Effects of zinc borate and microcapsulated red phosphorus on mechanical properties and flame retardancy of polypropylene/magnesium hydroxide composites

In this paper, the mechanical properties and flame retardancy of zinc borate (ZB) and microcapsulated red phosphorus (MRP) with modified magnesium hydroxide (MH) in flame-retardant polypropylene (PP) were studied by mechanical properties test, UL-94 test, and thermogravimetric analysis (TGA). The crystallization behaviors of the composites were investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The addition of ZB could improve tensile strength and elongation at break of PP/MH composite. The MRP powders had a little effect on the mechanical properties of the PP composites. DSC results showed the addition of ZB and MRP weakened the heterogeneous nucleation effect of MH on PP. The addition of ZB and MRP had a great effect on the flammability of the PP/MH/EG composites. The thermal stability of PP/MH/ZB and PP/MH/ZB/MRP composites was better than that of PP/MH composite.     

Flame retardancy and mechanical properties of EVA nanocomposites based on magnesium hydroxide nanoparticles/microcapsulated red phosphorus

The flame retardancy and mechanical properties of ethylene vinyl acetate (EVA) polymer nanocomposite based on magnesium hydroxide (MH) nanoparticles with lamellar‐shape morphological structures and synergistic agent microcapsulated red phosphorus (MRP) have been studied by limiting oxygen index (LOI), cone calorimeter test (CCT), UL‐94 test, tensile strength (TS), and elongation at break (EB). Results showed that LOI values of lamellar‐like nanosized MH (50 × 350 nm²) samples were 1–7 vol. % higher than those of the common micrometer grade MH (1–2 μm) in all additive levels. When 1–3 phr MRP substituted for nanosized MH filler, LOI value increased greatly from original 37 to 55, and met the V‐0 rating in the UL‐94 test. The values of TS for MH nanoparticles composites increased from 10.4 to 17.0 MPa as additive loading levels increased from 80 to 150 phr, respectively, while the corresponding values for common micrometer MH composites decreased steadily from 9.7 to 7.1 MPa. Thermogravimetric analysis (TGA) and dynamic Fourier‐transform infrared spectroscopy (FTIR) results revealed two‐step flame‐retardant mechanism. First, MH particles decompose endothermically with the release of 30.1% hydration water in the 320–370°C temperature range. Second, MRP promote the formation of compact charred layers slowly in the condensed phase in the 450–550°C temperature range. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Study on the flame retardancy of EVM/magnesium hydroxide composites optimized with a flame retardant containing phosphorus and silicon

A novel phosphorus‐silicon‐containing flame retardant, spirocyclic pentaerythritol bisphosphorate disphosphoryl chloride/9, 10‐dihydro‐9‐oxa‐10‐phosphaphanthrene‐10‐oxide/vinyl methyl dimethoxysilane (SPDV), was synthesized successfully and used for optimizing the flame retardancy of ethylene‐vinyl acetate copolymer (EVM) rubber/magnesium hydroxide (MDH) composites. The microstructure of SPDV was characterized and determined by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. Thermogravimetric analysis (TGA) showed that SPDV had good charring effect in air even at high temperature (800°C). The flame retardancy of the optimized EVM/MDH composites by SPDV was investigated by limiting oxygen index (LOI), cone calorimeter, and UL‐94 vertical burning tests. A higher LOI value (29.4%) and better UL‐94 rating (V‐0) can be achieved for the optimized EVM/MDH composite (EVM‐7) than EVM/MDH composite without SPDV (EVM‐3) with the total loading of additives. The HRR decreased and residual mass increased gradually as the loading of SPDV increased for the optimized EVM/MDH composites. There existed distinct synergistic intumescent flame‐retardant effect between SPDV and MDH in EVM matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Deformation mechanism of polypropylene composites filled with magnesium hydroxide

