Low‐melting sulfate glasses as additives to semirigid PVC and their flame retardant and smoke suppressant properties

The role of low‐melting sulfate glasses (LMSG) as additives on the flame retardant and smoke suppressant properties of semirigid poly(vinyl chloride) (PVC), as well as the mechanism for flame retardancy and smoke suppression, were studied through the Limiting Oxygen Index (LOI) test. Smoke Density Rating (SDR) test, DTA‐TG, and SEM. The results show that the LMSG have good smoke suppressant properties. When the PVC compound contains 40 parts of LMSG, the SDR value will be reduced by about 45%. The Cu²⁺, Zn²⁺, Mn²⁺, and Ni²⁺ sulfates, as well as MoO₃, cause PVC to crosslink and form char, and the melt can protect not only the char formed during combustion and thermal degradation, but also undecomposed polymer. That is the main mechanism for flame retardation and smoke suppression when the additives melt. The mechanical properties of the PVC compounds containing different levels of LMSG were also studied.     

Flame‐retardant properties of magnesium hydroxystannate and strontium hydroxystannate coated calcium carbonate on soft poly(vinyl chloride)

The flame‐retardant and smoke‐suppressant properties of soft poly(vinyl chloride) (PVC) treated with zinc hydroxystannate (ZHS), calcium carbonate (CaCO₃), magnesium hydroxystannate [MgSn(OH)₆], strontium hydroxystannate [SrSn(OH)₆], ZHS–MgSn(OH)₆, ZHS–SrSn(OH)₆, MgSn(OH)₆‐coated CaCO₃, SrSn(OH)₆‐coated CaCO₃, ZHS–MgSn(OH)₆‐coated CaCO₃, and ZHS–SrSn(OH)₆‐coated CaCO₃ were studied with the limited oxygen index, char yield, and smoke density rating methods; the mechanical properties were also studied. The results showed that, with the equivalent addition of the corresponding hydroxystannate, the soft PVC treated with hydroxystannate‐coated CaCO₃ had a higher limited oxygen index than the corresponding hydroxystannate, and the soft PVC treated with the agents containing magnesium had a higher limited oxygen index than the soft PVC treated with the agents containing strontium, except for ZHS–MgSn(OH)₆‐coated CaCO₃. The improvement in the char formation of the hydroxystannate‐coated CaCO₃ was better than that of the corresponding hydroxystannate in most cases, and the aforementioned agents reduced the smoke density rating, decreased the tensile strength, and increased the elongation and impact strength basically. Thermal analysis showed that the additives promoted the evolution of hydrogen chloride, early crosslinking, and rapid charring through the strong catalyzing effect of Lewis acids. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Metal hydroxystannates as flame retardants and smoke suppressants for semirigid poly(vinyl chloride)

Metal hydroxystannates were studied as flame retardants and smoke suppressants for semirigid poly(vinyl chloride) (PVC). The flame‐retardant and smoke‐suppression mechanisms were investigated by using limiting oxygen index (LOI), smoke density rating (SDR), the solid yield test (SY), scanning electron microscopy (SEM), thermogravimetry, differential thermogravimetry, and differential thermal analysis. Results showed that semirigid PVC treated with the flame retardants had a higher LOI, and solid yield, but a lower SDR and maximum smoke density, thereby indicating that the flame‐retardance and smoke‐suppression properties of the treated PVC were improved and that the hydroxystannate compounds could be used as highly effective flame retardants. The tin compounds may exert their action in both the condensed and vapor phases, but mainly in the condensed phase as Lewis acids. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers.     

系列羟基锡酸盐对半硬质PVC的阻燃消烟作用

研究了系列羟基锡酸盐阻燃剂对半硬质PVC的阻燃消烟作用。通过对样品燃烧后剩炭含量及扫描电镜(SEM)分析,探讨了锡酸盐体系阻燃抑烟的机理。结果表明:经阻燃处理的样品具有较高的极限氧指数(LOI)和剩炭率,较低的烟密度等级(SDR)和最大烟密度(MSD),与未处理的样品相比具有较好的阻燃和消烟性能。由于阻燃剂的添加量较少,对材料力学性能影响不大。     

