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.     

In situ polymerization of polyamide 66 nanocomposites utilizing interfacial polycondensation. II. Sodium montmorillonite nanocomposites

Interfacial polycondensation (IPC) is used to generate polyamide 66 (PA66) nanocomposite using sodium montmorillonite (NaMMT), which offers better thermal stability than organically modified montmorillonite. Several approaches are used to obtain different levels of dispersion for studying the factors affecting dispersion of NaMMT layered‐silicates. These approaches include dispersing NaMMT in either aqueous media or in a compatible nonaqueous medium. Moreover, clay slurry was added to the reaction media separately or in combination with the aqueous hexamethylenediamine solution, which includes either excess amine or sodium carbonate as the by‐product scavenger, in order to study the effect of sequencing on the dispersion of NaMMT. Several characterization techniques including dynamic mechanical analysis, wide angle X‐ray diffraction, and transmission electron microscopy are used to examine the structure and relate it to the mechanical properties of the nanocomposites. Results show that in situ polymerization techniques predominantly give rise to hybrid exfoliated–intercalated NaMMT structure. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Isothermal crystallization of intercalated and exfoliated polyethylene/montmorillonite nanocomposites prepared by in situ polymerization

Polyethylene/montmorillonite (PE/MMT) nanocomposites with different dispersion states of MMT were prepared by in situ polymerization. Isothermal crystallization of the intercalated nanocomposite, in which the PE chains were confined in the MMT layers, was studied and was compared with that of the exfoliated nanocomposite. It is observed that the intercalated sample has longer induction period, longer crystallization half time and larger crystallization activation energy than the exfoliated sample, showing that crystallization of PE is retarded due to confinement of the MMT layers. Analysis of crystallization kinetics shows that Avrami exponent (n) increases gradually with crystallization temperature. However, the maximal value of n is 2.0 for the intercalated sample, but it can reach 3.0 for the exfoliated sample. It is inferred that the stems of the PE crystals confined in the MMT layers are parallel to the MMT layers. The Hoffman-Weeks extrapolation method cannot be applied in the intercalated sample because of the small lateral surface of the PE crystals. Based on the depression of the melting temperature, the specific free energy of the PE/MMT interface was estimated, which is about 1.0 mJ/cm², much smaller than the free energy of the lateral surface of PE crystals. This is attributed to the origin of the strong nucleation effect of MMT.     

Synthesis and characterization of polyurethane/montmorillonite nanocomposites by in situ polymerization

In this paper, a new type of organophilic montmorillonite, co‐treated with cetyltrimethyl ammonium bromide (CTAB) and 4,4′‐diphenymethylate diisocyanate (MDI), was modified and applied to prepare polyurethane/montmorillonite nanocomposites via in situ polymerization. The nanoscale montmorillonite layers were exfoliated and dispersed relatively homogeneously in the polyurethane matrix, and characterized by X‐ray diffraction and transmission electron microscopy. The thermal degradation temperature of the nanocomposites increased, as compared with pristine polyurethane. Dynamic mechanical analysis confirmed the constraining effect of exfoliated montmorillonite layers on polyurethane chains, which benefited the increased storage modulus and increased glass transition temperature. Tensile tests showed that the exfoliated nanocomposites were reinforced and toughened by the addition of nanometer‐size montmorillonite layers. Copyright © 2006 Society of Chemical Industry     

Preparation of exfoliated isotactic polypropylene/alkyl-triphenylphosphonium-modified montmorillonite nanocomposites via in situ intercalative polymerization

Alkyltriphenylphosphonium-modified montmorillonite(PMMT) was used to prepare TiCl₄/MgCl₂/PMMT compound catalyst and exfoliated i-PP/PMMT nanocomposites were prepared by in situ intercalative polymerization of propylene with TiCl₄/MgCl₂/PMMT catalyst. The catalytic efficiency of the above catalyst under optimum polymerization condition could reach as high as 1300 kg/(molTi h) and the combining of PMMT with Z-N catalyst do not change the stereo-regulation catalytic properties of the Z-N catalyst. The synthesized PP possessed high isotacticity, melting point and molecular weight. Wide angle X-ray diffraction (XRD) and transmission electron microscopy (TEM) examinations evidenced the nanocomposites obtained were exfoliated ones.     

