It can be concluded that the mechanism of SSFR is a condensed‐phase mechanism. Moreover, one can conclude that the surface area can enhance the LOI. All the results showed that SSFR is effective and safe as a flame retardant in flexible PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3137–3142, 2003     

ATH对无卤阻燃型EPDM性能的影响

研究了不同粒径氢氧化铝（ATH）及用量对无卤阻燃型三元乙丙橡胶性能的影响。结果表明,小粒径ATH有助于保持硫化胶力学性能并提高阻燃性能;填充120目ATH的EPDM硫化胶拉伸强度仅为9.0MPa,填充7000目ATH的硫化胶拉伸强度为14.7MPa;ATH粒径变小对EPDM硫化胶的电绝缘性能影响不大。ATH用量增加,硫化胶力学性能下降,阻燃性能得到改善;当ATH用量为0份时,硫化胶氧指数仅为19.3%;当ATH用量为200份时,氧指数达到40.2%;ATH用量为140份时,垂直燃烧水平达到FV-0级。DMA数据显示,ATH粒径越小,EPDM胶料的贮能模量越大,tgδ值越小,Tg向低温方向偏移。     

Properties of poly(vinyl chloride) incorporated with a novel soybean oil based secondary plasticizer containing a flame retardant group

A novel bio‐based plasticizer containing flame retardant groups based on soybean oil (SOPE) was synthesized from epoxidized soybean oil (ESO) and diethyl phosphate through a ring‐opening reaction. PVC blends plasticized with ESO and SOPE were prepared, respectively. Properties including rheological behavior, thermal stability, flame retardant performance, mechanical properties of PVC plasticized with ESO and SOPE were carefully studied. The results showed that the plasticized PVC blends indicated better compatibility, thermal, and mechanical properties. As a novel bio‐based plasticizer containing flame retardant groups, the TGA data indicated that the thermal degradation temperature of PVC blends plasticized with SOPE could reach to 275.5°C. LOI tests and SEM indicated that the LOI value of PVC blends could increase from 24.2 to 33.6%, the flame retardant performance of SOPE was put into effect by promoting polymer carbonization and forming a consolidated and thick flame retardant coating quickly, which is effective to prohibit the heat flux and air incursion. The enhancement in flame retardancy will expand the application range of PVC materials plasticized with SOPE. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42111.     

Effect of core–shell zinc hydroxystannate nanoparticle–organic macromolecule composite flame retardant prepared by masterbatch method on flame‐retardant behavior and mechanical properties of flexible poly(vinyl chloride)

Macromolecule flame retardant melamine‐dicyandiamide‐formaldehyde‐phosphoric acid (denoted as MDFP) was used as the shell material to synthesize zinc hydroxystannate@MDFP (denoted as ZHS@MDFP), a novel composite flame retardant with core–shell structure, via masterbatch method. The morphology and structure of ZHS@MDFP were analyzed by means of transmission electron microscopy, X‐ray powder diffraction, Fourier transform infrared spectrometry, and thermal analysis. Moreover, the effect of ZHS@MDFP as a flame retardant on the flame‐retardant behavior and mechanical properties of flexible poly(vinyl chloride) (denoted as PVC) was investigated. It has been found that as‐synthesized ZHS@MDFP composite flame retardant has core–shell structure. Besides, as‐synthesized ZHS@MDFP as a core–shell flame retardant is superior to ZHS in increasing the limiting oxygen index and decreasing the smoke density rating of PVC, which is because the decomposition of MDFP shell as the blowing agent expands the char layer thereby improving the flame‐retarding capability of ZHS core. More importantly, ZHS@MDFP does not cause damage to the tensile strength and elongation at break of PVC matrix, which implies that the MDFP shell favors to improve the compatibility between ZHS and flexible PVC matrix. POLYM. ENG. SCI., 54:1983–1989, 2014. © 2013 Society of Plastics Engineers     

Phase dispersion–crosslinking synergism in binary blends of poly(vinyl chloride) with low‐density polyethylene: Entrapping phenomenon in PVC/LDPE/DCP blend

The co‐crosslinked products and the entrapping phenomenon that may exist in a poly(vinyl chloride)/low density polyethylene/dicumyl peroxide (PVC/LDPE/DCP) blend were investigated. The results of selective extraction show that unextracted PVC was due to not being co‐crosslinked with LDPE but being entrapped by the networks formed by the LDPE phase. SBR, as a solid‐phase dispersant, can promote the perfection of networks of the LDPE phase when it is added to the PVC/LDPE blends together with DCP, which leads to more PVC unextracted and improvement of the mechanical properties of PVC/LDPE blends. Meanwhile, the improvement of the tensile properties is dependent mainly on the properties of the LDPE networks. Finally, the mechanism of phase dispersion–crosslinking synergism is presented. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1296–1303, 2003     

