Novel nanocomposites based on epoxy resin and modified magnesium hydroxide: Focus on flame retardancy and mechanical properties

In this work, a novel multifunctional organic‐inorganic hybrid flame agent (AM‐MEL) was prepared from magnesium hydroxide nanosheets decorated by nitrilotrimethylene triphosphonic acid and melamine. Then, an intrinsic flame‐retardant epoxy resin (EP) was prepared by covalently incorporating AM‐MEL nanoparticles. Meanwhile, ammonium polyphosphate (APP) was added into EP to form an intumescent flame retardant system with AM‐MEL. The chemical structure of AM‐MEL was characterized by Fourier transform infrared spectra, X‐ray photoelectron spectroscopy, and scanning electron microscopy. With the incorporation of 5 wt% AM‐MEL and 15 wt% APP, EP/AM‐MEL/APP could reach a limiting oxygen index value of 32.0% and achieve UL‐94 V‐0 rating, along with 88.0%, 70.0%, 81.5%, and 87.3% decrease in the peak heat release rate, total heat release, total smoke production, and the peak CO production rate, respectively, with respect to that of pure EP. The mechanisms of its flame retardant and smoke suppression were investigated.     

Mechanical properties,thermal stability,sound absorption,and flame retardancy of rigid PU foam composites containing a fire‐retarding agent: Effect of magnesium hydroxide and aluminum hydroxide

Isocyanate, polyether polyol, a flame retardant (10 wt%), and aluminum hydroxide/magnesium hydroxide (0, 5, 10, 15, and 20 wt%) are used to form the rigid polyurethane (PU) foam, while nylon nonwoven fabrics and a polyester aluminum foil are combined to serve as the panel. The rigid PU foam and panel are combined to form the rigid foam composites. The cell structure, compressive stress, combustion resistance, thermal stability, sound absorption, and electromagnetic interference shielding effectiveness (EMI SE) of the rigid foam composites are evaluated, examining the effects of using aluminum hydroxide and magnesium hydroxide. Compared with magnesium hydroxide, aluminum hydroxide exhibits superior performance to the rigid foam composites. When aluminum hydroxide is 20 wt%, the rigid foam composite has an optimal density of 0.153 g/cm³, an average cell size of 0.2466 mm, a maximum compressive stress of 546.44 Kpa, an optimal limiting oxygen index (LOI) of 29.5%, an optimal EMI SE of 40 dB, and excellent thermal stability and sound absorption.     

Characterization of poly(ethylene-co-vinyl acetate) (EVA) filled with low grade magnesium hydroxide

Low-grade magnesium hydroxide (LG-MH) is a solid by-product that undergoes an endothermic decomposition in the temperature range of 300-750 °C. Due to its thermal behaviour and its lower cost relative to pure Mg(OH)₂, it was studied as a non-halogenated flame retardant filler in a 28% vinyl acetate (VA) content poly(ethylene-co-vinyl acetate) matrix. The solid was characterized by XRF and the crystalline phases determined by XRD, composed predominantly of Mg(OH)₂ and calcium and magnesium carbonates. Particle size reduction was performed by both mechanical as well as air jet milling in order to optimize the particle size distribution.Composites with different filler concentrations were prepared to evaluate the mechanical properties and flame retardancy by means of limiting oxygen index tests. LOI was also determined in specimens filled with commercial flame-retardants to analyse the effectiveness of this solid.     

Flammability and Thermal Oxidative Degradation Kinetics of Magnesium Hydroxide and Expandable Graphite Flame Retarded Polypropylene Composites

The flammability and the thermal oxidative degradation kinetics of expandable graphite (EG) with magnesium hydroxide (MH) in flame‐retardant polypropylene (PP) composites were studied by limiting oxygen index (LOI), UL‐94 test, and thermogravimetric analysis (TGA). The results show that EG is a good synergist for improving the flame retardancy of PP/MH composite and the effect is enhanced with decreasing EG particle size. The Kissinger method and Flynn‐Wall‐Ozawa method were used to determine the apparent activation energy (E) for degradation of PP and flame retarded PP composites. The data obtained from the TGA curve indicate that EG markedly increases the thermal degradation temperature of PP/MH composites and improves the thermal stability of the composites. The kinetic results show that the values of E for degradation of flame retarded PP composites is much higher than that of neat PP, especially PP/MH composites with suitable amount of EG, which indicates that the flame retardants used in this work have a great effect on the mechanisms of pyrolysis and combustion of PP.     

