碳酸钙/甲基乙基硅橡胶对EBA的阻燃及热降解行为

将碳酸钙(CaCO3)和甲基乙烯基硅橡胶(VMQ)一起添加到乙烯-丙烯酸丁酯共聚物(EBA)中制备了阻燃EBA材料,通过极限氧指数法(LOI)研究了材料的阻燃性能,通过拉伸测试研究了材料的力学性能,用热重分析技术(TGA)研究了阻燃材料的热降解行为,同时还研究了CaCO3与VMQ的不同配比与材料的阻燃性能之间的关系。测试结果表明:当CaCO3/VMQ体系的质量分数为35%时,EBA的氧指数从19.2%提高到了30%以上,说明该体系对EBA具有很好的阻燃性能。当CaCO3与VMQ的质量比为3:1时材料具有最高的LOI值,为33.9%,表现了很好的协同阻燃作用。随着阻燃剂的加入,材料的拉伸强度有所下降,当阻燃剂的质量分数固定为35%,随着VMQ含量的增加,材料的拉伸强度逐渐降低。CaCO3/VMQ体系的加入提高了材料的起始热分解温度和材料的成炭性能,在600℃时的残炭量为31.85%,抑制了材料的进一步降解,从而提高了材料的阻燃性能。     

可膨胀石墨-硼酸锌/硬质聚氨酯泡沫的性能研究

采用氧指数测定(LOI)、动态热机械分析(DMA)与热重分析(TG)等研究硼酸锌(ZB)和可膨胀石墨(PEG)复配对硬质聚氨酯泡沫阻燃性能和力学性能的影响。采用扫描电镜(SEM)观察样品的形态、pEG和ZB粒子在硬质聚氨酯泡沫中的分布情况。结果表明:硼酸锌和可膨胀石墨复配阻燃硬质聚氨酯泡沫具有一定的协同增效作用,同时可改善复合材料的压缩强度和压缩模量及储能模量。     

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。     

CaCO_3和EG与APP/PER/ZB体系协同阻燃交联EVAC基复合材料的研究

采用膨胀型阻燃剂[聚磷酸铵/季戊四醇/硼酸锌(APP/PER/ZB)体系]对交联乙烯–乙酸乙烯酯塑料(EVAC)进行阻燃改性,然后分别用CaCO3和可膨胀石墨(EG)进一步优化EVAC/APP/PER/ZB复合材料。采用极限氧指数(LOI)仪、锥形量热仪和扫描电子显微镜(SEM)研究了复合材料的阻燃性能及阻燃机理,并测试了复合材料的力学性能和介电性能。结果表明,随着APP/PER/ZB体系含量的增加,复合材料的LOI逐渐升高,热释放速率峰值、平均热释放速率、热释放总量逐渐降低;拉伸强度、断裂伸长率和介电常数逐渐下降,但介电损耗变化极小。CaCO3和EG优化的复合材料阻燃性能和拉伸性能均比未优化的有所提高,起到一定的协同阻燃效果,其中EG的优化效果最好;CaCO3对复合材料介电性能的影响与APP/PER/ZB体系大致相同,但高频下EG的影响较为显著,均明显降低了复合材料的介电常数和介电损耗峰值。     

APP/ADP体系阻燃木塑复合材料研究

选用聚磷酸铵(APP)与二乙基次膦酸铝(ADP)复配用于木塑复合材料(WPC)的阻燃并研究了材料的阻燃性能。结果表明,纯WPC的氧指数(LOI)值为23.5%,当单独添加19%(wt)的APP时,材料通过了垂直燃烧测试UL-94 V-0级,LOI值为28.9%。当APP与ADP以质量比为6∶1复配,阻燃剂总添加量仅为15%(wt)时,材料通过了UL-94 V-0级,LOI值达到了28.7%,表明ADP/APP体系对WPC具有很好的协同阻燃效应。力学性能测试表明,APP/ADP体系的加入对材料的力学性能影响较小。热重分析测试表明,APP/ADP体系促进了材料的初期热降解,但提高了材料的成炭性能。锥形量热测试及扫描电镜对残炭的测试表明,APP/ADP体系的加入使得材料在燃烧过程中形成了膨胀、连续的炭层,很好地抑制了材料的燃烧,使得材料的热释放速率、总热释放量显著降低。     