The fracture behavior and deformation mechanism of polypropylene (PP) composites filled with magnesium hydroxide [Mg(OH)₂] were investigated. The incorporation of Mg(OH)₂ particles into the PP matrix led to an increase in Young's modulus and a significant reduction in the tensile yield strength and elongation at break. Surface modification on filler particles with stearic acid could reduce the interfacial adhesion between the filler and PP matrix and improve the stress transferability. The deformation mechanism of the Mg(OH)₂/PP composites depended on the interfacial adhesion and the deformability of ligaments between microvoids caused by debonding. The deformability of the ligaments could be significantly improved by surface modification on the particle surface. The dependence of the deformation behavior of the Mg(OH)₂/PP composites on the filler content was in accordance with percolation theory. The agglomeration of microvoids and fibrillation of ligaments in the PP composites with excessive filler content indicated the weak resistance of the polymer matrix to crack propagation and premature fracture in a brittle manner. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1922–1930, 2005     

Investigation of the synergistic effect of red phosphorus and magnesium hydroxide on the thermal degradation behavior and flame resistance of the intumescent fire-retardant polypropylene system

High fire-resistance polypropylene (PP) composites were prepared by using environment-friendly flame retardants including expandable graphite (EG), red phosphorus (RP), and magnesium hydroxide (MH). Synergism between EG, RP, and MH on the thermo-oxidation behavior and flame resistance of PP was found. The incorporation of MH and RP formed highly thermally stable mixtures of magnesium phosphates consisting of Mg₃(PO₄)₂, Mg(PO₃)₂, and α-Mg₂P₂O₇ at both amorphous and crystalline phases in the burning process. The mixture not only covered the surface of burning materials but also could reinforce the char structure of the PP/EG composites, thereby significantly enhancing the condensed phase flame retardant mechanism of the composites. Mass ratios of the flame retardants were also optimized to obtain the composite with the highest flame retardant efficiency. The result revealed that the combination of EG, RP, and MH in PP at MH/RP mass ratio of 3/2 with only a total additive content of 18 wt.% could make its limiting oxygen index (LOI) increase from 16.8% to 27.2% and the UL-94 rating was improved from none to V-0. In addition, the mechanical properties of the composites were improved via the surface treatment of MH and RP with calcium stearate and silicone oil, respectively.     

Enhanced flame retardancy,smoke suppression,and acid resistance of polypropylene/magnesium hydroxide composite by expandable graphite and microencapsulated red phosphorus

Low flame retardant efficiency and poor acid resistance of filled polymer composites are two main drawbacks of magnesium hydroxide (MH) as a flame retardant (FR). To solve these problems, expandable graphite (EG) and microencapsulated red phosphorus (MRP) were introduced into polypropylene/magnesium hydroxide (PP/MH) composite by melt compounding. The obtained PP/MH/EG/MRP quadruple composite was studied regarding its fire behavior as well as acid resistance. Obvious flame retardant synergism among MH, EG, and MRP is found in PP, which diminishes the loading of FR from 63.0 to 37.5 wt% to obtain V-0 rating in UL-94 test and low smoke release. Compact intumescent char with high thermo-oxidative stability was generated on composite surface, which plays a vital role in flame retardancy. The removal of MH by acid erosion on PP/MH/EG/MRP composite surface does not affect production of intumescent char and fire behavior of this composite. The composite displays good fire retardancy, smoke inhibition, and acid resistivity concurrently. This article renders an easy and cheap route to overcome the main faults of MH.     

Structure and properties of polypropylene composites filled with magnesium hydroxide

Silane and silicone oil modified superfine magnesium hydroxide (MH) was filled into polypropylene (PP) as a flame retardant. The PP and flame‐retarded PP composites were studied for their mechanical properties and rheological behaviors by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), limiting oxygen index (LOI), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The results showed that the addition of MH improved flame retardancy of PP/MH composites, but seriously deteriorated mechanical properties of the composites. Surface treatment of MH could significantly improve tensile and impact strength of PP/MH composite because of its enhanced interfacial adhesion between MH and PP matrix. DSC results showed that MH had heterogeneous nucleation effect on PP. Surface treatment of MH weakened its heterogeneous nucleation effect. POM results showed that the dispersion of MH particles played an important role in the crystalline morphology and spherulite size of PP crystals. TGA indicated that MH greatly enhanced the thermal stability of PP. The introduction of treatment agent further improved the thermal oxidative stability of the composite. According to LOI, silane‐treated MH greatly enhanced flame retardancy of PP/MH composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4943–4951, 2006     

Crystallization and melt behavior of magnesium hydroxide/polypropylene composites modified by functionalized polypropylene