氢氧化镁分解动力学的研究

以硼泥为原料与硫酸反应制备出七水硫酸镁,以氢氧化钠为沉淀剂制备出符合标准HG/T 3607-2000的氢氧化镁.利用XRD,SEM和TEM对氢氧化镁进行了表征,DTA-TG对氢氧化镁的热分解动力学进行了研究.XRD结果表明:制备粉体为单一Mg(OH)2.SEM和TEM结果表明:样品为片状或针状纤维,片直径大小不一,在20～50 nm之间,针状纤维形状不规则,大小不一致,长度在20～100 nm之间.利用Kissinger法和Ozawa法计算出的氢氧化镁热分解反应活化能分别为135.14和141.61 kJ·mol-1.利用Coats-Redfern法和Dolye法判断氢氧化镁热分解反应机理函数为A1.5.     

Polypropylene/layered double hydroxide nanocomposites: Synergistic effect of designed filler modification and compatibilizing agent on the morphology,thermal, and mechanical properties

This work addresses the optimization of the morphology, thermal, and mechanical properties of polypropylene/layered double hydroxide (LDH) nanocomposites. For this, the nanofillers were modified by a calcination rehydration process using two surfactants, sodium dodecylsulfate (SDS) and sodium dodecylbenzenesulfonate, respectively. The nanofillers were characterized at each step of the modification process by thermal gravimetry, X‐ray diffraction, and Infra red spectroscopy. Furthermore, the impact of anionic modifiers on the filler surface energy and on the interactions toward water was analyzed. Polypropylene (PP)/LDH nanocomposites were then prepared by a melt intercalation process and a high molar mass maleic anhydride functionalized polypropylene (PPgMA) was introduced as a compatibilizer. The dispersion of LDH in the PP matrix was characterized and the thermal and mechanical properties of the corresponding nanocomposites were determined and discussed as a function of the filler modification, of the nanocomposite morphology, and of the filler/matrix interfacial properties. The nanocomposites prepared from SDS modified LDH and PPgMA exhibited superior properties thanks to an optimized filler dispersion state and improved interfacial interactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 782–794     

Tensile and flexural properties of polypropylene composites filled with highly effective flame retardant magnesium hydroxide

The reinforcing effects of highly effective flame retardant magnesium hydroxide (FMX) content on the tensile and flexural properties of filled polypropylene (PP) composites were investigated within the FMX weight fraction range from 5 to 60 wt%. It was found that the Young's modulus and flexural modulus increased approximately linearly while the tensile yield strength and tensile fracture strength decreased slightly with increasing the FMX weight fraction. When the FMX weight fraction was lower than 20%, the tensile elongation at break decreased considerably, and then decreased slightly; the flexural strength increased when the FMX weight fraction was lower than 30%, and then decreased slightly. The tensile properties increased with increasing rate of tension. Moreover, the tensile yield strength of the composites was estimated using an equation proposed in previous work, and good agreement was shown between the predicted and the measured data.     

Effects of polystyrene-encapsulated magnesium hydroxide on rheological and flame-retarding properties of HIPS composites

In this study, polystyrene (PS)-encapsulated magnesium hydroxide (Mg(OH)₂) was successfully prepared by in situ polymerization of styrene on the surface of Mg(OH)₂ in a high-speed mixer. A large amount of PS chemically bonded on Mg(OH)₂ surface was confirmed by means of FT-IR, TGA and SEM. A series of composites of high impact polystyrene (HIPS) were prepared by melt blending in a co-rotating twin-screw extruder. The effects of PS-encapsulated filler on the properties of HIPS composites were studied by SEM, rheology and combustion tests (horizontal burning tests and cone calorimetry). The dispersion and adhesion patterns of PS-encapsulated Mg(OH)₂ in HIPS matrix were investigated through FT-IR and SEM. The experimental results demonstrated that comparing to the composites containing untreated filler, the rheological and flame retardant properties of those containing PS-encapsulated filler were found to be significantly improved. This improvement is mostly attributed to a better dispersion of the encapsulated filler and a strong adhesion between the filler and matrix.     

