A novel method to prepare zinc hydroxystannate-coated inorganic fillers and its effect on the fire properties of PVC cable materials

Fire-retardant (FR) properties, including limiting oxygen index, peak rate of heat release, and smoke parameter have been measured and compared for unfilled and filled polyvinyl-chloride (PVC)-based cable formulations, containing 15 wt% amounts of uncoated and zinc-hydroxystannate (ZHS)-coated magnesium hydroxide (MH) and calcium carbonate (CaCO₃) fillers at the same addition level. Of the uncoated fillers, MH was more effective at lowering flammability than CaCO₃. When the ZHS coating was applied to MH and CaCO₃, CaCO₃ became the most effective additive at lowering PVC flammability and smoke output. POLYM. ENG. SCI., 47:1163–1169, 2007. © 2007 Society of Plastics Engineers     

羟基锡酸锌的制备及其对PVC电缆材料的阻燃消烟作用

研究了在Sn4+和Zn2+共存的水溶液中,以氢氧化钠为沉淀剂合成的纳米羟基锡酸锌（ZHS）。采用X射线粉末衍射、傅里叶红外和环境扫描电镜表征证明合成的ZHS是边长为380nm左右的纳米立方体。采用"熔融共混法"制备PVC电缆材料,通过极限氧指数、烟密度、环境扫描电镜炭渣形貌表征比较了ZHS与三氧化二锑（AO）对PVC的阻燃消烟作用。通过真空裂解气相色谱－质谱联用分析了阻燃PVC电缆材料的裂解产物,并结合燃烧性能的测试结果,推断了ZHS对PVC电缆材料阻燃消烟作用的机理。结果表明,用量相同时,ZHS对PVC电缆材料的成炭作用总是优于AO。添加量小于10份时,AO对LOI和SDR的影响优于ZHS;但添加量大于15份后,增加ZHS的用量可以进一步提高氧指数和降低烟密度值。     

Computerized PVC formulating for optimized cost/performance

The versatility of poly(vinyl chloride) is largely a result of its capability to be modified by a wide variety of formulating additives, especially plasticizers and fillers. These additives vary widely with respect to their chemical composition, and the concentrations used in PVC, which impart significant effects on costs and performance properties. Computerized formulating programs have begun to replace laboratory testing directed at developing cost effective PVC formulations. A broad data base is required to capitalize on the many cost effective options posed to the PVC formulator. The Marketing Technical Service function of Exxon Chemical Co. utilizes COPPCO, COmputerized Profit/Performance COnsulting, to evaluate the options. The coherent data base contains 34 different plasticizers ranging from 25 to 90 phr, and can accommodate filler effects over a range of zero to 100 phr. COPPCO performs the following functions: cost and performance properties are predicted for specific formulations; lowest cost formula is defined to satisfy a specified set of performance properties; cost and performance properties are predicted for blends of plasticizers in unfilled and filled PVC compositions; performance properties are graphically presented as a function of PHR of plasticizer and plasticizer blends; graphic contours define constant property values as a function of plasticizer and of filler levels; and three dimensional response surfaces reflect the coincidental variation of both plasticizer and filler levels. COPPCO utilizes SAS (Statistical Analysis System) and Telegraph graphics, combined with sophisticated mainframe programs developed specifically to provide the desired output. Unlimited cost and performance options of the PVC formulator can be evaluated in milliseconds, vs. the traditional laboratory exercises which result in limited data after one to two weeks of sample preparation and testing.     

