The relationship between thermal degradation behavior of polymer and the fire retardancy of polymer/clay nanocomposites

The change in the degradation pathway of a polymer by incorporation of clay has a significant effect on the fire retardancy of polymer/clay nanocomposites. Since the clay layers act as a barrier to mass transport and lead to superheated conditions in the condensed phase, extensive random scission of the products formed by radical recombination is an additional degradation pathway of polymers in the presence of clay. The polymers that show good fire retardancy upon nanocomposite formation exhibit significant intermolecular reactions, such as inter-chain aminolysis/acidolysis, radical recombination and hydrogen abstraction. In the case of the polymers that degrade through a radical pathway, the relative stability of the radical is the most important factor for the prediction of the effect that nanocomposite formation has on the reduction in the peak heat release rate. The more stable is the radical produced by the polymer, the better is the fire retardancy, as measured by the reduction in the peak heat release rate, of the polymer/clay nanocomposite.     

Morphology evolutions of organically modified montmorillonite/polyamide 12 nanocomposites

Organically modified montmorillonites (OMMTs) by octadecylammonium chloride with two adsorption levels were dispersed in polyamide 12 (PA12) matrices with two molecular weights for different melt mixing times in order to investigate morphology evolutions and factors influencing fabrication of PA12 nanocomposites. Different adsorption levels of the modifier in the OMMTs provide different environments for diffusion of polymer chains and different attractions between MMT layers. Wide-angle X-ray diffraction (WAXD), transmission electron microscope (TEM) and gas permeability were used to characterize morphologies of the nanocomposites. Both OMMTs can be exfoliated in the PA12 matrix with higher molecular weight, but only OMMT with lower adsorption level can be exfoliated in the PA12 matrix with lower molecular weight. It was attributed to the differences in the levels of shear stress and molecular diffusion in the nanocomposites. The exfoliation of OMMT platelets results from a combination of molecular diffusion and shear. After intercalation of PA12 into interlayer of OMMT in the initial period of mixing, further dispersion of OMMTs in PA12 matrices is controlled by a slippage process of MMT layers during fabricating PA12 nanocomposites with exfoliated structure.     

Thermal degradation of ethylene-vinyl acetate coplymer nanocomposites

The degradation pathway of ethylene-vinyl acetate copolymers and their nanocomposites is investigated using TGA/FT-IR, TGA, GC-MS, cone calorimetry and UV techniques to determine if the presence of the clay has an effect on the degradation pathway. The first step of the degradation, the loss of acetic acid by chain stripping, has been shown to be accelerated by the presence of clay. In this work we show that clay does affect the degradation pathway and that the presence of hydroxyl groups on the edges of the clay could be the cause of the accelerated initial step. The products of the second step of the degradation are changed in quantity and some new products are produced, showing that the clay also has an effect on this step of the degradation pathway. A scheme is suggested to account for the role of the clay in the degradation.     

The influence of carbon nanotubes, organically modified montmorillonites and layered double hydroxides on the thermal degradation and fire retardancy of polyethylene, ethylene-vinyl acetate copolymer and polystyrene

Nanocomposites of polyethylene, ethylene-vinyl acetate copolymer and polystyrene with single- and multi-wall carbon nanotubes, organically modified montmorillonites and layered double hydroxides were prepared by melt blending. Their morphologies were assessed by X-ray diffraction and transmission electron microscopy, while the flammability properties were evaluated by thermogravimetric analysis and cone calorimetry. The relative amounts and the identity of the degradation products are changed when both well-dispersed cationic and anionic clays are used, but there is no difference in the degradation products when carbon nanotubes were utilized. When the nano-dimensional material is not well-dispersed, the degradation products are not changed. Unlike their smectite counterparts, polymer/layered double hydroxide nanocomposites give reasonably good reductions in peak heat release even when good nano-dispersion has not been obtained. These data suggest that the enhancement in the fire behavior must be, at least in part, due to different mechanisms for montmorillonite, layered double hydroxides and carbon nanotube-based nanocomposites.     