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     

SnO2和SiO2用于PVC的阻燃消烟及协同作用

研究了二氧化锡和二氧化硅对软PVC阻燃消烟性的影响。通过对极限氧指数、剩炭率、烟密度的测定和DTATG曲线的分析证明,添加8g二氧化锡/二氧化硅复合阻燃剂的PVC的氧指数和剩炭率比未添加的分别增高5.5个单位和4.1%,烟密度降低16.4%,降解活化能分别降低38kJ/mol和23.1kJ/mol,从而证明二氧化锡/二氧化硅复合阻燃剂对于PVC是一种很好的阻燃消烟剂,二氧化锡和二氧化硅有很好的协同作用。同时证明这种复合阻燃剂能代替三氧化二锑,使产品的成本进一步降低。     

活性炭模板制备铝酸铁及其在软PVC中的阻燃应用

以硫酸铁和硫酸铝为原料,以磷酸处理过的活性炭为模板制备铝酸铁阻燃剂。并通过X射线衍射（XRD）和红外吸收光谱（FT-IR）对合成铝酸铁阻燃剂做了表征。用极限氧指数、烟密度测试其对PVC的阻燃消烟性,当铝酸铁阻燃剂的添加量为5%（质量分数）时,阻燃后软PVC的极限氧指数达到32.8%,烟密度等级为55.45%,拉伸强度为18.36 MPa,断裂伸长率为214%,并通过热重分析对阻燃前后PVC的热降解行为做了研究。结果表明：以活性炭为模板制备的铝酸铁阻燃剂对软质PVC具有较好的阻燃消烟性能。     

ZnO与Mg(OH)2在软PVC中的协同阻燃消烟作用

用热分析的方法研究了ZnO和Mg(OH)2复合阻燃剂对软PVC的协同阻燃消烟作用,考察了经阻燃处理的软PVC从室温到800℃的热降解过程,用Kissinger方程给出了热降解反应的活化能。通过极限氧指数(LOI)、剩炭率、烟密度等级(SDR)和最大烟密度(MSD)的测定以及用电子扫描显微镜(SEM)对燃烧后所生成炭层的观察,探讨了协同体系阻燃抑烟的机理。结果表明:经阻燃处理的样品尤其是加入适量ZnO和Mg(OH)2复合阻燃剂的样品具有较高的极限氧指数(LOI)和剩炭率、较低的烟密度等级(SDR)和最大烟密度(MSD),与未处理的样品相比具有较好的阻燃和消烟性能。ZnO的加入可改变PVC的热降解过程,使起始降解温度降低,并且使反应的活化能增大,可能属于固相Lewis酸催化机理。     

Zn2SnO4的制备及其对软质聚氯乙烯的阻燃研究

以结晶四氯化锡和硝酸锌为原料,通过2步煅烧法制备锡酸锌(Zn2SnO4)阻燃剂;通过极限氧指数、烟密度等级和残炭量研究了Zn2SnO4对软质聚氯乙烯（PVC）的阻燃和消烟性能的影响,同时对力学性能进行了研究。结果表明,Zn2SnO4的用量为15份时,对软质PVC的阻燃消烟效果明显,其极限氧指数可达36.0 %、烟密度等级为86.2 %、残炭率为29.7 %、拉伸强度为25.47 MPa、断裂伸长率为168 %;利用热重分析、差热分析和扫描电子显微镜等方法对阻燃PVC进一步进行表征,结果表明Zn2SnO4的加入促使软质PVC的起始分解温度降低,残炭量增加,燃烧后剩炭结构致密,阻燃效果明显。     

Synergistic flame retardant effects of activated carbon and molybdenum oxide in poly(vinyl chloride)

The synergistic effects of activated carbon (AC) and molybdenum oxide (MoO₃) in improving the flame retardancy of poly(vinyl chloride) (PVC) were investigated. The effects of AC, MoO₃ and their mixture with a mass ratio of 1:1 on the flame retardancy and smoke suppression properties of PVC were studied using the limiting oxygen index and cone calorimeter tests. It was found that the flame retardancy of the relatively cheaper AC was slightly weaker than that of MoO₃. In addition, the incorporation of AC and MoO₃ greatly reduced the total heat release and improved smoke suppressant property of PVC composites. When the total content of AC and MoO₃ was 10 phr, PVC/AC/MoO₃ had the lowest peak heat release rate and peak smoke production rate values of 173.80 kW m^?2 and 0.1472 m² s^?1, which represented reductions of 47.3 and 59.9%, respectively, compared with those of PVC. Furthermore, thermogravimetric analysis and gel content tests were used to analyze the flame retardant mechanism of AC and MoO₃, with results showing that AC could promote early crosslinking in PVC. Char residue left after heating at 500 °C was analyzed using scanning electron microscopy and Raman spectroscopy, and the results showed that MoO₃ produced the most compact char, with the smallest and most organized carbonaceous microstructures. © 2017 Society of Chemical Industry     

