Mechanism on flame retardancy of polystyrene/clay composites-The effect of surfactants and aggregate state of organoclay

Effects of organically modified montmorillonites (OMMTs) with different type and amount of modifiers on flame retardancy of polystyrene (PS) have been studied. The results from morphology analysis, gas chromatography–mass spectrometry and cone calorimeter have showed different mechanisms for the flame retardancy of PS/OMMTs composites, depending on surface property of OMMTs. One is the catalysis of acid sites formed on the surface of octadecylammonium modified MMT (c-MMT) via Hoffman decomposition on the carbonization of degradation products, which promotes the formation of clay-enriched char barrier. The other is related to chemical effect of inherent properties of MMT sheets on reactive intermediates during combustion, which work in PS/Na-MMT and PS/sodium dodecylsulfonate modified MMT (a-MMT) composites. Furthermore, the effect of the aggregate states of a-MMT on the flame retardancy of PS/a-MMT composites was studied. In the case of a-MMTs from spraying drying, a good protective layer with foam-like aggregate state of MMT sheet was formed in the residue, which results in low peak value of heat release rate of PS/a-MMT composites.     

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     

Polypropylene nanocomposites prepared with natural and ODTABr‐modified montmorillonite

In this study, the main goal is to obtain montmorillonite nanocomposites of polypropylene (PP). To achieve this goal, a two‐phase study was performed. In the first part of the work, organomodified clay (OMMT) was synthesized and characterized. Octadecyltrimethylammonium bromide (ODTABr) cationic surfactant was added to the clay (Na‐activated montmorillonite, MMT) dispersions in different concentrations in the range of 5 × 10^?5–1 × 10^?2 mol/L. Rheologic, electrokinetic, and spectral analyses indicated that ODTABr has interacted with MMT at optimum conditions when the concentration was 1 × 10^?2 mol/L. In the second part, modified (OMMT) and unmodified (MMT) montmorillonite were used to obtain PP nanocomposites (OMMT/PP and MMT/PP, respectively). The nanocomposites were prepared by melt intercalation where the montmorillonite contents were 1 or 5% (w/w) for each case. The thermal analyses showed that the thermal properties of OMMT/PP nanocomposites were better than MMT/PP, and both of them were also better than pure polymer. Increase in the concentration of MMT (or OMMT) decreased the thermal resistance. Based on the IR absorption intensity changes of regularity and conformational bands, it is found that the content of the helical structure of macromolecular chains has increased with increasing concentrations of both MMT and OMMT in the nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structure and Property of PU/MMT Nanocomposites by In-Situ Polymerization

A montmorillonite modified by octadecylammonium salt (OMMT) was prepared. A polyurethane (PU)/montmorillonite nanocomposite was synthesized by in-situ polymerization using the OMMT, poly(propylene glycol), 4,4-diphenylmethylate diisocyanate, and 1,4-butanediol. The MMT platelets were dispersed in PU matrix on a 10 ～ 50 nm scale. Compared to that of pure PU, the tensile strength and tear strength of the PU/OMMT nanocomposites increased, respectively, and the MMT platelets dispersed on a nanometer scale enhanced the PU. The temperature of initial weight loss of the PU/OMMT nanocomposites was lower than that of pure PU because of the acid catalytic action of protonated MMT platelets in the first thermodegradation step. But its temperature of initial weight loss was higher than that of pure PU because of the barrier effect of the MMT platelets in the second thermodegradation step.     

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.     

Effect of polymer matrix/montmorillonite compatibility on morphology and melt rheology of polypropylene nanocomposites

