Synthesis and characterization of poly(methyl methacrylate)/montmorillonite nanocomposites by in situ bulk polymerization

Poly(methyl methacrylate)/montmorillonite (MMT) nanocomposites were prepared by in situ bulk polymerization. The results showed that the silicone coupling agent affected the structure and properties of hybrid materials. XRD analysis showed that the dispersion of clay in nanocomposites with silicone‐modified organophilic MMT was more ordered than that in nanocomposites with unmodified organophilic MMT. The glass transition temperature (T_g) of the nanocomposites was 6–15°C higher and the thermal decomposition temperature (T_d) was 100–120°C higher than those of pure PMMA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2256–2260, 2003     

Morphology,thermal, and mechanical properties of flame‐retardant silicone rubber/montmorillonite nanocomposites

Flame‐retardant methyl vinyl silicone rubber (MVMQ)/montmorillonite nanocomposites were prepared by solution intercalation method, using magnesium hydroxide (MH) and red phosphorus (RP) as synergistic flame‐retardant additives, and aero silica (SiO₂) as synergistic reinforcement filler. The morphologies of the flame‐retardant MVMQ/montmorillonite nanocomposites were characterized by environmental scanning electron microscopy (ESEM), and the interlayer spacings were determined by small‐angle X‐ray scattering (SAXS). In addition to mechanical measurements and limited oxygen index (LOI) test, thermal properties were tested by thermogravimetric analysis (TGA). The decomposition temperature of the nanocomposite that contained 1 wt % montmorillonite can be higher (129°C) than that of MVMQ as basal polymer matrix when 5% weight loss was selected as measuring point. This kind of silicone rubber nanocomposite is a promising flame‐retardant polymeric material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3275–3280, 2006     

Synthesis and characterization of poly(methyl methacrylate)/polysiloxane composites and their coating properties

A series of poly(methyl methacrylate) (PMMA)/polysiloxane composites and their coatings were prepared as designed. A copolymer (PMMAVTEOS) containing methyl methacrylate (MMA) and vinyltriethoxysilane (VTEOS) was prepared by free radical polymerization and then condensed with methyl triethoxysilane (MTES) to fabricate PMMA/polysiloxane composites; their corresponding coatings were obtained via a curing process in an oven (at 75 °C). The polymers were characterized by gel permeation chromatography and Fourier transform infrared spectroscopy. The surface property, hardness, water contact angle, thermal stability, and optical property of the coatings were investigated by scanning electron microscopy, pencil hardness testing, water contact angle testing, thermogravimetric analysis, and ultraviolet–visible spectroscopy, respectively. The results showed that, after addition of MMA, the pencil hardness of the coatings was reduced from 6H to 2H and the thermal stability decreased from 365 to 314 °C. However, it increased the flexibility and adhesion properties (the water contact angle increased from 94.7° to 102.1°). The transparent PMMA/polysiloxane coatings showed excellent scratch resistance, a smooth surface, high thermal stability, and a strong adhesion property. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46358.     

Preparation and characterization of poly(methyl methacrylate)/reactive montmorillonite nanocomposites

The poly(methyl methacrylate) (PMMA)/reactive montmorillonite nanocomposites were prepared by emulsion polymerization. The double bonds were introduced to both the surfaces and interlayers of the montmorillonites to obtain the reactive montmorillonites. The structure of the nanocomposites measured by wide angle X‐ray diffraction (WAXD) indicated that the montmorillonites were exfoliated. The average molecular weight of the nanocomposites revealed by gel permeation chromatography (GPC) was larger than that of pure PMMA. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicated that the thermal properties of the nanocomposites were enhanced and could be affected by the amount of the reactive montmorillonites. In addition, the tensile properties of the nanocomposites measured by an Instron testing machine improved and the nanocomposites including 3 wt% reactive montmorillonites showed the best tensile strength. The Young's modulus increased with the addition of the reactive montmorillonites. The aging properties of the nanocomposites had an improvement compared with pure PMMA. The optical properties assessed by UV‐Visible spectroscopy revealed that the transmittance decreased as the amount of the reactive montmorillonites increased. Finally, the mechanism to prepare PMMA/reactive montmorillonite nanocomposites was proposed. POLYM. COMPOS., 37:2396–2403, 2016. © 2015 Society of Plastics Engineers     