Expandable graphite systems for halogen‐free flame‐retarding of polyolefins. II. Structures of intumescent char and flame‐retardant mechanism

The structures of the intumescent charred layers formed from polyolefin (PO) blends with expandable graphite (EG) and/or the other free‐halogen flame retardant (HFFR) and their flame‐retardant mechanism were studied by Fourier transform infrared (FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), laser Raman spectroscopy (LRS), scanning electron microscopy (SEM), differential thermal analysis (DTA), and thermal conductivity (TC) measurements. The FTIR, XPS, and LRS data showed that the carbonaceous structures of intumescent charred layers consist of EG and various numbers of condensed benzene rings and/or phosphocarbonaceous complexes attached by the P—O—C and P—N bonds or quaternary nitrogen or dehydrated zinc borate (ZB). These results and the morphologic structures observed by SEM have demonstrated that the compact structures of charred layers slow down heat and mass transfer between the gas and condensed phase and prevent the underlying polymeric substrate from further attack by heat flux in a flame. The DTA data provide the positive evidence for the flame‐retardant mechanism of the PO/EG/HFFR systems, which works by increasing the oxidation temperature and decreasing thermal oxidation heat. At the same time, the TC data reveal the flame‐retardant essence of the charred layers as good heat‐insulated materials whose TC value is only about 1/10 of the corresponding blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1190–1197, 2001     

Zinc hydroxystannate and zinc stannate as flame‐retardant agents for flexible poly(vinyl chloride)

The flame‐retardant and smoke‐suppressant properties of inorganic tin compounds such as zinc hydroxystannate (ZHS) and zinc stannate (ZS) were investigated in a comparison with alumina trihydrate, magnesium hydroxide, and Sb₂O₃ through the limiting oxygen index test and smoke density test. The flame‐retardant mechanisms were studied through the char yield test, SEM, quantitative analysis, thermogravimetry and differential thermal analysis. The thermal degradation in air of flexible PVC treated with the above compounds was studied by thermal analysis from ambient temperature to 800°C. The results showed that tin compounds such as ZHS and ZS could be used as a highly effective flame retardant for flexible PVC, and it appears that the tin compound may exert its action in both the condensed and vapor phases, but mainly in condensed phases as a Lewis acid. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1469–1475, 2005     

A study of the flame‐retardant properties of polypropylene/Al(OH)3/Mg(OH)2 composites

Polymeric materials are used extensively, but their applications are limited because many of them are flammable. Therefore ways to make them flame retardant have received much attention. In this work, polypropylene (PP) was used as the matrix resin, aluminium hydroxide (Al(OH)₃) and magnesium hydroxide (Mg(OH)₂) as flame‐retardant additives and zinc borate (ZB) as a flame‐retardant synergist. PP/Al(OH)₃/Mg(OH)₂ and PP/Al(OH)₃/Mg(OH)₂/ZB flame‐retardant composites were prepared with a twin‐screw extruder. The flame‐retardant properties, i.e. oxygen index (OI), burning velocity and smoke density, of the composites were measured. The results showed that OI increased with an increase of the filler content and decreased with an increase of the filler particle diameter. The burning velocity decreased with an increase of the filler content, while it first increased and then decreased with an increase of the filler particle diameter. The smoke density decreased with an increase of the filler content and increased with an increase of the filler particle diameter. There was a flame‐retardant synergy between Al(OH)₃/Mg(OH)₂ and ZB in the composites, and the smoke suppression effect was marked when ZB was added. Copyright © 2009 Society of Chemical Industry     

Mechanical properties and morphology of PP/ABS blends compatibilized with PP‐g‐2‐HEMA

Polypropylene (PP) and acrylonitrile–butadiene–styrene blends of different composition were prepared using a single‐screw extruder. The binary blend of PP/ABS was observed to be incompatible and shows poor mechanical properties. PP‐g‐2‐hydroxyethyl methacrylate (2‐HEMA) was used as a compatibilizer for the PP/ABS blends. The ternary compatibilized blends of PP/ABS/PP‐g‐2‐HEMA showed improvement in the mechanical properties. Electron micrographs of these blends showed a homogeneous and finer distribution of the dispersed phase. The mechanical performance increased particularly in the PP‐rich blend. The 2.5‐phr (part per hundred of resin) compatibilizer was observed to bring improvement to the properties. The suitability of various existing theoretical models for the predication of the tensile moduli of these blends was examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 72–78, 2003     