Effect of GMA polymer compatibilizers on highly filled composites of low density polyethylene/magnesium hydroxide

Functional polymers such as polyethylene grafted glycidyl methacrylate （PE-g-GMA） and ethylene-methyl acrylate-glycidyl methacrylate terpolymer （E/MA/GMA） were used as compatibilizers in the preparation of highly filled composites of polyethylene/magnesium hydroxide（PE/MH）. Comparative studies were performed on the effect of magnesium hydroxide and stearic acid on the interface within polymer and magnesium hydroxide composites. The effect of polymeric compatibilizers on the properties of the composites was studied using tensile and impact tests, torque rheological analysis, differential scanning calorimetry and environmental scanning electron microscopy （ESEM）. The microstructure of highly filled PE/MH composites changed after the addition of functional polymers. The mechanical properties of the composite material increased after compatibilization. The compatibilization processes of PE-g-GMA and E/MA/GMA were different. The grafted polymer was more compatible with polyethylene, which led to a polar polymer phase. In contrast, the tercopolymer tended to adhere to the surface of MH particles.     

Reprocessed High Impact Polypropylene Containing Oil Pollutant Exhibiting Flame Retardant Properties

Summary: In this work, the reaction to fire of reprocessed polypropylene (PP)/Ethylene Propylene Rubber (EPR) materials containing engine oil as pollutant was investigated by mass loss calorimetry. It was compared to the behaviour of the corresponding original high impact PP material. In order to flame retard the polymers, an intumescent system was studied in combination with zinc borate (ZB) as potential synergistic agent. It is shown that 20% of additives are necessary to obtain good FR properties. The use of ZB greatly improves the reaction to fire of original PP/EPR materials due to the formation of borophosphates during the degradation process that permit to reinforce the char structure. In the case of the polluted and reprocessed formulations, ZB has no influence on the fire performance because the minerals included in the engine oil act also as a flame retardant. For the two types of materials, it is demonstrated that the expansion rate at the beginning of the intumescent process plays a crucial role in the formation of an efficient insulating layer at the surface of the substrate. On the contrary, the fire performance is not related to the thickness of the carbonaceous shield.     

Flame‐retardant epoxy resins from o‐cresol novolac epoxy cured with a phosphorus‐containing aralkyl novolac

A novel phosphorus‐containing aralkyl novolac (Ar‐DOPO‐N) was prepared from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) first with terephthaldicarboxaldehyde and subsequently with phenol. The chemical structures of the synthesized compounds were characterized with Fourier transform infrared, ¹H and ³¹P NMR, and elemental analysis. Ar‐DOPO‐N blended with phenol formaldehyde novolac was used as a curing agent for o‐cresol formaldehyde novolac epoxy, resulting in cured epoxy resins with various phosphorus contents. The epoxy resins exhibited high glass‐transition temperatures (159–177 °C), good thermal stability (>320 °C), and retardation on thermal degradation rates. High char yields and high limited oxygen indices (26–32.5) were observed, indicating the resins' good flame retardance. Using a melamine‐modified phenol formaldehyde novolac to replace phenol formaldehyde novolac in the curing composition further enhanced the cured epoxy resins' glass‐transition temperatures (160–186 °C) and limited oxygen index values (28–33.5). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2329–2339, 2002     

Synergistic effects of layered double hydroxide with hyperfine magnesium hydroxide in halogen-free flame retardant EVA/HFMH/LDH nanocomposites