Thermal properties and processability of talc‐ and calcium carbonate‐filled poly(vinyl chloride) hybrid composites

The main objective of this investigation was to study and compare the thermal rigidity, thermal stability, and processability of poly(vinyl chloride) (PVC) composites filled with single fillers of talc and uncoated ground CaCO₃ (SM 90) or a hybrid filler consisting of talc/SM 90. To produce the composites, the PVC resin, fillers, and other additives were dry‐blended in a laboratory mixer before being milled into sheets by using a two‐roll mill. Test specimens were prepared by compression molding, after which the thermal properties and processability of the composites were determined. Single and hybrid filler loadings used were fixed at 30 phr (parts per hundred parts of resin). Talc‐filled PVC composite showed slightly better thermal stability and rigidity than the composite filled with SM 90, and its thermal stability and rigidity slightly decreased with SM 90 content increasing from 5 to 25 phr in order to replace talc filler in the hybrid composites. The fusion time of talc‐filled PVC composite was shorter than that of SM 90‐filled PVC composite; thus, the fusion time of hybrid composites increased with increasing SM 90. The fusion torque showed an opposite behavior. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

羟基锡酸锌-还原氧化石墨烯杂化材料与氢氧化镁对PVC的协效阻燃作用

将自制的羟基锡酸锌（ZHS）还原氧化石墨烯（RGO）杂化材料（ZHS-RGO）和氢氧化镁（MH）协效应用于软质聚氯乙烯（PVC）中。通过氧指数测定仪、微型量热测定仪和锥形量热仪分析了ZHS和ZHS-RGO杂化材料分别与MH协效对软质PVC阻燃及消烟性能的影响。结果表明,ZHS和ZHS-RGO与MH协同应用在PVC中具有很好的协同阻燃抑烟效果;样品PVC/10ZHS-RGO/5MH的热释放速率峰值为436 kW/m2,烟释放总量为23.62 m2,相比于PVC/10ZHS/5MH分别降低了38.8 %和12.0 %;杂化材料中的RGO具有良好的物理阻隔作用。     

低熔点硫酸盐对软质PVC的阻燃与消烟性能研究

制得的硫酸盐混合物熔点低，在适当温度下熔融时，能有效地保护PVC降解过程中形成的剩磷，从而能提高剩碳率，提高阻燃与消烟性能。氧指数、烟密度、DTA、TG、SEM等证明了低熔点的硫酸盐是一种优良的填料性的、具有阻燃与消烟性的阻燃消烟剂，具有很好的消烟性，当添加量达40份时，烟密度能下降45％。研究表明其对力学性能的影响比其它填料小。     

Preparation and properties of some filled poly(vinyl chloride) compositions

Different samples of filled poly(vinyl chloride) (PVC) compositions were formulated from PVC, a polar plasticizer mixture consisting of dioctylphthalate (DOP) and a chlorinated paraffin, and variable proportions of a white filler such as barite, calcium carbonate, kaoline, quartz, or talc; a conductive filler such as High Abrasion Furnace (HAF) carbon black; or a hydrated mineral filler such as aluminium hydroxide, magnesium hydroxide, or calcium hydroxide. Epoxidized soybean oil as a heat stabilizer and sandorin red (BRN) pigment were added. Electrical and mechanical studies show that the incorporation of white fillers produces a plasticized PVC of good electrical insulation character whereas the addition of HAF carbon black produces a sample with some electrical conductivity; both of them have good mechanical properties. Of the hydrated fillers studied aluminium hydroxide has been found to impart the best fire retardancy and good electrical properties for electric wires and cables. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2657–2670, 1999     

Highly filled potable water pipe

Profitable production and sale of rigid PVC water pipe is difficult even in the best of economic times. The industry is intensively cost driven. The development of lower cost formulations is, therefore, of great interest. Conventional pressure pipe formulas do not provide sufficient hydrostatic strength when calcium carbonate filler levels exceed 5 parts per hundred resin (phr). This paper will describe the development of a pressure pipe formulation which contains up to 10 phr filler while maintaining physical properties exceeding all of the required minimum standards. The presentation will include the physical property testing required to develop the formulation including cell classification and long-term hydrostatic design stress tests. These will be contrasted with data obtained from conventional formulas containing 10 phr of fillers. The quality of commercially extruded pressure pipe made with the new formula will be discussed as a function of raw material selection, blending, and extrusion conditions.     