The crystallization and melting behavior of Mg(OH)₂/polypropylene (PP) composites modified by the addition of functionalized polypropylene (FPP) or acrylic acid (AA) and the formation of in situ FPP were investigated by DSC. The results indicated that addition of FPP increased crystallization temperatures of PP attributed to the nucleation effect of FPP. The formation of in situ FPP resulted in a reduced crystallization rate, melting point, and degree of crystallization because of the decreased regularity of the PP chain. For the Mg(OH)₂/PP composites, addition of Mg(OH)₂ increased the crystallization temperatures of PP attributed to a heterogeneous nucleation effect of Mg(OH)₂. Addition of FPP into Mg(OH)₂/PP composites further enhanced the crystallization temperatures of PP. It is suggested that there is an activation of FPP to the heterogeneous nucleation effect of Mg(OH)₂ surface. The addition of AA also increased the crystallization temperatures of PP in Mg(OH)₂/PP composites, but crystallization temperatures of PP were not influenced by the AA content, a phenomenon explained by the heterogeneous nucleation effect of the Mg(OH)₂ surface activated by FPP and AA. A synergistic effect on crystallization of PP in Mg(OH)₂/PP composites further increased the crystallization temperatures of PP. However, the crystallization temperatures of Mg(OH)₂/PP composites modified by in situ FPP were lower than those of Mg(OH)₂/PP composites modified by the addition of FPP or AA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3899–3908, 2004     

Flame‐retarded polyethylene terephthalate with carbon microspheres/magnesium hydroxide compound flame retardant

A novel compound flame retardant (carbon microspheres/magnesium hydroxide, abbreviated as CMSs/MH) was used to improve the fire performance of polyethylene terephthalate (PET). LOI, UL94, and Cone test results showed that CMSs/MH/PET composites obtained the best fire performance at the mass ratio of CMSs to MH, which was 5:5, where the CMSs/MH content was 1.0 wt. % of PET. The Py‐CS‐MS, TGA‐DSC results, and morphology of char residue revealed the flame‐retardant mechanism. CMSs/MH increased the thermal stability of PET by increasing the activation energy at the initial combustion stage. At the second stage of combustion, CMSs/MH increased the chance of recombination of free radicals and slowed the combustion. Additionally, CMSs/MH promoted the cross‐linking of pyrolysis products and further improved the continuity of the char layer. Thus, a dense and continuous char layer of CMSs/MH/PET composites was produced; this char layer reduced the heat release rate and increased the amount of char residue.     

Tensile properties and stress whitening of polypropylene/polyolefin elastomer/magnesium hydroxide flame retardant composites for cable insulating application

Flame retardant polypropylene (PP) composites were prepared by combining random polypropylene with uncoated and surface‐treated forms of magnesium hydroxide filler and elastomeric modifiers, with and without maleic anhydride functionalization. Four types of magnesium hydroxide (MDH) with different surface treatments were compounded at amounts up to 60% by weight to PP/polyolefin elastomer (POE) matrix resin to obtain a series of composites. The tensile strength and elongation at break were measured. MDH coated with polymeric material was found to give a high elongation at break value compared with the values obtained with uncoated and vinyl silane and amino silane coated MDH. Two types of POE, i.e., neat and maleic anhydride grafted POE (POEgMA), were used to investigate the stress whitening of composites in bending deformation. POEgMA used composites showed no stress whitening while neat POE used composites showed whitening when bended. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2311–2318, 2005     

MQ硅树脂微胶囊红磷阻燃剂的制备工艺研究

采用原位聚合法制备了MQ硅树脂微胶囊红磷阻燃剂,并用差示扫描量热仪(DSC)对产品的热分解温度进行表征。探讨了相关工艺条件对产品热分解温度的影响,所得优惠工艺条件:M/Q值为0.6,水用量为8倍的六甲基二硅氧烷(MM)和正硅酸乙酯(TEOS)物质的量之和,无水乙醇与六甲基二硅氧烷的质量比为0.9,盐酸用量占总物料质量的1%,反应温度为65℃,反应时间为4.0 h。在优惠工艺条件下所得产品的热分解温度为257.6℃。     