羟基锡酸锌包覆纳米氢氧化镁在PVC中的应用

通过均匀沉淀法制备了羟基锡酸锌包覆纳米氢氧化镁并将其应用到聚氯乙烯(PVC)中。利用XRD、TG、DTA对羟基锡酸锌包覆纳米氢氧化镁的性能进行了研究,并通过氧指数、烟密度研究了羟基锡酸锌包覆纳米氢氧化镁对PVC的阻燃和抑烟性能的影响,同时对其力学性能也进行了研究。结果表明:纳米氢氧化镁表面均匀地包覆了羟基锡酸锌;羟基锡酸锌包覆纳米氢氧化镁对PVC的阻燃和抑烟性能明显优于单独添加羟基锡酸锌、纳米氢氧化镁以及羟基锡酸锌包覆微米氢氧化镁和羟基锡酸锌与纳米氢氧化镁混和物时的阻燃、抑烟性能;纳米材料的加入对PVC的力学性能也产生了有利的影响。     

锡酸锌包覆碳酸钙阻燃剂在聚氯乙烯电缆料中的应用

通过氧指数(OI)、烟密度等级(SDR)、热性能和力学性能的测定,研究了锡酸锌包覆碳酸钙阻燃剂对聚氯乙烯(PVC)电缆料性能的影响。利用TG、DTG和DTA等分析方法,探讨了锡酸锌包覆碳酸钙对PVC的阻燃抑烟机理。结果表明:锡酸锌包覆碳酸钙的加入使PVC电缆料的SDR明显下降,而OI仅略有下降,对PVC电缆料的力学性能和热性能影响不大。     

Metal chelates as synergistic flame retardants for flexible PVC

The thermal degradation of flexible PVC treated with various metal chelates containing Cr, Al, Fe, Co, Ni, Cu, or Zn combined with two compounds, Al(OH)₃ and Mg(OH)₂, was studied by thermal analysis. Limiting Oxygen Index (LOI), Smoke Density Rating (SDR), and mechanical properties were investigated. The structure of the char formed after combustion of the PVC compounds was observed through scanning electron microscopy (SEM). The high LOI and char yield of flexible PVC treated with flame retardants showed that there was a good synergistic effect between Al(OH)₃, Mg(OH)₂, and metal chelates. J. VINYL. ADDIT. TECHNOL., 11:70–75, 2005. © 2005 Society of Plastics Engineers.     

锡酸锌包覆碳酸钙对聚氯乙烯的阻燃消烟作用

用氧指数、剩炭率、烟密度等方法测试了锡酸锌包覆碳酸钙对PVC的阻燃作用,同时采用热分析、扫描电镜的方法研究了锡酸锌包覆碳酸钙的阻燃机理。实验表明在锡酸锌含量相同的情况下,锡酸锌包覆碳酸钙对PVC的阻燃和消烟性能优于锡酸锌;在添加量为10份时,锡酸锌包覆碳酸钙阻燃PVC样品和三氧化二锑阻燃PVC样品具有相同的氧指数,但当添加量为20份时,前者的氧指数比后者的高3%,前者的烟密度等级比后者低约10%。     

The Effect of Different Smoke Suppressants with APP for Enhancing the Flame Retardancy and Smoke Suppression on Vinyl Ester Resin

Flame retarded and smoke suppressed vinyl ester resin (VER) were prepared through ammonium polyphosphate (APP) coupled with different smoke suppressants. The flame retardancy of these composites was tested by the limiting oxygen index and UL-94 tests. The typical combustion parameters including heat release rate (HRR), peak of HRR (p-HRR), total heat release, smoke production rate, and total smoke production were detected using a cone calorimeter. The smoke suppressants CaCO₃, ZnMoO₄, Cu₂O, and Fe₂O₃ show different effect on flame retardancy and smoke suppression of VER composites when they are coupled with APP, the synergistic action of APP and CaCO₃ is more effective on decreasing the HRR and smoke release rate than several other smoke suppressants. This is attributed to the fact that CaCO₃ could promote the formation of a dense carbon layer with high thermal stability and anti-oxidation property, which could act as an effective physical barrier. The flame retardant performances and mechanisms of APP and CaCO₃ were evaluated and analyzed at length by thermogravimetric coupled with a Fourier transform infrared spectrometer (FTIR), scanning electron microscopy, FTIR, and X-ray diffraction. POLYM. ENG. SCI., 60: 314–322, 2019. © 2019 Society of Plastics Engineers     