Enhanced mechanical properties and fire retardancy of polyamide 6 nanocomposites based on interdigitated crystalline montmorillonite–melamine cyanurate

Polyamide 6 (PA6)–montmorillonite (MMT)–melamine cyanurate (MCA) nanocomposites were prepared by the incorporation of interdigitated crystalline MMT–MCA. Their morphologies were assessed by X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, thermal stability measurement by thermogravimetric analysis, mechanical properties measurement by tensile tests, and fire retardancy measurement by limiting oxygen index testing and vertical burning testing (UL‐94). The results indicate that MMT–MCA was homogeneously nanodispersed in PA6. Compared with PA6–MCA, the PA6–MMT–MCA nanocomposites showed enhanced thermal stability. The mechanical properties and fire retardancy show that the PA6–MMT–MCA nanocomposites with 5 wt % total loading of MMT–MCA reached UL‐94 V‐2 rating (3.2 mm) and significantly increased the tensile strength of PA6 up to 24.8 % with only 1 wt % MMT in PA6. Through the control the weight ratio of MMT and MCA in MMT–MCA, the Young's modulus of PA6 could be adjusted in a very wide range (300–1100 MPa) because of the dual role of the rigid MMT and nonrigid MCA layers. The reinforced mechanism of the mechanical properties was also investigated. Consequently, the PA6–MMT–MCA nanocomposites with a good nanodispersing ability, improved thermal stability, excellent mechanical properties, and good flame retardancy were obtained and could provide broad prospects for wider applications for PA6 materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46039.     

Investigation on effects of aluminum and magnesium hypophosphites on flame retardancy and thermal degradation of polyamide 6

Two hypophosphites, aluminum hypophosphite (AlHP) and magnesium hypophosphite (MgHP), were applied to obtain flame retardant polyamide 6 (FR-PA6) composites. UL-94 and limiting oxygen index results indicated that AlHP contributed both good flame retardance and antidripping ability for PA6, while MgHP did not. Based on thermogravimetric analysis (TGA), AlHP and MgHP presented the different thermal degradation behavior. That is, the quick decomposition of AlHP took place at lower temperature than that of MgHP. AlHP promoted the early thermal degradation of PA6 and formed more char residue. The thermal decomposition mechanisms of AlHP and MgHP in nitrogen or air were suggested. Scanning electron microscope and X-ray photoelectron spectroscopy indicated that in the existence of AlHP, the morphological structures of char residue were more homogenous, and compact, and more char residue was formed. These results well illustrated the difference of the flame retardancy between AlHP and MgHP. Mechanical properties of PA6/AlHP and PA6/MgHP were also obtained. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influences of catalysis and dispersion of organically modified montmorillonite on flame retardancy of polypropylene nanocomposites

The degradation and flame retardancy of polypropylene/organically modified montmorillonite (PP/OMMT) nanocomposite were studied by means of gas chromatography‐mass spectrometry and cone calorimeter. The catalysis of hydrogen proton containing montmorillonite (H‐MMT) derived from thermal decomposition of (alkyl) ammonium in the OMMT on degradation of PP strongly influence carbonization behavior of PP and then flame retardancy. Brønsted acid sites on the H‐MMT could catalyze degradation reaction of PP via cationic mechanism, which leads to the formation of char during combustion of PP via hydride transfer reaction. A continuous carbonaceous MMT‐rich char on the surface of the burned residues, which work as a protective barrier to heat and mass transfer, results from the homogeneous dispersion of OMMT in the PP matrix and appropriate char produced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

软质PVC阻燃抑烟的研究

介绍了各类阻燃剂(如氢氧化铝、氢氧化镁、锑系、磷系、硼系、钼系)的性能及阻燃机理,并对软质PVC材料的阻燃抑烟性能进行了实验。结果表明：经偶联剂处理过的阻燃剂,由于增强了其与基体的界面结合力。从而使其力学性能得到提高;三氧化钼的用量对聚合物的阻燃效果影响不明显,而随着硼酸锌和三氧化二锑用量的增加,其阻燃效果越来越好。     

聚合物基蒙脱土纳米复合材料热稳定性能及阻燃性能

综述了近年来国内外聚合物基蒙脱土纳米复合材料热性能和阻燃性能方面的研究进展及机理,并对蒙脱土与其他绿色阻燃剂协同阻燃的前景进行了展望。     

Effect of organoclay structure on morphology and properties of nanocomposites based on an amorphous polyamide