Preparation and characterization of thermally stable phosphonium organoclays and their use in poly(ethylene terephthalate) nanocomposites

Purification of montmorillonite rich bentonite followed by surface modification using organic salts was performed. The bentonite was purified by sedimentation and then surface modified by ion exchange using alkyl‐ and aryl‐based phosphonium salts. The thermal stability, morphology, melt flow, and mechanical properties of the poly(ethylene terephthalate) (PET) nanocomposites prepared with these organoclays were studied with and without using a reactive elastomeric compatibilizer. TEM results showed that the alkyl based organoclay exhibited better dispersion and thus, higher tensile strength and elongation at break in the PET/organoclay/elastomer ternary nanocomposites than the aryl‐based organoclay did. The notched Charpy impact strength of PET increased from 2.9 to 4.7 kJ m^?2 and 3.4 kJ m^?2 for alkyl and aryl phosphonium organoclay‐based ternary nanocomposites, respectively. Upon compounding PET with alkyl and aryl phosphonium organoclays, the onset decomposition temperature of PET increased from 413°C to 420°C and 424°C, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polymerization kinetics and thermal properties of poly(alkyl methacrylate)/organomodified montmorillonite nanocomposites

The effect of the presence of organomodified nano‐montmorillonite (MMT) on the free radical polymerization kinetics of either ethyl methacrylate or butyl methacrylate was investigated. The in situ polymerization technique was selected with dispersion of the MMT nanoparticles into the corresponding monomer and subsequent bulk radical polymerization. Different types and amounts of MMT were used, including a sodium and several organomodified clays under the trade names Cloisite Na⁺ and Cloisite 15A, 25A and 30B. Reaction kinetics was measured gravimetrically and the nanocomposites formed were characterized with X‐ray diffraction (structure), gel permeation chromatography (molar mass distribution) and differential scanning calorimetry (glass transition temperature). Thermal degradation characteristics were measured with thermogravimetric analysis. Additional experiments with styrene as monomer were carried out in order to make clear the effect of the nanofiller on the polymerization kinetics. It was found that the presence of the bulk ammonium salt used as the organic modifier in MMT could influence the reaction kinetics when diffusion‐controlled phenomena occur. Reaction rate was slightly enhanced and nanocomposites with improved thermal stability were formed. In addition, the average molar mass and glass transition temperature of the polymer in the nanocomposites were slightly higher compared to the neat polymer. Copyright © 2012 Society of Chemical Industry     

Synthesis and characterization of sPS/montmorillonite nanocomposites

The present work analyzed the possibility of obtaining and producing syndiotactic polystyrene (sPS)–based nanocomposites. The work first focused on possible technology to use for intercalation from solution and melt intercalation. Using a blend of sPS with atactic polystyrene (aPS) as the matrix was also considered. Thermal analysis techniques, such as differential scanning calorimetry (DSC) and thermogravimetry (TGA), were used to study the thermal properties and stability of the nanocomposites obtained and to select the most appropriate nanocharges. The effect of the introduction of nanofillers on these properties also was evaluated. X–ray diffraction was used to investigate the degree of clay exfoliation. Finally, mechanical characterization of the nanocomposites obtained was performed and compared to that of the pure material. The tests demonstrated that nanodispersion of phyllosilicate layers improved the mechanical behavior of the polymers analyzed, especially the annealed sPS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4957–4963, 2006     

Effect of flake size on thermal properties of graphene oxide/poly(methyl methacrylate) composites prepared via in situ polymerization

The effect of graphene oxide (GO) flake size on thermal properties of GO/poly(methyl methacrylate) (GO/PMMA) composites prepared via in situ polymerization was investigated. Two styles of GO sheets were synthesized from different sizes of graphite powders by modified Hummers' method and GO/PMMA composites with GO of different sizes were prepared via in situ polymerization. Transmission electron microscopy verified that GO sheets produced from large graphite powders was obviously larger than that from small graphite powders. The similar number of layers and disorder degree of two types of GO sheets were proved by X‐ray diffraction and Raman, respectively. X‐ray diffraction and scanning electron microscopy results of GO/composites proved the homogenous dispersion of both two types of GO sheets in polymer matrix. Dynamic mechanical analysis and thermogravimetric analysis results showed that large GO sheets exhibit better improvement than small GO sheets in thermal properties of the composites. Compared with neat PMMA, the glass transition temperature and decomposition temperature of the composites with large GO sheets (0.20 wt %) were increased by 15.9 and 25.9 °C, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46290.     