磷系阻燃剂/硼酸锌复合阻燃PET的制备及性能研究

在聚对苯二甲酸乙二醇酯(PET)的酯化过程中添加含磷共聚型阻燃剂2-羧乙基苯基次膦酸(CEPPA)(其中磷质量分数相对PET为0.6%)和硼酸锌(ZB)(相对PET质量分数为0.05%~0.2%)分别作为主阻燃剂和助阻燃剂制备复合阻燃PET,研究了阻燃PET的热性能、燃烧性能和燃烧前后的成炭形貌。结果表明:与纯PET比较,单独添加质量分数为0.05%~0.2%的ZB时制备的阻燃PET,其热性能变化不明显,极限氧指数(LOI)提高到27%,残炭量提高,抑烟效果比较明显,抗熔滴性能得到改善;在PET中共同添加ZB和CEPPA所制得的复合阻燃PET的热降解残炭率最高为14.4%,LOI进一步提高到29%,燃烧残炭表面致密,综合阻燃性能更好。     

Extrudate swell behavior of polypropylene composites filled with microencapsulated red phosphorus

The microencapsulated red phosphorus (MRP) filled polypropylene (PP) composites were prepared using a twin‐screw extruder. The effects of load and temperature on the extrudate swell behavior of the PP/MRP composite melts were investigated by means of a melt flow indexer. The test temperatures and loads were varied from 180 to 205°C and from 2.16 to 12.5 kg, respectively. The results showed that the die‐swell ratio (B) of the composite melts increased roughly linearly with increasing load while decreased slightly with a rise of test temperature. The sensitivity of the die‐swell ratio of the composite melts to load was significant. When the test temperature or load was constant, the values of the B of the composite melts decreased slightly with increasing MRP weight fraction. The findings can provide useful information for processing of these composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

脲醛树脂微胶囊包覆红磷阻燃剂制备工艺的研究——Ⅱ．包覆工艺研究

研究了脲醛树脂的预聚物通过原位聚合对红磷进行包覆的一些影响因素。实验表明,影响包覆条件的主要因素是预聚物与水的质量比、包覆温度、pH值和包覆时间。通过正交实验得到了进行微胶囊包覆的最佳条件为：红磷与水的质量比为1∶30,反应温度为75℃,pH值为3．5,反应时间为2h。颜色为白色,吸湿量为4．01％,用微胶囊红磷去阻燃聚氯乙烯,当含量为9．0％时,在500℃下残余物为14．45％。     

氢氧化镁阻燃剂的表面改性及其在聚丙烯中的应用

采用不同改性剂对氢氧化镁进行表面改性处理，通过实验发现采用4％的硬脂酸钠处理后的氢氧化镁阻燃剂在聚丙烯体系中分散均匀，当氢氧化镁在聚丙烯体系中的添加量达65％时，达到了理想的阻燃效果。     

Investigation of the influence of red phosphorus,expansible graphite and zinc borate on flame retardancy and wear performance of glass fiber reinforced PA6 composites

The flame retarded materials were prepared which used wear‐resistant PA6 composite (PA6/GF/PTFE/UHMWPE/CG, 85/15/5/5/5 by weight) as matrix, red phosphorus (RP), expansible graphite (EG), and zinc borate (ZB) as fire retardant. The flame retarded properties were characterized by LOI and UL‐94 testing. PA6 composite with 15 wt% RP reached V0 rating and had a high LOI value (27.3 vol%). When a combination of 7 wt% ZB and 8 wt% RP was added, increases in LOI (27.9 vol%) and UL‐94 rating(V0) were both observed. Thermogravimetric analysis (TGA) and char residue characterization showed that the combination of RP and ZB can promote the formation of char barrier, reduce the mass loss rate, and thus improve the flame retardancy of PA6 composites. The wear test showed that, the composite filled by 15 wt% RP or a combination of 7 wt% ZB and 8 wt% RP both possessed a low wear rate and a much stable friction coefficient. The presence of EG could also improve the flame retardance but was harmful to the mechanical property as well as wear performance. The results indicated that ZB and RP had synergy effect on improving both flame retardance and wear performance of PA6 composites. POLYM. COMPOS., 38:2090–2097, 2017. © 2015 Society of Plastics Engineers     