In this study, Ca²⁺‐montmorillonite (Ca²⁺‐MMT) and organo‐montmorillonite (OMMT) were modified by three compatibilizers with different degrees of polarity [poly(ethylene glycol) (PEG), alkyl‐PEG, and polypropylene (PP)‐g‐PEG]. PP/MMT nanocomposites were prepared by melt blending and characterized using X‐ray diffraction and transmission electron microscopy. The results showed the degree of dispersion of OMMT in the PP/PP‐g‐PEG/OMMT (PMOM) nanocomposite was considerably higher than those in the PP/PEG/OMMT and PP/alkyl‐PEG/OMMT nanocomposites, which indicated that the dispersion was relative to the compatibility between modified OMMT and PP matrix. Linear viscoelasticity of PP/MMT nanocomposites in melt states was investigated by small amplitude dynamic rheology measurements. With the addition of the modified MMT, the shear viscosities and storage modulus of all the PP/MMT nanocomposites decreased. It can be attributed to the plasticization effect of PEG segments in the three modifiers. This rheological behavior was different from most surfactant modified MMT nanocomposites which typically showed an increase in dynamic modulus and viscosity relative to the polymer matrix. The unusual rheological observations were explained in terms of the compatibility between the polymer matrix and MMT. In addition, the mechanical properties of PP/MMT nanocomposites were improved. A simultaneous increase in the tensile strength and toughness was observed in PP/PMOM nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of clay modification on the morphological,mechanical, and thermal properties of polyamide 6/polypropylene/montmorillonite nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic montmorillonite (OMMT) were prepared by melt compounding. The sodium montmorillonite (Na‐MMT) was modified using three different types of alkyl ammonium salts, namely dodecylamine, 12‐aminolauric acid, and stearylamine. The effect of clay modification on the morphological and mechanical properties of PA6/PP nanocomposites was investigated using x‐ray diffraction (XRD), transmission electron microscopy (TEM), tensile, flexural, and impact tests. The thermal properties of PA6/PP nanocomposites were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and heat distortion temperature (HDT). XRD and TEM results indicated the formation of exfoliated structure for the PA6/PP nanocomposites prepared using stearylamine modified montmorillonite. On the other hand, a mixture of intercalated and exfoliated structures was found for the PA6/PP nanocomposites prepared using 12‐aminolauric acid and dodecylamine modified montmorillonite. Incorporation of OMMT increased the stiffness but decreased the ductility and toughness of PA6/PP blend. The PA6/PP nanocomposite containing stearylamine modified montmorillonite showed the highest tensile, flexural, and thermal properties among all nanocomposites. This could be attributed to better exfoliated structure in the PA6/PP nanocomposite containing stearylamine modified montmorillonite. The storage modulus and HDT of PA6/PP blend were increased significantly with the incorporation of both Na‐MMT and OMMT. The highest value in both storage modulus and HDT was found in the PA6/PP nanocomposite containing stearylamine modified montmorillonite due to its better exfoliated structure. POLYM. COMPOS., 31:1156–1167, 2010. © 2009 Society of Plastics Engineers     

Preparation and characterization of polystyrene–clay nanocomposites by free‐radical polymerization

The polymerizable cationic surfactant, vinylbenzyldimethylethanolammouium chloride (VBDEAC), was synthesized to functionalize montmorillonite (MMT) clay and used to prepare exfoliated polystyrene–clay nanocomposites. The organophilic MMT was prepared by Na⁺ exchanged montmorillonite and ammonium cations of the VBDEAC in an aqueous medium. Polystyrene–clay nanocomposites were prepared by free‐radical polymerization of the styrene containing intercalated organophilic MMT. Dispersion of the intercalated montmorillonite in the polystyrene matrix determined by X‐ray diffraction reveals that the basal spacing is higher than 17.6 nm. These nanocomposites were characterized by differential scanning calorimetry (DSC), transmission electron micrograph (TEM), thermal gravimetric analysis (TGA), and mechanical properties. The exfoliated nanocomposites have higher thermal stability and better mechanical properties than the pure polystyrene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1370–1377, 2002     

尼龙12/OMMT纳米复合粉末的制备及性能

利用十八烷基三甲基溴化铵(OTAB)对蒙脱土(MMT)进行有机改性,并通过溶液插层法制备尼龙12/有机蒙脱土(PA12/OMMT)纳米复合粉末。利用X射线衍射、傅立叶变换红外光谱、扫描电子显微镜等手段对改性后的MMT及PA12/OMMT纳米复合粉末的结构和微观形貌进行表征,并将复合粉末热压成型制成标准件,测试其力学性能和热性能。结果表明,经过有机改性,MMT的层间距由1.24 nm增加到了2.13 nm,且改性后的MMT能均匀地分散在PA12基体中,PA12/OMMT纳米复合粉末的成型件在拉伸强度、弯曲强度、冲击强度和热性能方面都优于纯PA12粉末。PA12/OMMT纳米复合粉末为选择性激光烧结技术(SLS)提供了一种性能良好的粉末材料。     