Improving the flame‐retardant efficiency of aluminum hydroxide with fullerene for high‐density polyethylene

The influence of fullerene (C₆₀) on the flame retardancy and thermal stability of high‐density polyethylene (HDPE)/aluminum hydroxide (ATH) composites was studied. After the addition of three portions of C₆₀ to an HDPE–ATH (mass ratio = 100:120) composite, a V‐0 rating in the UL‐94 vertical combustion test was achieved, and the limiting oxygen index increased by about 2%. The results of cone testing also showed that the addition of C₆₀ effectively extended the time to ignition and the time to maximum heat‐release rate while cutting down the peak heat‐release rate. Thus, fewer flame retardants were needed to achieve a satisfactory flame retardance. Consequently, the adverse effects on the mechanical properties because of the high level of flame‐retardant loading was reduced, as evidenced by the obvious enhancements in the tensile strength, elongation at break, and flexural strength. Electron spin resonance spectroscopy proved that C₆₀ was an efficient free‐radical scavenger toward HO· radicals. Thermogravimetric analysis coupled to Fourier transform infrared spectroscopy demonstrated that in both N₂ and air atmospheres, C₆₀ increased the onset temperature of the matrix by about 10 °C because of its enormous capacity to absorb free radicals evolved from the degradation of the matrix to form crosslinked network, which was covered by aluminum oxide. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44551.     

Influence of fumed silica on the flame‐retardant properties of ethylene vinyl acetate/aluminum hydroxide composites

The flammability and synergistic flame‐retardant effects of fumed silica (SiO₂) in ethylene vinyl acetate (EVA)/aluminum hydroxide (ATH) blends were studied with limiting oxygen index measurements, UL 94 testing, cone calorimeter testing (CONE), and thermogravimetric analysis (TGA). The results show that the addition of a given amount of fumed SiO₂ can apparently improve UL 94 rating. The CONE data indicated that the addition of fumed SiO₂ greatly reduced the heat release rate. The TGA data showed that this synergistic flame‐retardant mechanism of fumed SiO₂ in the EVA/ATH materials was mainly due to the physical process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of hydrated fillers and red phosphorus on the limiting oxygen index of poly(ethylene‐co‐vinyl actate)‐poly(vinyl butyral) and low density polyethylene‐poly(ethylene‐co‐vinyl alcohol) blends

The limiting oxygen index (LOI) values of EVA‐PVB and low density polyethylene (LDPE)‐poly(ethylene‐co‐vinyl alcohol) (EVOH) polymer blends containing hydrated filler‐type flame retardants and red phosphorus were measured. When used as the sole flame retardant, magnesium hydroxide [Mg(OH)₂] and alumina trihydrate (ATH) performed best in EVA and PVB, respectively. Magnesium hydroxide addition had a limited effect on the LOI of plasticized PVB, and addition of red phosphorus made little difference. This result is attributed to a mismatch between the decomposition temperature of Mg(OH)₂ and the temperature at which the PVB plasticizer vaporizes. Otherwise, low‐level addition of red phosphorus significantly improved LOI values. The presence of hydroxyl groups on the polymer backbone had a beneficial effect with respect to LOI values in ATH‐filled blends. An LOI value of 30 was achieved in EVOH with as little as 32% of ATH and 3% of red phosphorus. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers     

Development of halogen‐free flame‐retardant thermoplastic elastomer polymer blend

Ethylene‐propylene diene rubber (EPDM) and isotactic polypropylene (iPP) blends have widest industrial applications that require a degree of flame retardancy. Halogen‐free intumescent technology based on phosphorous salt is a significantly advanced approach to make the polymer flame‐retardant. Both ammonium polyphosphate and ethylenediamine phosphate are important intumescent compounds. Their combination with carbonific and spumific agents were studied in binary blends of EPDM/PP. The polymer system was vulcanized online during melt mixing. Intumescent flame‐retardant polymer systems exhibit good flame‐retardancy with optimum comparable physiomechanical, electrical, and fluid resistance properties, including lower smoke emission, which is essential to protect people because the visibility remains unaffected in the event of fire. Pronounced charring and intumescent effect appear to enhance the flame‐retardancy of the polymers. Possible expected intumescent mechanism is proposed based on the nonpyrolysis mechanism for the flame‐retarded polymer and the intumescent components. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 407–415, 2004