多聚芳基磷酸酯与乙烯基硅树脂复合改性聚乳酸研究

将多聚芳基磷酸酯(PX-220)和微米级乙烯基硅树脂微球(VSR)加入到聚乳酸(PLA)中,通过红外测式、扫描电镜、氧指数、垂直燃烧测试、热重分析和力学性能测试等研究方法研究了PX-220与VSR对PLA阻燃性能、热稳定性及力学性能的影响。结果表明,只添加15%PX-220能使材料的极限氧指数(LOI)提高至33%,但力学性能下降明显;当9%PX-220与6%VSR并用时,材料的(LOI)为30.5%,初始分解温度提高了10℃,且拉伸强度达到最大值,材料的综合性能达到最佳。     

氢氧化铝对乙烯-丙烯酸丁酯共聚物力学与阻燃性能及热降解行为的影响

采用极限氧指数、热重分析（TG）和差示扫描景热分析（DSC）等技术和手段研究了乙烯-丙烯酸丁酯共聚物（EBA）／氢氧化铝（ATH）复合材料的阻燃性能和热降解行为，探讨了ATH的添加量对EBA力学性能和熔体流动速率的影响。实验数据表明，ATH的引入能恶化材料的力学性能和加工性能；但可提高材料的阻燃性能，当ATH的添加量为60％时，阻燃材料的极限氧指数可达33．1％。ATH提高了EBA在高温下的热稳定性，降低了EBA的热降解速率，扩大了热失熏温度范围。ATH以吸热方式在凝缩相和气相中发挥阻燃作用；此外，ATH分解形成的活性Al2O3对EBA还具有成炭催化作用，在一定程度上显示出了ATH的凝缩相阻燃作用。     

碳酸钙对乙烯-丙烯酸丁酯共聚物阻燃与力学性能及热降解行为影响研究

采用极限氧指数法、热重分析和差示扫描量热分析等研究了碳酸钙（CaCO3）对乙烯-丙烯酸丁酯共聚物（EBA）阻燃及热降解行为的影响，探讨了CaCO3对EBA力学性能和熔体流动速率的影响。结果表明，CaCO3降低了EBA的拉伸强度、断裂伸长率和熔体流动速率，但复合阻燃材料仍具有良好的加工性能；当CaoCO3含量为60％（质量分数，下同）时，阻燃材料的极限氧指数可达28．5％。CaCO3通过EBA在热降解过程中与之发生化学反应来改变EBA的热降解行为，提高在高温下的热稳定性，降低EBA的热降解速率，促进高温下成炭在凝缩相中发挥阻燃作用。此外，CaCO3与EBA在热降解过程中形成隔热、隔氧的多孔泡沫膨胀结构，可进一步加强阻燃效果。     

硼酸锌对氮磷协效阻燃玻纤增强尼龙66性能的影响

为提高三聚氰胺聚磷酸盐(MPP)和二乙基次膦酸盐(OP)协效阻燃玻纤(GF)增强尼龙66(PA66)的综合性能,引入少量的无机阻燃剂硼酸锌(ZB)作为协效剂,系统研究了不同添加量的ZB对阻燃材料的阻燃性能、热稳定性、力学性能和白度的影响。结果表明,当MPP和OP的总添加量为15%,复配0.5%的ZB时,阻燃GF增强PA66的垂直燃烧阻燃等级达到UL94 V–0级,且热释放总量由MPP/OP体系的15.4 k J/g降为13.7 k J/g;ZB的引入促进了连续、致密炭层的形成,增强了凝聚相阻燃;ZB增强了阻燃材料的热稳定性,ZB复配量为1.0%的阻燃材料的初始降解温度提高到了301℃,有效避免了加工过程中的降解;当ZB添加量为1.0%时,阻燃材料的拉伸强度和缺口冲击强度分别为100.9 MPa和4.22 k J/m~2,均优于未添加阻燃剂的纯GF增强PA66;同时,样品的白度得到了明显提升,有利于阻燃GF增强PA66的工业化应用。     