Preparation and properties of poly(lactic acid)/lignin-modified polyvinyl acetate composites

Poly(lactic acid)(PLA) has good application in the field of packaging because of its good biodegradability, tensile strength, and film-forming properties. However, the disadvantages of high brittleness and high cost limit the wider application of PLA. PLA/lignin-modified polyvinyl acetate (L-PVAc) composites with excellent toughness were prepared by melt blending PLA with modifier L-PVAc. The mechanical properties, thermal properties and morphology of the composites were characterized to evaluate the effect of L-PVAc content on the properties of the composites. The results showed that the introduction of L-PVAc could increase the impact strength, elongation at break, glass transition temperature, melting temperature and the degree of crystallinity of PLA/L-PVAc composites. When the L-PVAc content reached up to 20.0 wt%, the impact strength, elongation at break, glass transition temperature, melting temperature and the degree of crystallinity of the composites were increased by 298.2%, 167.5%, 3.8%, 1.8%, and 78.8%, respectively compared to pure PLA due to the good toughness of PVAc and heterogeneous nucleation of lignin. This research can promote the high-value utilization of lignin and the application of PLA in the fields of clothing, agriculture, medical and hygiene.     

Suspension polymerization of poly(methyl methacrylate)/clay nanocomposites

Polymer/clay nanocomposites (PCNs) of poly(methyl methacrylate) and an organically modified clay, Cloisite 15a, were synthesized in situ with a suspension polymerization technique. The amount of clay present in the PCNs was varied to provide a better understanding of the effect of the clay on the properties of the polymer matrix. However, unexpectedly, we found that the concentration of clay had a dramatic impact on the molecular weight of the polymer matrix, and a relationship between the clay concentration and polymer molecular weight was determined. The PCNs were characterized with size exclusion chromatography (SEC), X‐ray diffraction, transmission electron microscopy, and oscillatory shear rheology. From oscillatory shear rheology, the full master curves for the PCNs were obtained by application of the time–temperature superposition principle. To enable the effect of the clay on the rheology to be quantified, the experimental data was compared to the time‐dependent diffusion model of des Cloizeaux for polydisperse polymer melts, which enabled the polydispersity to be incorporated through the use of the molecular weight distribution obtained via SEC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and thermal properties of hybrid nanocomposites of poly(methyl methacrylate)/octavinyl polyhedral oligomeric silsesquioxane blends

A series of poly(methyl methacrylate) (PMMA)/octavinyl polyhedral oligomeric silsesquioxane (POSS) blends were prepared by the solution‐blending method and characterized with Fourier transform infrared, X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis techniques. The glass‐transition temperature (T_g) of the PMMA–POSS blends showed a tendency of first increasing and then decreasing with an increase in the POSS content. The maximum T_g reached 137.2°C when 0.84 mol % POSS was blended into the hybrid system, which was 28.2°C higher than that of the mother PMMA. The X‐ray diffraction patterns, transmission electron microscopy micrographs, and Fourier transform infrared spectra were employed to investigate the structure–property relationship of these hybrid nanocomposites and the T_g enhancement mechanism. The results showed that at a relatively low POSS content, POSS as an inert diluent decreased the interaction between the dipolar carbonyl groups of the homopolymer molecular chains. However, a new stronger dipole–dipole interaction between the POSS and the carbonyl of PMMA species formed at the same time, and a hindrance effect of nanosize POSS on the motion of the PMMA molecular chain may have played the main role in the T_g increase of the hybrid nanocomposites. At relatively high POSS concentrations, the strong dipole–dipole interactions that formed between the POSS and carbonyl groups of the PMMA gradually decreased because of the strong aggregation of POSS. This may be the main reason for the resultant T_g decrease in these hybrid nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(vinyl chloride)/metallic oxides/organically modified montmorillonite nanocomposites: Preparation,morphological characterization,and modeling of the mechanical properties