An amorphous polyamide (a-PA) and three organoclays, M₃(HT)₁, M₂(HT)₂ and (HE)₂M₁T₁, were melt processed to explore the effect of the organoclay structure on the extent of exfoliation and properties of these nanocomposites. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to determine the degree of exfoliation of the nanocomposites. For quantitative assessment of the structure of the nanocomposites, a detailed particle analysis was made to provide various averages of the clay dimensions and aspect ratio. The results evaluated from different methods were generally consistent with each other. Nanocomposites based on the organoclays with one alkyl tail and hydroxyl ethyl groups gave well-exfoliated structures and high matrix reinforcement while nanocomposites from two-tailed organoclay contain a considerable concentration of intercalated stacks. Nanocomposites from the organoclays with one alkyl tail showed slightly better exfoliation and matrix reinforcement than those from the organoclays with hydroxyl ethyl groups. The organoclay structure trends for a-PA are analogous to what has been observed for nylon 6; this suggests that a-PA, like nylon 6, has good affinity for the pristine silicate surface of the clay leading to better exfoliation and enhanced mechanical properties with one-tailed organoclay than multiple-tailed organoclay. Furthermore, heat distortion temperatures were predicted from the dynamic mechanical properties of nanocomposites.     

Investigation on flame retardancy and rheological and thermomechanical characterisation of multiwall carbon nanotube reinforced nanocomposites

Abstract

In the present work, the influence of multiwalled carbon nanotubes (MWCNTs) on the flame retardancy and rheological, thermal and mechanical properties of polybutilen terephthalate (PBT) and polypropylene (PP) matrixes has been investigated. The carbon nanotube content in the thermoplastic materials was 2 and 5?wt‐%. The nanocomposites were obtained by diluting a masterbatch containing 20?wt‐% nanotubes using a twin‐screw extruder and the thermal properties were analysed by differential scanning calorimetry and thermogravimetric analysis; thermomechanical properties were determined by dynamic mechanical thermal analysis and the rheological behaviour was studied by a Thermo Haake Microcompounder. The results concerning the flame retardancy show that the MWCNTs are not equally effective as flame retardants in PP and PBT. The ignition time is increased only for PBT whereas the extinguishing time is decreased for PP and PBT. The reinforcement of the thermoplastics with multiwall carbon nanotubes is improved regarding the mechanical and thermal properties of the nanocomposites compared to pristine materials and the behaviour of thermoplastic nanocomposites regarding fire retardancy depends on the nature of the polymeric matrix.     

Synthesis of modified graphene oxide and its improvement on flame retardancy of epoxy resin

In this work, the small molecule with double-phosphaphenanthrene structure was successfully grafted on the surface of graphene oxide (GO), which is called functionalized graphene oxide (FGO). The introduction of FGO improved the poor interfacial compatibility between graphene and epoxy matrix. And FGO could be used as the highly effective flame retardant. The thermogravimetric analysis results showed a significant improvement in the char yield of cured FGO/EP. When the content of FGO was 3 wt %, the limiting oxygen index value reached 30.4%. At the same time, the three-point bending and thermomechanical tests confirmed that the mechanical properties of the epoxy resin composites were improved. Based on the char analyses of SEM images and Raman spectroscopy, the flame retardant could promote the formation of a stable carbon layer. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47710.     

The investigation on the flame retardancy mechanism of nitrogen flame retardant melamine cyanurate in polyamide 6

Melamine cyanurate (MCA) flame retardant polyamide 6 (PA6) shows good flame retardancy, but the corresponding mechanisms have not been completely understood. In this paper, Fourier transform infrared spectra (FTIR), elemental analysis (EA), scanning electronmicroscope (SEM), energy dispersive scanning (EDS), thermogravimeric analysis (TGA) and pyrolysis-gas chromatogram-mass spectrometer (Py-GC-MS) were conducted to investigate the processes including melt-drip phase, gaseous phase and condensed phase of MCA/PA6 system. Compared with original PA6, it is found that MCA flame retardant PA6 mainly undergoes predominant weak bond-breakage degradation forming oligomers rather than oxidative degradation producing low-boiling point fuel as original PA6 does. The produced oligomers can accelerate the formation of the melt drips which effectively removes the combustion heat and latent fuel, also the self-condensation of these oligomers is advantageous to form stable cross-linking structure, thus greatly consolidating the char layer.     