Synergistic effect of talc/calcined kaolin binary fillers on rigid PVC: Improved properties of PVC composites

This study aims to develop poly(vinyl chloride) (PVC) composites prepared by melt mixing by using a combination of talc and calcined kaolin as filler in order to improve the disadvantages of rigid PVC, which is widely used in industry, such as poor mechanical properties and low thermal stability. In addition, PVC/talc and PVC/calcined kaolin composites were also examined for comparison. The calcined kaolin is modified with urea to increase the surface area (chemical treatment), while the surface of both fillers is coated with stearic acid for good compatibility with PVC (mechanical treatment). Scanning electron microscopy micrographs showed homogeneous distribution of mechanically processed fillers. Attenuated total reflectance–Fourier-transform infrared spectroscopy analysis revealed successful coating of the fillers with stearic acid. Also, new bands were detected in the spectrum of urea-treated calcined kaolin, showing an effective chemical treatment. It has been observed that the treatment of fillers improves the mechanical properties of PVC. Thermogravimetric results showed that delaminated calcined kaolin increased the thermal stability of PVC composites. The results of this study proved that binary filler composites combine good properties of both (synergistic effect) and good filler dispersion can be obtained by using stearic acid and urea.     

Effect of fillers and vulcanizing systems on the physicomechanical and electrical properties of EPDM vulcanizates

The physicomechanical and dielectric properties were investigated for ethylene propylene diene terpolymer (EPDM) rubber loaded with different white fillers, namely, kaolin, quartz, polyvinylchloride PVC, and talc. The white fillers were added at a fixed level of 20 phr. Two vulcanizing systems were used, tetramethyl thiuram disulfide (TMTD) and sulfur/N-cyclohexyl-2-benzothiazyl sulfenamide (S/CBS). It was found that the curing systems affect the dielectric properties more than the filler type. The effect of the curing system and type of filler on the physicomechanical properties before and after thermal aging were also investigated, and the data obtained were interpreted.     

Synergistic effects of hybrid carbon nanomaterials in room‐temperature‐vulcanized silicone rubber

This work examines nanocomposites based on nanofillers and room‐temperature‐vulcanized silicone rubber. The carbon nanofillers used were conductive carbon black (CB), carbon nanotubes (CNTs) and graphene (GE). Vulcanizates for CB, GE, CNTs as the only filler and hybrid fillers using CNTs, CB and GE were prepared by solution mixing. The elastic modulus for CNT hybrid with CB at 15 phr (4.65 MPa) was higher than for CB hybrid with GE (3.13 MPa) and CNTs/CB/GE as the only filler. Similarly, the resistance for CNT hybrid with CB at 10 phr (0.41 kΩ) was lower than for CB (0.84 kΩ) at 20 phr and CNTs as the only filler. These improvements result from efficient filler networking, a synergistic effect among the carbon nanomaterials, the high aspect ratio of CNTs and the improved filler dispersion in the rubber matrix. © 2016 Society of Chemical Industry     

两种形貌的羟基锡酸锌对聚氯乙烯的阻燃作用

以硫酸锌和锡酸钠为原料,制备了不同粒径尺寸的无定形羟基锡酸锌（ZHS）和球形ZHS;对比研究了上述2种ZHS对聚氯乙烯（PVC）的阻燃、消烟、拉伸和降解性能的影响及这2种ZHS在PVC基体中的分散情况。结果表明,当ZHS的添加量相同时,球形ZHS对PVC的阻燃、消烟和拉伸性能的有益影响优于无定形ZHS;ZHS能提高PVC的残炭率,降低其起始分解温度（T1 %）和第一阶段的最大失重峰温度（TM1）,且无定形ZHS比球形ZHS对T1 %和TM1的降低效果更明显;无定形ZHS在PVC基体中的分散性及与PVC基体结合的紧密性都优于球形ZHS。     