Poly(vinyl chloride), metallic oxides (from copper, molybdenum, and zinc), and organically modified montmorillonite (O‐MMT) nanocomposites were prepared in a melt‐blending or intercalation‐in‐the‐molten‐state process. The morphology of the nanocomposites was evaluated with X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Properties, such as the mechanical, thermal, and electrical properties, and the dynamic thermal stability against dehydrochlorination were also evaluated. Nanocomposites with a hybrid intercalated/exfoliated structure were obtained in all of the situations considered, as demonstrated by the XRD and TEM results and indirectly by the increment of Young's modulus of the formulations with increasing amount of O‐MMT incorporated. The modeling of Young's modulus by the Halpin–Tsai, Hui–Shia, and Lewis–Nielsen theories showed that the process of nanocomposite preparation allowed the aspect ratio of the clay particles to increase; these values were comparable to those nanocomposites obtained by other researchers with different polymeric matrices and methodologies. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The preparation and physical properties of UP/montmorillonite nanocomposite by UV radiation curing

This article describes the preparation and properties of unsaturated polyester (UP)/montmorillonite (MMT) nanocomposite by UV radiation. Benzildimethylketal and 1‐hydroxy cyclohexyl phenyl ketone (HCPK) as a photoinitiator in UP were photolyzed under nitrogen condition. Analysis of X‐ray diffraction patterns of the composites shows that the interlayer spacing of MMT is substantially increased. The type and amount of photoinitiator affects the level of improvement in mechanical properties, and our results suggest that HCPK is a more efficient photoinitiator of UP curing reaction. The interaction between photoinitiators and MMT should be considered to acquire the reinforcement effect of the dispersed MMT nanolayers. The properties of nanocomposite are dependent upon the amount of MMT. The effect of MMT concentration on thermal and dielectric properties is also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3609–3615, 2006     

Poly(methyl methacrylate)/montmorillonite nanocomposites prepared by bulk polymerization and melt compounding

This article focuses on structural, thermal, and mechanical properties of nanocomposites in dependence of preparation method and poly(methyl mathacrylate) (PMMA)/organically modified montmorillonite (OMMT) ratio. PMMA/OMMT nanocomposites were prepared by bulk polymerization and by melt compounding. Properties of nanocomposites of the same composition prepared by the two methods were compared. It was observed that nanocomposites prepared via melt compounding at 200°C had a highly oriented structure with lower interlayer spacing values than nanocomposites prepared via bulk polymerization. Two reasons for the observed smaller interlayer spacing obtained by melt compounding were identified. The first is enhanced PMMA penetration and/or formation between layers in the case of bulk polymerization, which was confirmed by determination of stronger interactions between OMMT and PMMA by Soxhlet extraction, infrared spectroscopy, and differential dynamic calorimery. The second reason for smaller interlayer spacing for nanocomposites prepared by melt compounding is organic modifier degradation during melt compounding process, which was confirmed by thermogravimetric analysis. Both reasons lead to the fracture of melt compounded nanocomposites on the OMMT‐polymer interface, which was observed by scanning electron microscopy. For nanocomposites with disoriented structure and larger interlayer spacing prepared via bulk polymerization the fracture occurred in the polymer matrix. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Reinforcement of graphene nanoplatelets on plasticized poly(lactic acid) nanocomposites: Mechanical,thermal, morphology,and antibacterial properties

Plasticized poly(lactic acid) (PLA)‐based nanocomposites filled with graphene nanoplatelets (xGnP) and containing poly(ethylene glycol) (PEG) and epoxidized palm oil (EPO) with ratio 2 : 1 (2P : 1E) as hybrid plasticizer were prepared by melt blending method. The key objective is to take advantage of plasticization to increase the material ductility while preserving valuable stiffness, strength, and toughness via addition of xGnP. The tensile modulus of PLA/2P : 1E/0.1 wt % xGnP was substantially improved (30%) with strength and elasticity maintained, as compared to plasticized PLA. TGA analysis revealed that the xGnP was capable of acting as barrier to reduce thermal diffusion across the plasticized PLA matrix, and thus enhanced thermal stability of the plasticized PLA. Incorporation of xGnP also enhanced antimicrobial activity of nanocomposites toward Escherichia coli, Salmonella typhimurium, Staphylococcus aureus, and Listeria monocytogenes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41652.     