新型磷系阻燃剂四苯基(双酚-A)二磷酸酯阻燃PC/ABS的研究

利用自制的四苯基(双酚-A)二磷酸酯(BDP)及其复配体系制备了阻燃PC/ABS,研究了阻燃PC/ABS的力学性能、氧指数(LOI)和垂直燃烧测试性能(UL94)、材料的阻燃性能和烟气释放。结果表明:采用15%的BDP阻燃PC/ABS,材料的冲击强度下降了12.82%,LOI达到30.0%,UL94阻燃性能达到V—0级,平均热释放速率(av-HRR)和最大热释放速率(pk-HRR)分别下降了35.84%和31.17%,点燃时间(TTI)延长18s,火势增长指数(FGI)下降了46.72%,比消光面积(SEA)上升了6.68%;采用BDP/APP复配阻燃PC/ABS,材料的冲击强度最大降幅为33.33%,LOI最大可达30.1%,UL94阻燃性能由V—0级降为V—1级,av-HRR和pk-HRR最大分别下降40.89%和31.2%,TTI最大延长20s,FGI最大降幅为50.37%,SEA最大涨幅为11.14%;采用BDP/纳米SiO2复配阻燃PC/ABS,当纳米SiO2的添加量为7%时,材料的冲击强度上升了5.13%,LOI达到31.1%,UL94阻燃性能达到V—0级,av-HRR和pk-HRR分别下降了43.18%和4069%,TTI延长20s,FGI降幅为59.12%,平均比消光面积(av-SEA)涨幅为8.09%,6min内av-SEA下降6.92%,(6min总发烟指数)TSPI6min下降5.54%,阻燃、抑烟效果最佳,对PC/ABS材料的力学性能影响最小。     

硼酸锌在膨胀型无卤阻燃ABS中的协同作用

采用熔融共混法制备了丙烯腈-丁二烯-苯乙烯共聚物(ABS)/膨胀型阻燃剂(IFR)/硼酸锌(ZB)无卤阻燃复合材料。利用热重分析仪、氧指数测定仪、扫描电子显微镜等研究了ZB对复合材料热失重行为、阻燃性能、微观结构及力学、加工性能的影响。较低含量的ZB与IFR存在较好的阻燃协同作用,且ZB可促进IFR成炭,使ABS/IFR复合材料的氧指数及其残炭量分别由未加ZB时的27.4%、21.29%提高到30.1%和23.05%。ZB的加入能够提高ABS/IFR复合材料的弯曲性能和加工性能,但对复合材料的冲击、拉伸性能产生了不利影响。     

聚氯乙烯(PVC)电缆料阻燃性能的研究

研究了纳米三氧化二锑、普通微米级三氧化二锑及纳米三氧化二锑/硼酸锌复配阻燃剂对PVC电缆料的阻燃性能及力学性能的影响。研究结果表明:纳米三氧化二锑对PVC氧指数的贡献大于微米级三氧化二锑,当氧指数为35%时,纳米三氧化二锑的添加量比微米级三氧化二锑减少20%;将纳米三氧化二锑与硼酸锌复合后材料的氧指数降低,但生烟量与成本降低;随着复配阻燃剂中硼酸锌比例的增加,PVC电缆料的拉伸强度与断裂伸长率的降低均不明显。     

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     

协效剂在ABS/APP/PETA体系中的阻燃协效性

为了提高苯乙烯一丁二烯一丙烯睛(ABS）/聚磷酸铵(APP)/聚对苯二甲酞乙二胺(PETA)膨胀阻燃体系的阻燃性能,将硼酸锌(ZB）、红磷(RP）添加到ABS/ APP/ PETA膨胀阻燃体系中。采用极限氧指数法、垂直燃烧法、热失重、扫描电镜探讨了不同含量协效剂ZB,RP对不同比例ABS/APP/PETA阻燃体系的协效阻燃效应。结果表明,加人协效剂使ABS/APP/PETA体系的阻燃性能得到显著提高;将2.5份(质量份,下同)ZB和4份RP加人到ABS/APP/PETA( 70/22. 5/7. 5)体系,体系的极限氧指数由未加协效剂的30%提高到41%,UL-94测试也达到V-0级;ZB提高了ABS/APP/PETA体系热稳定性和成炭率,RP能极大地促进成炭;加人ZB和RP ,阻燃体系燃烧表面能够形成更多膨胀、致密的炭层。     

Flame resistant properties of LDPE/PLA blends containing halogen-free flame retardant

In this study, mixing petroleum-based low-density polyethylene (LDPE) with biodegradable poly(lactic acid) (PLA) is used as polymer matrix. Boron compounds, metal hydroxides, melamine (MLM), ammonium polyphosphate (APP), and pentaerythritol (PER) were used as reinforcement materials to improve flame resistance of polymer matrix. The composite materials were characterized by Fourier transform infrared spectroscopy, limiting oxygen index (LOI), thermogravimetric analysis, mechanical test, and scanning electron microscopy analyses. The LOI analysis showed that for samples, which included MLM, APP, and PER, the LOI values were dramatically improved. Especially, the LOI value of sample Q (LDPE80/PLA20/APP30/PER15/MLM15/ZB3) was enhanced about 95.17% compared to polymer mixing. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48960.     