Influence of organo-montomorillonite on mechanical and rheological properties of polyamide nanocomposites

The effect of organically modified montmorillonite (OMMT) on polyamide nanocomposites was studied. OMMT/polyamide nanocomposites were prepared through direct melt compounding on a conventional twin screw extruder. With increasing the loading of OMMT, the Young modulus, elongation at break and tensile strength increased. 1 mass% loading of OMMT/polyamide resulted in 11% increase of the elongation at break compared to virgin polymer, while 4% loading showed 13%. Rheological data like torque, fusion time, viscosity and shear rate were also recorded on Brabender Plasticorder and were correlated with M = CS^a and τ = K(γ)ⁿ. The value n < 1 indicated pseudo-plastic nature of the polyamide/OMMT. The torque decreased with increased loading due to soft nature of OMMT, which acts as a lubricating agent. This improvement in mechanical properties with increase in amount of OMMT loading was also indicated by the reduction in shear viscosity and torque.     

Some comments on the modes of action of nanocomposites in the flame retardancy of polymers

Nanocomposites of polymers with montmorillonite (MMT) yield upon pyrolysis and combustion an MMT‐rich surface of the char. The prevalent approach considers this accumulation as due to the gasification of the polymer and subsequent gradual precipitation of the MMT on the surface. According to the present paper, the enrichment in MMT is postulated to be due to a migration or convection of the MMT to the surface driven mainly by the lower surface free energy of the MMT. The role of the surface free energy in the surface structure of polymer blends, especially those involving a silicon‐containing component, is discussed. The enrichment occurs above the glass transition temperature and is temperature dependent. XPS evidence for the accumulation of MMT on the surface of a polystyrene/MMT nanocomposite is reviewed. Its dependence on the stability of the nanocomposite structure, and particularly on the stability of the quaternary ammonium compounds that bind the polymer to the MMT, is pointed out. The importance of the surface free energy in the flame retardancy of polymer blends as well as polymer‐additive mixtures is discussed. Copyright © 2003 John Wiley & Sons, Ltd.     

Flame retardancy of glass fiber reinforced high temperature polyamide by use of aluminum diethylphosphinate: thermal and thermo‐oxidative effects

Glass fiber reinforced polyamide (PA) 6 T/DT flame retarded with aluminum diethylphosphinate (AlPi) was tested to assess its flame retardant properties. Models for the decomposition of PA 6T/DT with and without AlPi are presented. Thermal decomposition was measured by performing TGA with Fourier transform infrared (FTIR) spectroscopy and FTIR spectroscopy in the condensed phase. Fire behavior was studied using a cone calorimeter and flammability was tested with UL 94 and the limiting oxygen index. AlPi works as an effective flame retardant for glass fiber reinforced PA 6T/DT materials, acting in the gas phase. Also observed was condensed‐phase action, which occurs especially under oxidative conditions before the samples ignite. © 2013 Society of Chemical Industry     

盐对阴阳离子表面活性剂水溶液相行为的影响

以阴阳离子表面活性剂混合体系为研究对象,通过测定体系在不同种类盐溶液中的三元相行为,探索了盐对体系相行为中的双水相区位置及相区宽度的影响规律.研究发现,阴离子双水相区的位置与宽度主要受盐阳离子的影响,盐阳离子半径越大,极化率越高,阴离子双水相区向阴离子表面活性剂方向移动的趋势越大,相区越宽;而盐的阴离子是影响阳离子双水相区位置与宽度的主要因素.     

有机硅改性松香基环氧树脂的制备及阻燃性能

制备了聚甲基苯基硅氧烷（PMPS）改性松香基乙二醇二缩水甘油醚AR-EGDE。红外光谱(IR)、核磁共振（¹³C NMR）和环氧值测试结果表明有机硅成功接枝至环氧树脂。同时,将PMPS与AR-EGDE充分混合得到物理改性树脂。通过力学性能和极限氧指数测试探讨了改性方法对改性树脂力学及阻燃性能的影响：化学改性优于物理改性及未改性的AR-EGDE。热失重、炭层分析表明,PMPS改性的树脂在受热和燃烧过程中,都能形成含硅炭层,该炭层可延缓内部材料热分解,同时阻止可燃裂解气体的释放和熔滴发生,从而提高材料的耐热和阻燃性能。物理改性松香基环氧,燃烧时无法形成有效富硅炭层覆盖于底部材料,从而使其阻燃性劣于化学改性。