双子阳离子表面活性剂改性蒙脱土的制备与表征

合成了新型双子阳离子表面活性剂Gemini-16,并用其对钠基蒙脱土进行改性。红外光谱(FTIR)、热重(TGA)分析表明,Gemini-16已插层到蒙脱土片层间。X射线衍射(XRD)表明,改性后蒙脱土层间距从1.47 nm增加到3.48 nm。分散性实验表明,经Gemini-16改性的蒙脱土在液体石蜡中表现出很好的相容性和分散性,改性效果优于目前常用的CTAB处理效果,更有利于聚合物单体进入蒙脱土层间形成聚合物/蒙脱土纳米复合材料。     

Synthesis of Na+‐montmorillonite/amphiphilic polyurethane nanocomposite via bulk and coalescence emulsion polymerization

Polyurethane/clay nanocomposites have been synthesized using Na⁺‐montmorillonite (Na⁺‐MMT)/amphiphilic urethane precursor (APU) chains that have hydrophilic polyethylene oxide (PEO) chains and hydrophobic segments at the same molecules. Nanocomposites were synthesized through two different crosslinking polymerization methods. One is UV curing of melt mixed APU/Na⁺‐MMT mixtures; the other is coalescence polymerization of APU/Na⁺‐MMT emulsions. These two kinds of composites had intercalated silicate layers of Na⁺‐montmorillonite by insertion of PEO chains in APU chains, which was confirmed by X‐ray diffraction measurement and transmission electron microscopy. These composite films also showed improved mechanical properties compared to pristine APU films. Although the two kinds of nanocomposites exhibited the same degree of intercalation and were synthesized based on the same precursor chains, these nanocomposite films had the different mechanical properties. Nanocomposites synthesized using APU/Na⁺‐MMT emulsions, having microphase‐separated structure, had greater tensile strength than those prepared with melt‐mixed APU/Na⁺‐MMT mixtures. Location of intercalated Na⁺‐MMT by PEO chains at the oil–water interface also could be confirmed by rheological behavior of the APU/Na⁺‐MMT/water mixture. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3130–3136, 2003     

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.     

Nanocomposites Based on Chitosan-Graft-Poly(N-Vinyl-2-Pyrrolidone): Synthesis,Characterization, and Biological Activity

Organophilic montmorillonite (OMMT) was synthesized by cationic exchange between Na⁺-MMT and N-octyl-N-vinyl-2-pyrrolidonium bromide. Chitosan graft copolymer nanocomposites were synthesized by grafting N-vinyl-2-pyrrolidone onto chitosan in aqueous acetic acid in the presence of OMMT using free radical polymerization. The chemical structures were verified by FTIR. Scanning electron microscopy showed a surface roughness for chitosan graft nanocomposites. Wide-angle X-ray diffraction confirmed the intercalation of grafted chitosan chains between OMMT galleries. Thermogravimetric analysis indicated that the thermal stability of grafted chitosan was enhanced by OMMT incorporation. Preliminary studies showed that the nanocomposites exhibited antimicrobial activity compared with chitosan graft copolymer.     

聚酰胺6/环氧树脂改性蒙脱土纳米复合材料的制备与性能

采用环氧树脂改性蒙脱土（MMT）得到有机化蒙脱土（OMMT）,再用熔融插层法制备了聚酰胺6 （PA6）/ OMMT纳米复合材料。采用X射线衍射仪、透射电子显微镜、万能材料试验机、热重分析仪等研究了PA6/OMMT复合材料的形态结构、力学性能和热稳定性。结果表明,经环氧树脂改性得到的OMMT的层间距明显增加,从未改性的1.22 nm增加到5.13 nm,并以纳米尺度分散于PA6基体中;随着OMMT含量的增加,PA6/ OMMT复合材料的强度和模量增加,热变形温度提高,其拉伸强度可达76 MPa,弯曲模量达到3.462 GPa,热变形温度为134 ℃;PA6/ OMMT复合材料失重10 %时的温度为422 ℃,比纯PA6的406 ℃提高了16 ℃,改善了PA6的热稳定性。     