Flammability,thermal stability,and mechanical properties of ethylene-propylene-diene monomer/polypropylene composites filled with intumescent flame retardant and inorganic synergists

Three kinds of inorganic particles, zinc borate (ZB), organic montmorillonite (OMMT), and expanded graphite (EG) as synergistic flame retardants, are incorporated into ethylene-propylene-diene monomer/polypropylene (EPDM/PP) composites filled with intumescent flame retardants (IFR). The effect of three synergistic flame retardants on the combustion, thermal stability, and mechanical properties of the EPDM/PP/IFR composites are investigated by limiting oxygen index (LOI), UL-94 test, cone calorimeter test (CCT), thermogravimetric analysis (TGA), scanning electron microscopy, mechanical property testing, and dynamic mechanical analysis (DMA). The results from LOI, UL-94, and CCT show that the synergistic effect of IFR with ZB and EG is better than IFR with OMMT in the flame retardant EPDM/PP/IFR composites. The TGA results indicate that the thermal stability and char residues of the composites is improved with the addition of inorganic particles, which is attributed to the formation of dense char layers to isolate heat flow. DMA results including storage modulus (G'), loss modulus (G"), and loss factor (tan δ) suggest that the composites with inorganic particles exhibit more rubber-filler interaction, which limits the movement of the rubber chains.     

无机阻燃剂对PVC/木粉复合材料性能的影响

分别采用A1(OH)3、ZB以及Sb2O3等无机阻燃剂对PVC/木粉复合材料改性,研究不同的阻燃剂配方及阻燃剂含量对PVC/木粉复合材料阻燃性能和力学性能的影响。结果表明:随着A1(OH)3,ZB以及Sb2O3添加量的增加,PVC/木粉复合材料的氧指数(LOI)呈逐渐增大的趋势。Sb2O3阻燃效率最高,当添加量为9份时,氧指数达到35.2%;无机阻燃剂的加入普遍降低了PVC/木粉复合材料的冲击韧性,但对拉伸强度起到了一定的增强作用。     

PE基木塑复合材料的阻燃研究

采用无卤阻燃剂聚磷酸铵(APP)以及阻燃协效剂硼酸锌(ZB)、硅藻土,制备具有良好阻燃性能的木塑复合材料。结果表明:APP在改善木塑复合材料阻燃性能的同时,可提高材料的热稳定性,当其用量为20份时,复合材料垂直燃烧达到UL94V-0级,此时,体系的力学性能变化不大;ZB、硅藻土对木塑复合材料的协效阻燃规律不同于对塑料的阻燃规律,添加2份硅藻土的阻燃体系形成的炭层最致密,可有效地隔热隔氧。     

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     

Mechanochemical improvement of the flame‐retardant and mechanical properties of zinc borate and zinc borate–aluminum trihydrate‐filled poly(vinyl chloride)

In this study, the effect of the high‐energy mechanical milling of a mixture of poly(vinyl chloride) (PVC) with zinc borate (ZB) or ZB–aluminum trihydrate (ATH), a mixture of ZB and ATH, on the flame‐retardant and mechanical properties of ZB and ZB–ATH filled PVC was examined. The high‐energy mechanical milling of PVC/ZB and the PVC/ZB–ATH mixture produced chemical bonding between PVC and ZB or ZB–ATH, increasing the interfacial interaction of PVC/ZB and PVC/ZB–ATH blends, which resulted in a great increase in the limiting oxygen index, the impact and yield strengths, and the elongation at break of PVC/ZB and PVC/ZB–ATH blends. The results from ultraviolet spectroscopy and gas chromatography–mass spectroscopy show that mechanochemical modification of ZB and ZB–ATH much more effectively suppressed the release of aromatic compounds in PVC/ZB and PVC/ZB–ATH blends during burning. Mechanochemical modification provided an excellent route for the improvement of the flame‐retardant and mechanical properties of flame‐retardant‐additive‐filled PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 753–762, 2003