Thermal degradation of flame‐retarded polyethylene/magnesium hydroxide/poly(ethylene‐co‐propylene) elastomer composites

Magnesium hydroxide‐based halogen‐free flame retarded linear low‐density polyethylene (LLDPE) composites containing poly(ethylene‐co‐propylene) (EP) elastomer were prepared by a melt process and subsequently vulcanized thermally. The thermal degradation of the composites was studied using thermogravimetric (TG) analysis and real‐time Fourier transform infrared (RT‐FTIR) spectroscopy. The combustion residues from the composites were characterized by Raman spectroscopy and X‐ray photoelectron spectroscopy (XPS). The results from TG and RT‐FTIR tests show that the incorporation of a suitable amount of the elastomer into polyethylene/magnesium hydroxide composites after vulcanization increases the thermal stability. A graphite‐like char was found for the composites with EP elastomer, from Raman spectroscopy studies. XPS results indicate that there are several forms of carbon present in the combustion residues of the composites with EP elastomer, compared with only one form of carbon in the residues of the composites without the elastomer. Copyright © 2003 Society of Chemical Industry     

氢氧化铝和硼酸锌对乙烯-乙酸乙烯酯橡胶/丁腈橡胶共混胶阻燃性能的影响

以氢氧化镁(MDH)作乙烯-乙酸乙烯酯橡胶(EVM)/丁腈橡胶(NBR)共混胶的阻燃剂,运用极限氧指数(LOI)法和锥形量热仪,研究了分别并用少量氢氧化铝(ATH)和硼酸锌对共混胶阻燃性能的影响。结果表明,当添加相同份数的阻燃剂时,MDH与ATH并用和单独使用MDH相比,共混胶的LOI相差不大,但并用少量ATH可以明显延长点燃时间,降低总释放热。添加硼酸锌后,EVM/NBR/MDH体系的阻燃性能提高,添加20份以上硼酸锌,共混胶的点燃时间明显延长,热释放速率峰值明显下降;添加140份MDH时并用20份硼酸锌,共混胶的火灾性能指数最高,阻燃效果最好。     

One-step synthesis of hydrophobic magnesium hydroxide nanoparticles and their application in flame-retardant polypropylene composites

Hydrophobic magnesium hydroxide (MH) nanoparticles were prepared by a one-step synthesis method in a high-gravity environment generated by a novel impinging stream-rotating packed bed (IS-RPB) reactor. The reactant solutions were simultaneously and continuously pumped into the IS-RPB reactor, and then Tween 80 was added as a surface modifier. The morphology, structure, and properties of blank and hydrophobic MH were characterized. The effects of MH nanoparticles on the flame retardancy, thermal stability, and mechanical properties of PP/MH composites were also studied. We found that the obtained MH nanoparticles exhibited hexagonal lamella with a mean size of 30 nm, excellent hydrophobic properties (e.g., high water contact angle of 112°), and improved thermal stability of MH. The limiting oxygen index (LOI) further showed that increased MH loading can significantly improve flame-retardant performance, which reached 29.3% for PP/MH composites with 30 wt% hydrophobic samples. The thermal stability and mechanical properties of the PP/MH composites with hydrophobic samples were also much higher than those of PP/MH composites with blank MH. Results showed that the one-step synthesis had high potential application in the large-scale production of hydrophobic MH nanoparticles.     

Synergistic effects of expandable graphite with magnesium hydroxide on the flame retardancy and thermal properties of polypropylene

In this study, the flammability characterization and synergistic effects of different particle size of expandable graphite (EG) with modified magnesium hydroxide (MH) in flame‐retardant polypropylene (PP) composites were studied by limiting oxygen index (LOI), UL‐94 test, thermogravimetric analysis (TGA), and fourier transform infrared (FTIR) spectroscopy. The results showed that the particle size of EG had a great effect on the flammability of the PP/MH/EG composites. The EG2 with smaller particle size could apparently increase the LOI value and improved the UL‐94 flammability properties rating of the PP composites. The data obtained from the TGA and FTIR curves indicated that the thermo‐oxidative stability of PP/MH/EG composites increased with decreasing particle size of EG. And the smaller the particle size of EG, the higher the residues of the composite. POLYM. ENG. SCI., 47:1756–1760, 2007. © 2007 Society of Plastics Engineers