Resol/montmorillonite nanocomposites obtained by in situ polymerization

Nanocomposites based on resol resin and layered silicates were obtained by in situ polymerization. An increment in the viscosity and in the content of free formaldehyde in the prepolymer with the addition of clay was observed. It could be attributed to the entrance of small phenol molecules into the galleries modifying the concentration of reagent enabled to react outside the clay galleries. The composites were cured by temperature and it was observed that the type of clay affect their dispersion in the polymer. The unmodified Cloisite^® Na⁺ montmorillonite (CNa) was the best dispersed in the polymeric matrix, whereas the modified montmorillonites (MMTs) showed an interlayer contraction after curing. It seems to be due to the loss of modifiers from the clay or to the different rate of curing inside and outside the galleries. In addition, the composite containing CNa presented higher crosslinking density than the others with modified MMTs. More adhesive strength was observed in that composite as well. It was related with the void content and the polarity of the samples. These results were compared with the ones obtained when the nanocomposites were synthesized by mixing the clay with the prepolymer. The nanocomposites with the addition of CNa showed similar properties independent of the way of synthesis used. However, it seems that the modified clays are better dispersed by mixing with the prepolymer than by in situ polymerization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal degradation kinetics of epoxy/organically modified montmorillonite nanocomposites

Nanocomposites based on a commercial epoxy resin and organically modified montmorillonites (OMMTs), containing 5 and 10 phr OMMT, were prepared and characterized. Poly(oxypropylene) diamine (Jeffamine D400) and octadecylamine were used as organic modifiers. Another poly(oxypropylene) diamine (Jeffamine D230) was used as a curing agent. The thermal degradation kinetics of the neat resin system and nanocomposites were investigated by thermogravimetric analysis. The dispersion of silicate layers within the crosslinked epoxy matrix was verified by transmission electron microscopy. The activation energy of degradation for the investigated systems was determined by the isoconversional Kissinger–Akahira–Sunose method. The thermal behavior of the neat resin systems and nanocomposites was modeled with an empirical kinetic model. The influence of organic modifiers and the OMMT loading on the thermal stability of the nanocomposites was discussed. © 2007 Wiley Periodicals, Inc. JAppl Polym Sci, 2008     

Thermal degradation mechanism of polycarbonate/organically modified montmorillonite nanocomposites

There were contradictory results about the effect of clay on polycarbonate (PC) thermal stability in previous reported papers. For ascertainment of the actual role of clay, PC nanocomposites were prepared by direct melt‐mixing PC with hexadecyl trimethyl ammonium chloride modified montmorillonite (OMT). The results of X‐ray diffractometry, transmission electron microscopy, and high‐resolution electron microscopy experiments present the formation of uniformly intercalated structure. Thermogravimetric analyses show the onset decomposition temperature of PC/OMT nanocomposites is earlier 65°C than neat PC. The mechanism of PC thermal decomposition effected by OMT was discussed in detail. It reveals that OMT can catalyze thermal degradation of PC macromolecular chains and decrease thermal stability of the nanocomposites. POLYM. COMPOS., 37:2301–2305, 2016. © 2015 Society of Plastics Engineers     

用单体插层原位聚合制备丁二烯橡胶/蒙脱土纳米复合材料

将单体插层原位聚合法引入到通用橡胶聚合中,采用阴离子取合制备了丁二烯橡胶/蒙脱土纳米复合材料,XRD分析显示蒙脱土层间距明显增大,表明实现了丁二烯插层原位聚合,FTIR分析显示蒙脱土的加入使得丁二烯橡胶微结构发生了改变。     

Preparation and properties of elastomeric polyurethane/organically modified montmorillonite nanocomposites

Elastomeric polyurethane (PU) was mixed with 1, 3, 5, 7, and 10 wt% of Cloisite 30B to obtain PU-based nanocomposites. The thermal stabilities of the obtained products were characterized by thermal analysis using a thermogravimetric analyzer (TGA), which showed that the addition of 5 wt% of organoclay to the PU increased its stability, whereas thermal stabilization was less efficient at 10 wt%. The electrical conductivities of these composites were studied as a function of temperature, and it was found that the conductivity of PU was enhanced upon using 5 wt% of organoclay. The tensile strength, elongation (%), and Young’s modulus were considerably enhanced upon increasing the organoclay content to 5 wt%, but were then decreased to some extent upon further increasing the nanoparticle loading to 10 wt%. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to study these nanocomposite structures, and it was found that the PU molecular chains were intercalated into the galleries of the silicate layers in all of the nanocomposites, and that this reached a maximum when 5 wt% of Cloisite 30B was used.     