Interaction effects and property retention in poly(vinyl chloride) compounds

The influence of thermodynamic interactions among the components of a polymer system on mechanical properties and their retention on aging has been investigated. The systems considered involve plasticized poly(vinyl chloride)(PVC), and CaCO₃ fillers. Inverse gas chromatography was used to measure interaction parameters, and to express these in terms of acid-base concepts. Interaction data were obtained over a wide temperature range. It was shown that the volume of plasticizers retained by the PVC correlates with the measured interaction parameters. Similarly, the interaction parameters identify a CaCO₃ filler preferred for reinforcing rigid PVC, and a different CaCO₃ filler for use in given PVC-plasticizer combinations. The mechanical properties of filled PVC (up to 40 phr CaCO₃), and particularly the ultimate properties of the compounds, correlate with interaction concepts, as do property retention data after accelerated aging of the compounds at 100°C. It is concluded that component interaction parameters may provide useful guidelines to the formulation of compounds with superior properties and reduced property losses due to aging.     

超微细Mg(OH)2复合阻燃改性PP-R的研究

研制了超微细Mg(OH)2和少量的十溴联苯醚复配阻燃剂与无规共聚聚丙烯(PP-R)的填充共混复合材料,研究了复配阻燃剂的用量和硅烷偶联剂对复合材料力学性能和阻燃性能的影响。结果表明,复配阻燃剂用量的增加对材料拉伸强度有较明显的影响,用量在10份左右时缺口冲击强度达到最大;用硅烷偶联剂处理的填料可改善复合材料的各项性能。复配阻燃剂显著提高了复合材料的阻燃性能,在用量为15份时,氧指数达到27％;用量超过20份,垂直燃烧性为FV-1级。微量发烟。     

填料对反-1,4-聚异戊二烯性能的影响

研究了填料对反－1，4－聚异戊二烯（TPI）硫化胶和混炼胶的物理机械性能和结晶性能的影响。结果表明，在TPI中加入填料后，其硫化胶的300％定伸应力随填料用量的增加而增加，拉伸强度则在填料用量为20份时达到最大值；加入填料同时能降低TPI混炼胶的结晶度，填料用量增加，TPI混炼胶的结晶下降；且填料增强效果越好，结晶度下降越大。     

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     

水性纳米复合隔热涂料的研制

以纳米ATO(掺锑二氧化锡)浆料和纳米TiO2粉体配合高反射与高辐射性能的颜填料,制备了一种水性纳米复合隔热涂料.乳液、颜料和填料筛选实验表明,聚合物乳液种类对涂层隔热性能几乎没有影响;颜料中,金红石型二氧化钛是性能最好的反射填料,其用量在PVC=18%时,涂层隔热性能最好;绢云母具有一定的辐射隔热效果,当其质量分数为11%时,涂层性能最忧,辐射率可达0.86;纳米ATO浆料具有良好的隔热效果,其最佳用量为10%.当以质量比为1:2的添加量将纳米ATO和纳米TiO2加入到涂料中,所得涂层在全波段(200～2 500 nm)的太阳热反射比为86%,辐射率为0.86.     

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     

喷气燃料罐用浅色导静电防腐蚀涂料研究

针对喷气燃料罐用导静电防腐蚀涂料的特殊要求,研制出一种浅色导静电防腐蚀涂料。对浅色导静电材料种类、用量以及分散剂对涂膜导静电性能的影响进行了试验。试验结果表明:不同种类浅色导静电材料对涂膜导静电性能影响程度不同;导静电材料用量对涂膜导静电性能的影响与导静电填料在涂料配方中的颜料体积浓度有关,综合考虑涂膜导静电和防腐蚀性能之间的关系,确定了导静电填料的最佳颜料体积浓度范围。性能测试表明:所研制涂料各项性能指标均达到国家标准。通过对浸泡过涂膜的喷气燃料的性能指标测试表明,该涂料各组分对喷气燃料无污染,可广泛用于喷气燃料舱、运油车、输送管线内壁。     

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