阻燃型氢氧化镁制备及其影响因素探讨

以七水硫酸镁为原料、氨水为沉淀剂、选择适宜的表面活性剂。以样品XRD图中（001）面与（101）面衍射峰的相对强弱为考察指标，通过单因素实验，分别考察了反应温度、恒温反应时间、陈化时间、表面活性剂用量及氨镁摩尔比等因素对氢氧化镁样品XRD图中（001）面与（101）面衍射峰相对强弱的影响。实验结果表明，制备阻燃氩氧化镁较适宜的工艺条件为：反应温度40℃、恒温反应时间40min、陈化时间120min、表面活性剂A体积用量4ml、氨镁摩尔比6：1.     

Synergistic effects of organically modified montmorillonite in combination with metal oxides on the fire safety enhancement of intumescent flame-retarded epoxy resins

Synergistic effects of organically modified montmorillonite (OMMT) in combination with different metal oxides (Bi₂O₃, Sb₂O₃, and MoO₃) on the fire safety enhancement of the intumescent flame-retarded epoxy resins (EPs) were systematically evaluated. The results from X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses show that the OMMT and metal oxides acquire a uniform distribution in the EP matrix, and OMMT platelets exhibit a fully exfoliated state. The flammability and thermogravimetry (TG) tests show that the intumescent flame retardant (IFR)-OMMT-metal oxide ternary system can endow EPs with the higher synergistic efficiencies on the enhancement of flame retardancy, smoke suppression properties, and charring ability compared to those of IFR or IFR-OMMT system, and the synergistic efficiency is the following order: IFR/OMMT/Sb₂O₃ > IFR/OMMT/MoO₃ > IFR/OMMT/Bi₂O₃. In particular, the sample, filled with 1.5 wt% OMMT, 1.5 wt% Sb₂O₃, and 27 wt% IFR, passes the UL94 V-0 rating and acquires the highest limiting oxygen index value of 28.5% among the samples. The IFR-OMMT-metal oxide ternary system exerts a better synergistic effect on the generation of crosslinking and aromatic structures that supply the excellent charring effect and barrier effect for the EPs, and the synergistic efficiency of IFR-OMMT-metal oxide ternary system is varied with the types of metal oxides.     

Calcium carbonate and ammonium polyphosphate flame retardant additives formulated to protect ethylene vinyl acetate copolymer against fire: Hydrated or carbonated calcium?

In this study, the effect of the chemical nature of different calcium (Ca)-based minerals as flame retardant additives in combination with ammonium polyphosphate (APP), in 1:1 proportions, on the flame retardancy behavior and performance of ethylene vinyl acetate copolymer was discussed. Combining APP with partly and completely hydrated calcium oxide led to superior flame-retardant function detected in mass loss calorimeter measurements with respect to the corresponding system containing carbonated calcium. This privileged character was attributed to the higher reactivity of hydrated Ca-based fillers toward APP in comparison with Ca carbonate, which induced the formation of an intumescent residue. The difference between reactivity potential of hydrated and dry Ca was demonstrated by the newly formed thermally stable species, and further evidenced by thermogravimetric analysis performed on APP/fillers blends. Moreover, the presence of more crystalline domains in the Ca/phosphorus-based compounds was evidenced by XRD analysis of the mass loss calorimeter test residues. The results of this work highlight the role of blend additive systems on the performance of flame retardancy of polymer materials.     

Thermal cross-linking and anti-meltdrop properties of copolyester containing phosphorus/magnesium salt composites by in situ polymerization

Polyester is widely used in household products because of its good mechanical properties and wears resistance, but polyester is easy to ignite and inclined to produce droplet, so its application range is limited. The cross-linkable magnesium hydroxide nanoparticles were incorporated into flame-retardant polyester, which enables the phosphorus-containing copolyester with thermal cross-linking and anti-meltdrop properties. The nanoparticles were achieved by in situ polymerization and acted as a nucleating agent for improving the crystalline properties of the copolyester. Furthermore, the nanoparticles also enhanced anti-meltdrop properties and reduced the heat and gas release during the combustion process of the copolyester. The maximum heat release rate and total smoke release reduced by 39.8% and 74.4% compared with pure polyester. Specifically, the combustion products of the nanoparticles and phosphorus flame retardant could act a barrier role by covering the carbon layer to isolate air and heat, thereby resulting in excellent anti-meltdrop properties. The simple modification method reported here realizes the collaborative modification of flame retardant and anti-meltdrop properties of phosphorous flame-retardant copolyesters by thermal cross-linking.     

锆及锆合金中微量铝的测定

本文介绍在硫酸介质中,先用钽试剂-氯仿萃取分离除去锆以及钛、铁、铪等;再在pH=8.5左右,用苯萃取铝-钽试剂配合物,用稀盐酸反萃取;最后在pH=5.5—6时用铬天青S比色以测定铝的方法,确定了其测定条件。本方法准确性好,灵敏度高,测定范围为0.0025%—0.035%。     

酪素基rGO复合乳液的制备及其对皮革阻燃增强效果的研究

为制备具有增强阻燃效果的皮革涂饰材料,本研究首先以天然石墨为原料,采用Hummers法制备氧化石墨烯,并采用NaBH4对其进行还原得到还原氧化石墨烯（rGO）。通过FTIR,XRD和TEM等对其进行表征。结果表明,成功制备了rGO纳米材料。随后,采用物理共混法将rGO引入天然蛋白质酪素体系,制备酪素基rGO复合乳液并将其应用于皮革涂饰,对涂饰后革样的阻燃性能、力学性能和耐干湿擦性能进行测试。结果表明,当rGO的含量为酪素体系溶质质量的0.5%时,与未含rGO的酪素体系相比,涂饰后革样的燃烧速率下降47.2%,极限氧指数（LOI）由24.2%增加至26.3%,热释放速率（HRR）下降53.1%,总热释放率（THR）也有所降低。rGO的引入对涂饰后革样的力学性能和耐干湿擦性能影响不大。     