The synergistic effects of layered double hydroxide (LDH) with hyperfine magnesium hydroxide (HFMH) in halogen-free flame retardant ethylene-vinyl acetate (EVA)/HFMH/LDH nanocomposites have been studied by X-ray diffraction (XRD), transmission electron spectroscopy (TEM), thermogravimetric analysis (TGA), limiting oxygen index (LOI), mechanical properties' tests, and dynamic mechanical thermal analysis (DMTA). The XRD results show that the exfoliated EVA/HFMH/LDH can be obtained by controlling the LDH loading. The TEM images give the evidence that the organic-modified LDH (OM-LDH) can act as a disperser and help HFMH particles to disperse homogeneously in the EVA matrix. The TGA data demonstrate that the addition of LDH can raise 5-18 °C thermal degradation temperatures of EVA/HFMH/LDH nanocomposite samples with 5-15 phr OM-LDH compared with that of the control EVA/HFMH sample when 50% weight loss is selected as a point of comparison. The LOI and mechanical tests show that the LDH can act as flame retardant synergist and compatilizer to apparently increase the LOI and elongation at break values of EVA/HFMH/LDH nanocomposites. The DMTA data verify that the T_g value (−10 °C) of the EVA/HFMH/LDH nanocomposite sample with 15 phr LDH is much lower than that (T_g = −2 °C) of the control EVA/HFMH sample without LDH and approximates to the T_g value (−12 °C) of pure EVA, which indicates that the nanocomposites with LDH have more flexibility than that of the EVA/HFMH composites.     

氢氧化镁纳米片的合成及其润滑性能的研究

以硫酸镁和氢氧化钠为原料,油酸为表面修饰剂,采用原位合成的方法制备出了疏水性的Mg(OH2)纳米片.研究了反应温度、反应物浓度等因素对氢氧化镁纳米片平均粒径的影响.用X-射线粉末衍射(XRD)、红外(IR)和热重(DTA-TGA)及扫描电子显微镜(SEM),对制备出的Mg(OH)2纳米片的结构和形貌进行了表征,证实制备出的Mg(OH)2纳米片具有良好分散性,纳米片尺度为200～300nm,厚度10nm.摩擦实验证明Mg(OH2)纳米片可以作为润滑油中的添加剂来应用.     

Study on mechanical properties and phase morphology of polypropylene/polyolefin elastomer/magnesium hydroxide ternary composites

In this work, elastomer‐toughened polypropylene (PP)/magnesium hydroxide (MH) composites with ethylene–octene copolymer (POE) were prepared in a twin‐screw extruder and then injection‐molded. The structure, mechanical properties, phase morphology, and rheological behaviors of PP/POE/MH ternary composites were studied. The mechanical properties and fracture behaviors of PP/POE/MH ternary composites are strongly influenced by the incorporation of POE copolymer. The addition of POE causes a significant improvement in the impact strength of the composites, from 3.6 kJ/m² in untoughened composites to 47.4 kJ/m² in PP composites containing 30 phr POE. This indicates that POE is very effective in converting brittle PP composites into tough composites. Conversely, the tensile strength and the Young's modulus of the composites decrease with respect to the PP composites, as the weight fraction of POE is increased to 40 phr. Scanning electron microscopy (SEM) study shows a two‐phase morphology where POE, as droplets, is dispersed finely and uniformly in the PP matrix. The rheological behaviors show that the interfacial interaction in the composites is enhanced with increase in POE content. Interparticle interactions give rise to the formation of interparticle network. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation,thermal properties,and flame retardance of epoxy–silica hybrid resins

A novel epoxy system was developed through the in situ curing of bisphenol A type epoxy and 4,4′‐diaminodiphenylmethane with the sol–gel reaction of a phosphorus‐containing trimethoxysilane (DOPO–GPTMS), which was prepared from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) with 3‐glycidoxypropyltrimethoxysilane (GPTMS). The preparation of DOPO–GPTMS was confirmed with Fourier transform infrared, ¹H and ³¹P NMR, and elemental analysis. The resulting organic–inorganic hybrid epoxy resins exhibited a high glass‐transition temperature (167 °C), good thermal stability over 320 °C, and a high limited oxygen index of 28.5. The synergism of phosphorus and silicon on flame retardance was observed. Moreover, the kinetics of the thermal oxidative degradation of the hybrid epoxy resins were studied. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2354–2367, 2003     

Novel approach to the chemical modification of poly(vinyl alcohol): Phosphorylation

The chemical modification of poly(vinyl alcohol) (PVA) was performed through oxidation followed by nucleophilic addition. PVA was oxidized by KMnO₄ to form vinyl ketone units along the polymer backbone. The chemical modification of PVA was then conducted through the reaction of the carbonyl group of the vinyl ketone unit with 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) as a nucleophile. Through this approach, the phosphorous DOPO group was attached onto the carbon atom of the polymer main chain rather than onto the pendent hydroxyl groups of PVA. The formed DOPO‐containing PVA showed improved thermal stability, organosolubility, and flame retardance. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1107–1113, 2003     

不同金属离子层状双氢氧化物制备及表征

本文采用恒定pH值共沉淀法制备六种层板金属离子不同的层状双氢氧化物(LDH).通过傅立叶变换红外光谱仪(FT-IR)、X-射线衍射仪(XRD)和扫描电子显微镜(SEM)对LDH进行了表征,并利用热重分析(TG)研究了LDH的热分解行为.研究表明,不同金属离子对LDH的层间距、晶粒尺寸等参数有一定影响,团聚程度也有较大的差异.     

Effects of elastomer on morphology,flammability and rheological properties of HIPS/PS‐encapsulated Mg(OH)2 composites

The effects of elastomer type on morphology, flammability and rheological properties of high‐impact polystyrene/Mg(OH)₂ based on encapsulated by polystyrene have been investigated. The ternary composites characterized by cone calorimetry, horizontal burning rate, limiting oxygen index (LOI), rheology and SEM. Morphology was controlled using poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] triblock copolymer (SEBS) or the corresponding maleinated SEBS (SEBS‐g‐MA). As revealed by SEM observations, composites of HIPS/SEBS/Mg(OH)₂ exhibit separation of the filler and elastomer and good adhesion between SEBS and the filler, whereas composites of HIPS/SEBS‐g‐MA/Mg(OH)₂ exhibit encapsulation of the filler by SEBS‐g‐MA. The flame retardant and rheological properties of ternary composites were strongly dependent on microstructure. The rheological test showed that the composites with encapsulation structure exhibit a stronger solid‐like response at low frequency than those of the composites with separate dispersion structure. The combustion tests showed that the composites with encapsulation structure showed higher flame retardant properties than those of separate dispersion structure at optimum use level of SEBS‐g‐MA. However, with the increase of the content of SEBS‐g‐MA, the flame retardancy of the composite declined somewhat which can be explained that the SEBS‐g‐MA coating acts as a heat and mass transfer barrier due to the formation of encapsulation structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2023–2030, 2007     

Surface modification of magnesium hydroxide particles using silane coupling agent by dry process

In order to improve the dispersion and compatibility of magnesium hydroxide (MH) when added in the polymer matrix as fillers, the surface of MH was modified by dry process using vinyltrimethoxysilane (VTMS), and the interfacial interaction between MH and VTMS was also studied. Scanning electronic microscopy, transmission electron microscopy, and X‐ray powder diffraction analyses showed that the agglomerations of MH particles were effectively relieved, and a thin layer was formed on the surface of modified MH. Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy analyses showed that the VTMS molecules bound strongly to the surface of MH particles and chemical bond (Si―O―Mg) was formed after modification. The effect of surface modification was evaluated by contact angle, the settlement curve, and thermogravimetric analysis. The results showed that the surface of MH particles was transformed from hydrophilic to hydrophobic, with the dispersibility and the compatibility of MH particles significantly improved in the organic phase. Additionally, the thermal stability of the VTMS modified MH particles had improved significantly.     

Flame retardancy and smoke suppression of magnesium hydroxide filled polyethylene

In this work, halogen‐free, flame‐retarded polyethylene was investigated to study the effect of inorganic fillers on the improvement of flame retardancy and the suppression of smoke density. Through analyses on the thermal stability and smoke density, it was found that the flame retardancy developed by magnesium hydroxide could effectively be increased by the additional incorporation of zinc borate and talc. Furthermore, a synergistic effect was observed when zinc borate and talc were incorporated together. This result was confirmed by the observation of fire performance with cone calorimetry. A morphological study supported the idea that the improvement in the flame retardancy and the suppression of smoke density was due to hard and compact charred layers formed by the interactions between polymer and inorganic fillers. The charred layers provided a good thermal and flame barrier. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 936–944, 2003