Preparation,characterization, and thermal properties of poly (methyl methacrylate)/boron nitride composites by bulk polymerization

Poly (methyl methacrylate)/boron nitride (PMMA/BN) composites were prepared by dispersing BN particles into methyl methacrylate monomer phase by bulk polymerization method. BN particles modified with silane coupling agent, γ‐methacryloxypropyl trimethoxy silane, were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Effects of modified BN particle content on thermal conductivity were investigated, and the experimental values were compared with those of theoretical and empirical models. With 16 wt% of BN particles, the thermal conductivity of the composite was 0.53 W/(m·K), 1.8 times higher than that of pure PMMA. The microstructures of the PMMA/BN composites were examined by scanning electron microscopy, energy‐dispersive X‐ray analysis, and transmission electron microscopy. Dynamic mechanical analysis and thermogravimetric analysis traces also corroborated the confinement of the polymer in an inorganic layer by exhibiting an increase in glass‐transition temperatures and weight loss temperatures in the thermogram. Mechanical properties and electrical insulation property of the PMMA/BN composites were also determined. These results showed that PMMA/BN composites may offer new technology and business opportunities. POLYM. COMPOS., 36:1675–1684, 2015. © 2014 Society of Plastics Engineers     

Preparation and properties of poly(methyl methacrylate)/iron carbonate(p) nanocomposites

The mass transport of methanol mixed with ferric chloride hexahydrate (FeCl₃ · 6H₂O) in poly(methyl methacrylate) and poly(methyl methacrylate)/iron carbonate particulate_(p) nanocomposites is prepared by chemical vapor crystallization and the resulting materials, which are subjected to characterization to evaluate thermal and optical properties, have been investigated. Mass transport is an anomalous and endothermic process and satisfies the van't Hoff plot. We have prepared successfully poly(methyl methacrylate)(PMMA)/iron carbonate particulates nanocomposites using CO₂ gas slowly diffused into saturated solvent mixture‐treated poly(methyl methacrylate) for 48 h. After SEM observation, approximately 80 nm iron carbonate particulates were precipitated and evenly distributed in the poly(methyl methacrylate) matrix. In comparison with solvent mixture‐treated PMMA, the cut‐off wavelength of transmittance in nanocomposites shifts to the shorter wavelength side (red shift). The presence of nanoscale iron carbonate particulates increased the glass transition temperature of the nanocomposites as determined by differential scanning calorimeter, and the glass transition temperature increased with increasing content of nanoscale iron carbonate particulates. The FTIR spectra of solvent mixture‐treated poly(methyl methacrylate) and nanocomposites are also studied. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2329–2338, 2005     

Synthesis and characterization of poly(glycidyl methacrylate)/Na‐montmorillonite nanocomposites

Poly(glycidyl methacrylate)/Na–montmorillonite nanocomposites were synthesized by free‐radical polymerization of glycidyl methacrylate containing dispersed montmorillonite. By changing the concentration of glycidyl methacrylate several polymer–clay nanocomposites were prepared and the resulting nanocomposites were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The results indicated that the properties of the composite were significantly improved. The thermogravimetric analysis results revealed that the degradation temperatures of nanocomposites were higher than that of pure polymer and the thermal degradation rates decreased. Examination of these materials by scanning electron microscopy showed that the clay layers are dispersed homogenously in the polymer matrix and the formation of intercalation nanostructure. Furthermore, adsorptive, moisture regain, and water uptake properties of nanocomposites were also investigated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1532–1538, 2004     

Synthesis,characterization, and conductivity studies of polypyrrole/copper sulfide nanocomposites

Nanocomposites of polypyrrole (PPy) containing copper sulfide (CuS) were synthesized by an in situ chemical oxidative polymerization. The nanocomposites were characterized by FTIR, SEM, XRD, DSC, TGA, and conductivity studies. The FTIR spectra ascertained the chemical interlinking of polypyrole with metal sulfide nanoparticles. Morphological analysis showed that the nanoparticles were uniformly covering the entire substrate. The XRD pattern reveals that the nanoparticle incorporated polypyrrole showed a crystalline nature and the crystallinity of the polymer increases with increase in concentration of CuS nanoparticles. From DSC, an increase in glass transition temperature shows the increased orderness in the polymer composite than in the pure polypyrrole. Thermal analysis (TGA) of the composite showed a progressive increase in the thermal stability with increase in content of CuS. The frequency dependent electrical properties (a.c. conductivity) of the nanocomposites were higher than that of polypyrrole. The d.c. electrical conductivity increased with increase in amount of nanoparticles in the polymer matrix. The results obtained for these composites have greater scientific and technological interest. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013