Polypropylene/organically modified Sabah montmorillonite nanocomposites: Surface modification and nanocomposites characterization

The aim of the work is to extract, purify, and organically modify montmorillonite (MMT) of Lahad Datu, Sabah bentonite. The octadecylamine treated Sabah MMT (S‐OMMT) (2–8 wt%) was then melt blended with polypropylene (PP) and maleated polypropylene (PPgMAH) (10 wt%) via single screw nanomixer extruder followed by injection molding into test samples to examine the mechanical, thermal, and morphological properties of PP/S‐OMMT nanocomposites. Unmodified Sabah MMT (S‐MMT) and commercial grade MMT (Nanomer 1.30P) filled PP nanocomposites were also characterized for comparison purpose. X‐ray diffraction results showed that the interlayer spacing of S‐MMT increased after organic modification as Fourier transform infra‐red and elemental analysis evidenced the presence of octadecylamine. PP/S‐OMMT nanocomposites showed a better dispersion and strength compared to PP/Nanomer 1.30P nanocomposites due to its smaller MMT platelet size. differential scanning calorimetry and Thermogravimetry analysis revealed that the thermal stability and crystallinity of neat PP improved with the addition of all types of MMT. Dynamic mechanical analyzer showed that PP nanocomposites have higher storage modulus (E′) values than the neat PP over the whole temperature range. The new PP/S‐OMMT nanocomposites showed a comparable performance with PP/Nanomer 1.30P nanocomposites exhibiting promising future applications of S‐MMT in polymer/MMT nanocomposites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Preparation and properties of polyethylene/montmorillonite nanocomposites by in situ polymerization

Polyethylene (PE)/montmorillonite (MMT) nanocomposites were prepared by in situ coordination polymerization using a MMT/MgCl₂/TiCl₄ catalyst activated by Al(Et)₃. The catalyst was prepared by first diffusing MgCl₂ into the swollen MMT layers, followed by loading TiCl₄ on the inner/outer layer surfaces of MMT where MgCl₂ was already deposited. The intercalation of MMT layers by MgCl₂ and TiCl₄ was demonstrated by the enlarged interlayer spacing determined by WAXD. The nanoscale dispersion of MMT layers in the polyethylene matrix was characterized by WAXD and TEM. As a consequence, the crystallinity of the nanocomposite decreased sharply, whereas the tensile strength was significantly improved compared to that of virgin polyethylene of comparable molecular weight. The confinement of the nanodispersed MMT layers to molecular chain and the strong interaction between the nanoscale MMT layers and the resin matrix were thought to account for the decrease of crystallinity and the remarkable enhancement of strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3680–3684, 2003     

Synthesis and interfacial properties of montmorillonite/polypyrrole nanocomposites

Montmorillonite/polypyrrole (MMT/PPy) nanocomposites were prepared by the in situ polymerization of pyrrole in the presence of MMT. The morphology of the MMT/PPy nanocomposites as examined by scanning electron microscopy differs slightly from that of the untreated MMT but markedly from that of polypyrrole. X-ray photoelectron spectroscopy (XPS) showed that the materials have MMT-rich surfaces, an indication that polypyrrole is essentially intercalated in the host clay galleries. The transmission electron microscopy showed, that the interlamellar spacing of the untreated MMT increased from 1.25 to 18.9 nm, when compared to nanocomposite MMT/10.8% PPy. Moreover, XPS highlighted the cation exchange of Na⁺ from montmorillonite by K⁺ (from the oxidant) and by the positively charged polypyrrole chains. Inverse gas chromatography indicated that the nanocomposites are high surface energy materials with a dispersive contribution to the surface energy reaching 200 mJ/m² at 150 °C, for a PPy loading of 21.4 wt%. The values of the MMT/PPy nanocomposites were correlated to the changes in the specific surface area of the MMT induced by the intercalation of polypyrrole.     

Orientation of montmorillonite clay in dicyclopentadiene/organically modified clay dispersions and nanocomposites

Highly delaminated dispersions of the organically modified clay I‐28 (Nanocor, Inc.) in liquid dicyclopentadiene (DCPD) were prepared. In situ ring‐opening metathesis polymerization of I‐28/DCPD nanodispersions generated I‐28/poly(DCPD) nanocomposites. When clay/DCPD dispersions were cured under shear, alignment of clay platelets, tactoids, and small particles was captured. This orientation was confirmed by X‐ray diffraction and transmission electron microscopy. The Herman's orientation parameters were calculated for the oriented nanocomposites. Viscosities of these liquid nanodispersions exhibited thixotropic flow behavior, prior to curing. The time‐dependent viscosity effects became more pronounced with an increase in delamination. Initial viscosities increased with progressive clay platelet generation during delamination and nanodispersion within the liquid monomer. Viscosity can be used to follow clay exfoliation/delamination. Etching the surface of a 2 wt % I‐28 clay/poly(DCPD) nanocomposite with oxygen plasma eroded the matrix, exposing clay tactoids protruding from the surface. These surfaces were examined by SEM and energy dispersive X‐ray spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2743–2751, 2006     

Structure and properties of polybutadiene/montmorillonite nanocomposites prepared by in situ polymerization