阻燃OMMT/WPU纳米复合材料的制备及性能研究

采用端羟基聚丁二烯（HTPB）剥离层状有机蒙脱土（OMMT）为纳米片层,并与异佛尔酮二异氰酸酯（IPDI）、二羟甲基丙酸（DMPA）等单体通过原位聚合法制备了OMMT纳米片改性的水性聚氨酯（OWPU）纳米乳液及胶膜。利用小角XRD、TEM、DLS、EDS、TGA、LOI、CONE以及SEM对样品的结构和性能进行了表征。结果表明,HTPB剥离的OMMT纳米片的衬度均匀,完整性较好;改性后OWPU的乳液粒径增大,胶膜的弹性模量、热稳定性、抗熔滴性和阻燃性能均得到明显地改善,其中弹性模量可提高59.4%,热释放速率峰值可降低36.9%;燃烧炭渣表面形貌显示,瓦片状蒙脱土相互穿插形成了具有团簇结构的蒙脱土覆盖层。     

Zirconium-Embedded Polyhedral Oligomeric Silsesquioxane Containing Phosphaphenanthrene-Substituent Group Used as Flame Retardants for Epoxy Resin Composites

A zirconium hybrid polyhedral oligomeric silsesquioxane derivative (Zr–POSS–bisDOPO) is synthesized by the corner-capping and Kabachnik–Fields reactions. It is characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR), and then used as a flame retardant in diglycidyl ether of bisphenol A (DGEBA) to endow epoxy resin (EP) with flame retardancy. The flame retardancy, thermal stability, and mechanical properties of the cured EP/Zr–POSS–bisDOPO composites are investigated. The results show that when Zr–POSS–bisDOPO is added by 5–7 wt%, the EP/Zr–POSS–bisDOPO composites pass the UL-94 V-0 rating test. In addition, they have a better flame-retardant effect than pure EP. The combination of Zr atom embedded in the Si O cubic cage and the two phosphaphenanthrene substituent groups in one corner of cubic cage is expected to realize the Zr/Si/P ternary intramolecular hybrid synergistic effect and achieve the possibility of dispersing metal–POSS cages at a sub-micrometer-scale level into polymer matrix. It also proves that Zr–POSS–bisDOPO produces phosphorus-containing free radicals and terminates the chain reactions in gas phase. Meanwhile the Si O Si and Zr O units are retained in the solid phase, which promote the char formation and enhance the flame retardancy. This kind of Zr-doped POSS will be helpful for developing the new metal–POSS hybrid flame-retardant and polymer composites.     

Synergistic Flame Retardant Effects of Carbon Nanotube-Based Multilayer Nanocoatings

In an effort to develop highly functionalized flame retardant materials, hybrid nanocoatings are prepared by alternately depositing a positively charged polyaniline (PANi) and negatively charged montmorillonite (MMT) using the layer-by-layer (LbL) assembly technique. Carbon nanotubes (CNTs) are employed in polymer nanocomposites as effective reinforcement, where nanotubes are stabilized in MMT aqueous solution. The 3D structure and high density of CNTs deposited in the PANi/CNTs-MMT multilayers produce thicker and heavier coatings in comparison to the LbL assemblies without CNTs. Vertical and horizontal flame testing show that the incorporation of CNTs improves fire resistance. Additionally, cone calorimetry reveals that stacking two nanomaterials (MMT and CNTs) in a single coating shows a significant reduction in peak heat release rate (up to 51%), total smoke release (up to 47%), and total heat release (up to 37%) for the polyurethane foam. The enhancement of flame retardancy is attributed to a synergistic effect; MMT serves as a physical barrier that retards the diffusion of heat and gas. The addition of CNTs strengthens the thermal stability and high char yield. These results, coupled with the simplicity with which the LbL deposition is applied, present a viable alternative to halogen-free flame retardant nanocoatings to natural and synthetic fibers.     

Bioderived Bilayer Shell Modification β-FeOOH Nanorods via Self-Assembly Technique as Sustainable Flame Retardants for Enhancing Flame Retardancy of Epoxy Resin

The design and application of bioderived flame retardants have been widely conducted to meet the concept of green and sustainable development. Here, self-assembly technique is used to prepare core–shell bioderived additives by using β-FeOOH as the core and polydopamine (PDA)/tannic acid (TA) bilayer as the shell, following adsorption of nickel ions to enhance the thermal stability, flame retardancy, and mechanical properties of epoxy resin (EP). The molecular structure of biobased resources is rich in hydroxyl groups and carbon content, which can be dehydrated and carbonized during combustion and promote the formation of robust protective char layer. With the addition of 5 wt% β-FeOOH@PTNi, the EP composites can pass V-0 rating in the UL-94 test. The peak heat release rate and total heat release decrease by 28.4% and 17.4% compared with pure EP. The bioderived nanorods can capture the oxygen free radicals, contributing to flame retarding in gaseous phase. Thus, the release of high-toxic CO and flammable gaseous is significantly suppressed. Besides, the storage modulus of EP composites increases by 16.0% with the addition of 5% β-FeOOH@PTNi compared with pure EP. This work provides a sustainable methodology for the design of bioderived flame retardants for EP.