Evaluation of amine functionalized polypropylenes as compatibilizers for polypropylene nanocomposites

The compatibilization effects provided by amine functionalized polypropylenes versus those of a maleated polypropylene, PP-g-MA, for forming polypropylene-based nanocomposites were compared. Amine functionalized polypropylenes were prepared by reaction of maleated polypropylene, PP-g-MA, with 1,12-diaminododecane in the melt to form PP-g-NH₂ which was subsequently protonated to form PP-g-NH₃⁺. Nanocomposites were prepared by melt processing using a DSM microcompounder (residence time of 10 min) by blending polypropylene and these functionalized materials with sodium montmorillonite, Na-MMT, and with an organoclay. X-ray and transmission electron microscopy plus tensile modulus tests were used to characterize those nanocomposites. Composites based on Na-MMT as the filler showed almost no improvement of tensile modulus compared to the polymer matrix using any of these functionalized polypropylenes, which indicated that almost no exfoliation was achieved. All the compatibilized nanocomposites using an organoclay, based on quaternary ammonium surfactant modified MMT, as the filler had better clay exfoliation compared to the uncompatibilized PP nanocomposites. Binary and ternary nanocomposites using amine functionalized polypropylenes had good clay exfoliation, but no advantage over those using PP-g-MA. The PP-g-MA/organoclay and PP/PP-g-MA/organoclay nanocomposites showed the most substantial improvements in terms of both mechanical properties and clay exfoliation.     

蒙脱石有机化对PVA/蒙脱石复合薄膜的性能影响

以精制钠基蒙脱石(Na-MMT)、有机化蒙脱石(OMMT)和聚乙烯醇(PVA)为原料,通过水溶液插层-流延成膜法制备纳米复合薄膜。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和热重分析(TGA)对复合材料的结构和性能进行表征,重点探讨蒙脱石有机化对PVA/MMT复合薄膜性能的影响。结果表明Na-MMT和OMMT纳米颗粒在PVA基体中均得到了良好分散;有机改性剂的存在促使PVA/MMT复合薄膜的MMT片层间距扩撑更大,但由于其与PVA相容性较差,导致有效插入MMT片层间的PVA分子较少,PVA/MMT复合薄膜的热稳定性改善效果不明显。     

Water absorption behavior of different types of organophilic montmorillonite‐filled polyamide 6/polypropylene nanocomposites

The water absorption behavior of different types of organophilic montmorillonite (OMMT)‐filled polyamide 6/polypropylene nanocomposites with and without compatibilizers (maleated PP or PP‐g‐MA and maleated styrene‐ethylene/butylene‐styrene or SEBS‐g‐MA) was evaluated. Four different types of OMMT, i.e., dodecylamine‐modified MMT (D‐MMT), 12 aminolauric acid‐modified MMT (A‐MMT), stearylamine‐modified MMT (S‐MMT), and commercial organo‐MMT (C‐MMT) were used as reinforcement. The water absorption response of the nanocomposites was studied and analyzed by tensile test and morphology assessment by scanning electron microscopy (SEM). The kinetics of water absorption of the nanocomposites conforms to Fick's law. The M_m and D are dependent on the types of OMMT and compatibilizers. The equilibrium water content and diffusivity of PA6/PP blend were increased by the addition of OMMT but decreased in the presence of compatibilizers. On water absorption, both strength and stiffness of the nanocomposites were drastically decreased, but the ductility was remarkably increased. Both PP‐g‐MA and SEBS‐g‐MA played an effective role as compatibilizers for the nanocomposites. This was manifested by their higher retention ability in strength and stiffness (in the wet and re‐dried states), reduced the equilibrium water content, and diffusivity of the nanocomposites. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Investigation of corrosion protection performance of epoxy coatings modified by polyaniline/clay nanocomposites on steel surfaces