半硬质聚氯乙烯塑料的阻燃性研究

本文研究了用于增塑半硬质聚氯乙烯材料的锑、硼、硅、钼、铝、锌等的化合物的复配阻燃体系。结果表明,该阻燃体系的协同作用是显著的,使用５～１０份复配阻燃剂的增塑半硬质聚氯乙烯材料的氧指数［０Ｉ］可提高８％～１２％,且发烟量较少     

The flammability of expandable polystyrene foams coated with melamine modified urea formaldehyde resin

Urea formaldehyde resin (UF) was modified by introducing melamine during the condensation in order to reduce the amount of free formaldehyde and increase the solid content. The melamine modified UF (MUF) was firstly mixed with intumescent flame retardant (IFR) and then coated on the surface of pre‐expanded polystyrene (PS) particles to prepare flame retardant expandable PS (EPS) foams. The flammability of EPS foam samples was characterized by limiting oxygen index (LOI), UL‐94 vertical burning and cone calorimeter tests, and the results indicated that the peak heat release rate was significantly reduced from 406 to 49 kW/m² and LOI value could reach 36.3 with V‐0 rating in UL‐94 test after coated with IFR. The smoke density test indicated that the maximum smoke density was decreased by the addition of IFR. Thermal analysis suggested that the thermal stability and char formation were significantly improved by the presence of coated flame retardants. The residual char observation revealed that MUF and IFR were beneficial to form integrated char layers with hollow stents, which could be the main reason for the improvement of flame retardant properties. The mechanical properties of flame retardant EPS foams can still meet the standard requirements for industrial applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44423.     

Thermal behavior and flame retardancy of flexible poly(vinyl chloride) treated with zinc hydroxystannate and zinc stannate

The flame‐retardant and smoke‐suppressant properties of inorganic tin compounds such as zinc hydroxystannate (ZHS) and zinc stannate (ZS) were studied in comparison with those of alumina trihydrate and magnesium hydroxide through the limiting oxygen index test and a smoke density test. The thermal degradation in air of flexible poly(vinyl chloride) (PVC) treated with the above compounds was studied by thermal analysis from ambient temperature to 800°C. The activation energy was calculated by using the Vyazovkin model‐free kinetic method and the Kissinger method. The results showed that tin compounds such as ZHS and ZS could be used as highly effective flame retardants for flexible PVC; these flame retardants enhanced the stability and the activation energy of the oxidation of the char. J. VINYL ADDIT. TECHNOL, 2008. © 2008 Society of Plastics Engineers     

金属配合物对软聚氯乙烯的阻燃消烟作用

利用热分析的方法研究了以Al(OH)3和Mg(OH)2为基础，含有Fe、Co、Ni或Cu的金属配合物的复合阻燃剂对软聚氯乙烯(PVC)的阻燃消烟作用。研究了软PVC从室温到1073K的热降解过程。利用Kissinger方程给出了其动力学参数。结果表明：阻燃处理过的软PVC具有较好的阻燃消烟性能，如较高的氧指数和剩炭率，较低的烟密度等级和最大烟密度，力学性能有所降低。     

模板法合成锡酸钴及其对PVC的阻燃应用

以活性炭为模板、五水四氯化锡和六水硝酸钴为原料,制备纯相的多孔锡酸钴（CoSnO3）阻燃剂,通过X射线衍射（XRD）和扫描电镜（SEM）对其结构、形貌进行表征,并将其应用于PVC的阻燃研究中。当CoSnO3的添加量为15份时,其极限氧指数（LOI）达到35.6％、烟密度等级（SDR）为75.2％、断裂伸长率为168.32%、拉伸强度为 22.50 MPa。通过热重分析（TGA）对阻燃前后PVC的热降解行为进行了初步探讨,研究发现： 经CoSnO3阻燃处理后,PVC样品的初始降解温度降低,高温时的剩炭量增加,表明CoSnO3对PVC材料具有较好的阻燃消烟性能。