Polybutadiene (PB)/Montmorillonite nanocomposites (NCs) were prepared by in situ polymerization through the anionic polymerization technique. The effects of treating method of organophilic MMT (OMMT), the type of OMMT, and the solvent used in polymerization were studied. The structure and properties of NCs were characterized using X‐ray Diffraction (XRD), transmission electron micrograph (TEM), H‐NMR spectrum, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). The consumption of BuLi was varied with different treating methods. The molecular weight distribution of PB added with OMMT (DK1) was wide, and the molecular weight distribution became narrow when OMMT‐DK1B and DK4 were added. OMMT did not disperse stably in cyclohexane, but could form a homogeneous solution in toluene and xylene. XRD and TEM showed that exfoliated NCs were obtained by in situ polymerization through the anionic polymerization technique. From the H‐NMR spectrum of PB and PB/OMMT NCs, it could be seen that the content of 1, 2 units of PB increased ～100%, while 1, 4 units decreased when 6.2 wt % of OMMT was added. The results of DSC and DMA indicated that T_g and T_dc were increased when compared with those of PB. Both storage modulus and loss modulus were increased with the addition of OMMT, and tan δ was decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3615–3621, 2006     

原位法与超临界二氧化碳法合成聚丁二烯/蒙脱土纳米复合材料

以原位插层法和超临界CO2,法合成了顺式-1,4-聚丁二烯/有机蒙脱土纳米复合材料,有机蒙脱土以剥层形态均匀地分散于聚丁二烯基体中,且有机蒙脱土的加入并没有改变聚丁二烯的微观结构,顺式结构摩尔分数高达95％以上.     

原位悬浮聚合制备酸性酚醛树脂 /蒙脱土纳米复合材料

在酸性催化剂作用下,采用悬浮聚合的方法制备了酸性酚醛树脂/蒙脱土纳米复合材料。XRD和TEM的实验结果表明该材料结构为部分剥离、部分插层型,即一部分蒙脱土被剥离为单层,而另一部分为几个片层的聚集体。     

In‐situ polymerization of polyamide 66 nanocomposites utilizing interfacial polycondensation,Part 1: Organoclay nanocomposites

Effective dispersion of organically modified montmorillonite‐layered silicates in nylon 66 is addressed by synthesizing nanocomposites in situ via interfacial polycondensation from a suspension of silicate platelets in one of the monomer phases using either a stirred or unstirred reactor, while avoiding the detrimental heat history associated with melt compounding of this high melting polymer system. The effects of mixing methodology, reaction conditions, concentration ratio, and clay content are evaluated to elucidate process mechanisms and produce high molecular weight product. Enhanced stiffness of the nanocomposites measured by tensile modulus is related to their nanoscale morphology as characterized by transmission electron microscopy and wide angle X‐ray diffraction. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Synthesis and characterization of some polyacrylate/montmorillonite nanocomposites by in situ emulsion polymerization using redox initiation system

Intercalated modification of Montmorillonite clay (MMT) with three different amino acids—Alanine, Leucine, and Phenylalanine—in the presence of hydrochloric acid followed by surface modification by methyl triethoxy silane coupling agent to produce double modified Montmorillonite clay which is characterized by X‐ray diffraction (XRD) and Thermogravimetric analysis (TGA). The data shows an increase in d‐spacing of modified clay as a result of cationic exchange. Double modified MMT clay was used in the preparation of Polyacrylate/clay nanocomposites by using an in situ redox emulsion polymerization of polyglycidylmethacrylate (PGMA) and polymethylmethacrylate (PMMA). The structure and properties of the prepared nanocomposites were achieved by XRD, TGA, and SEM. The results show that all weight loses temperatures for the nanocomposite samples are higher than that of pure polymer in both PGMA and PMMA. It is also obvious that the increasing in the clay content plays an effective role in the increasing of thermal stability of these materials. SEM shows that the clay is more homogenously dispersed in PMMA than in PGMA matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of ultraviolet‐cured bisphenol A epoxy diacrylate/montmorillonite nanocomposites with a bifunctional,reactive, organically modified montmorillonite as the only initiator via in situ polymerization

A bifunctional reactive surfactant containing a polymerizable methacrylate group and a benzophenone group, [2‐(methacryloyloxy)ethyl](4‐benzoylbenzyl)dimethylammonium bromide (MDAB), was synthesized to modify montmorillonite (MMT) for the preparation of nanocomposites via photoinduced polymerization. Fourier transform infrared, thermogravimetric analysis, and X‐ray diffraction results indicated that MDAB‐modified MMT was obtained and had intercalated structures. The morphology of the ultraviolet‐cured bisphenol A epoxy diacrylate/MMT nanocomposites prepared from the organically modified MMTs was studied with X‐ray diffraction and transmission electron microscopy, and the results showed an intercalated structure with partial exfoliation for all the samples. Experimental results from thermogravimetric analysis, differential scanning calorimetry, and mechanical property testing also indicated that the thermal and mechanical properties of the ultraviolet‐cured nanocomposites were significantly enhanced by the presence of this bifunctional, reactive, organically modified MMT. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009