In this study, polyaniline (PANI) and polyaniline/clay nanocomposites were prepared via in situ oxidative polymerization. The morphology of nanocomposites structures was investigated by X-ray diffraction (XRD). The chemical structures of PANI and PANI/clay nanocomposites were examined via Fourier transform infrared (FT-IR) spectroscopy. Polyaniline-based pigments were introduced into epoxy paint and applied on steel substrates. The effect of clay addition and the type of clay cation, including Na⁺ in natural clay (MMT) and alkyl ammonium ions in organo-modified montmorillonite (OMMT), on the anticorrosion performance of epoxy-based coatings was investigated through electrochemical Tafel test, electrochemical impedance spectroscopy and immersion measurements in NaCl solution. The stability of the adhesion of the neat and modified epoxy coatings to the steel surface was also examined. The results indicated that introduction of PANI/OMMT nanocomposite into epoxy paint results in improved anticorrosion properties in comparison with PANI/MMT and neat PANI.     

Effects of acid neutralization on the morphology and properties of organoclay nanocomposites formed from K+ and Na+ poly(ethylene-co-methacrylic acid) ionomers

Nanocomposites were prepared by melt blending various sodium (Na⁺) and potassium (K⁺) ionomers formed from poly(ethylene-co-methacrylic acid) and the M₂(HT)₂ organoclay formed from montmorillonite (MMT). The effects of the neutralization level of the acid groups and the precursor melt index on the morphology and properties of the nanocomposites were evaluated using stress-strain analysis, wide angle X-ray scattering (WAXS), and transmission electron microscopy (TEM) coupled with particle analysis. The aspect ratio generally increases as the neutralization level increases, except for Na⁺ ionomer nanocomposites with neutralization levels >50%. It appears from both WAXS and TEM analyses that Na⁺ ionomer nanocomposites have higher levels of MMT exfoliation and particle orientation in the flow direction than K⁺ ionomer nanocomposites. DSC results indicate that the level of crystallinity in the Na⁺ ionomers generally increases slightly with MMT addition, while the crystallinity in the K⁺ ionomers decreases slightly with MMT addition. The relative modulus of K⁺ ionomer nanocomposites increases as the degree of neutralization increases. The relative moduli of Na⁺ ionomer nanocomposites are higher than the relative modulus of K⁺ ionomer nanocomposites, likely due to the increased crystallinity of the Na⁺ ionomers and the decreased crystallinity of the K⁺ ionomers upon addition of MMT, the higher exfoliation levels measured by the aspect ratios and the particle densities, and the higher particle orientation indicated by TEM and WAXS. The relative modulus generally increases as the aspect ratio increases. The elongation at break generally decreases as the MMT content increases and as the neutralization level increases for both ionomer types. The fracture energy of most of the ionomers increases with the addition of MMT, reaches a maximum between 2.5 and 5 wt% MMT, and then decreases upon further MMT addition.     

Rigid PVC/(layered silicate) nanocomposites produced through a novel melt‐blending approach

On the basis of the fusion behavior of poly(vinyl chloride) (PVC), the influence of compounding route on the properties of PVC/(layered silicate) nanocomposites was studied. Four different compounding addition sequences were examined during the melt compounding of PVC with montmorillonite (MMT) clay, including (a) a direct dry mixing of PVC and nanoclay, (b) an addition of nanoclay at compaction, (c) an addition of nanoclay at the onset of fusion, and (d) an addition of nanoclay at equilibrium torque. Both unmodified sodium montmorillonite (Na⁺‐MMT) and organically modified montmorillonite (Org.‐MMT) clays were used, and the effect of the addition sequence of the clay during compounding on its dispersion in the matrix was evaluated by X‐ray diffraction and transmission electron miscroscopy. The surface color change, dynamic mechanical analysis, and flexural and tensile properties of PVC/clay nanocomposites were also studied. The experimental results indicated that both the extent of property improvement and the dispersion of nanoparticles in PVC/(layered silicate) nanocomposites are strongly influenced by the degree of gelation achieved in PVC compounds during processing. The addition of nanoclay to PVC must be accomplished at the onset of fusion, when PVC particles are reduced in size, in order to produce nanocomposites with better nanodispersion and enhanced mechanical properties. Overall, rigid PVC nanocomposites with unmodified clay (Na⁺‐MMT) were more thermally stable and exhibited better mechanical properties than their counterparts with organically modified clay (Org.‐MMT). J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers