Kinetic investigations on the UV‐induced photopolymerization of nanocomposites by FTIR spectroscopy

The kinetics of the photopolymerization for nanocomposites containing nanosilica with 2,2‐dimethoxy‐1,2‐diphenylethan‐1‐one or benzophenone/n‐methyl diethanolamine (BP/MDEA)as photoinitiators were studied by FTIR spectroscopy. It was found that nanocomposites containing nanosilica had higher conversion in comparison with pristine EA. The presence of MPS and ethanol accelerated the photopolymerization of nanocomposites, while the presence of water decelerated it. The photopolymerization of nanocomposites was more sensitive to oxygen than that of pristine EA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99:1429–1436, 2006     

Preparation and characterization of ultraviolet‐curable nanocomposite coatings initiated by benzophenone/n‐methyl diethanolamine

A series of ultraviolet‐curable nanocomposite coatings were prepared with condensed nanosilica particles and with benzophenone/n‐methyl diethanolamine as the initiator. The nanosilica that incorporated into the nanocomposites did not aggregate even when the nanosilica concentration was as high as 22.5%. Adding nanosilica increased the curing speed, thermal stability, and ultraviolet shielding properties of the nanocomposites without reducing the transparency of the ultraviolet‐curing coatings. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 912–918, 2005     

Synthesis and properties of polystyrene‐g‐mSiO2 filled polypropylene nanocomposites

Hydrophobically modified nanosilica was prepared from tetraethoxysilane (TEOS) and γ‐methacryloxypropyltrimethoxysilane (MPS) by a two step sol‐gel process. The polystyrene‐grafted‐modified nanosilica (PS‐g‐mSiO₂) hybrid particles were prepared by grafting polystyrene onto the resulting hydrophobically modified nanosilica by dispersion polymerization. The hybrid nanoparticles were subsequently used as the filler to fabricate polypropyrene (PP) nanocomposites. The crystallization kinetics, crystal morphology and crystallization phase component of PS‐g‐mSiO₂/PP nanocomposite were studied using a differential scanning calorimeter (DSC), polarizing optical microscopy (POM) and X‐ray diffraction (XRD). Crystallization half life (t_1/2) decreased, while the Arami exponent (n) of PS‐g‐mSiO₂/PP nanocomposite increased compared with that of virgin PP. A rheological study allowed the unambiguous characterization of the dispersibility of nanosilicas in PS‐g‐mSiO₂/PP nanocomposite. The storage modulus, melt viscosity and the elongation to break of the PS‐g‐mSiO₂/PP nanocomposite were found to be strongly dependent on the grafting of PS on nanosilicas. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Effects of epoxy resin‐modified zinc‐ion‐coated nanosilica on structural,thermal and dynamic mechanical properties of propylene‐ethylene copolymer

This paper reports a comparative study of propylene–ethylene copolymer (EP) nanocomposites synthesized using zinc‐ion (Zn²⁺)‐coated nanosilica (ZNS) and the diglycidyl ether of bisphenol‐A (DGEBA, an epoxy resin)‐modified zinc‐ion‐coated nanosilica (EZNS) as nanofillers. These nanocomposites were prepared using the ‘melt mixing’ method at a constant loading level of 2.5 wt%. This loading level is much lower than that used for fillers in conventional composites. The EP nanocomposites were characterized using wide‐angle X‐ray diffractometer (WAXD), a thermo gravimetric analyzer (TGA), a differential scanning calorimeter (DSC), a dynamic mechanical analyzer (DMA) and scanning electron microscopy (SEM). DMA results showed a higher storage modulus for EP‐epoxy‐modified Zn²⁺‐coated nanosilica nanocomposite (EP‐EZNS) with respect to EP and EP‐Zn²⁺‐coated nanosilica nanocomposite (EP‐ZNS). In addition, TGA thermograms showed an increase in degradation temperature of EP in the presence of EZNS. Copyright © 2006 Society of Chemical Industry     

The surface modification of nanosilica,preparation of nanosilica/acrylic core‐shell composite latex,and its application in toughening PVC matrix

The properties and morphology of nanosilica modified with silane coupling agent, methacryloxypropyltrimethoxysilane (MPS), were characterized by fourier transform infrared, zeta potentials, thermogravimetric analysis, and transmission electron microscopy. The results showed that the grafting ratio of MPS on the surface of nanosilica increased with the MPS content. MPS‐silica/PBA/PMMA core‐shell latexes (MPS‐Si/ACR) were prepared by seeded emulsion polymerization. Then they were used to mix with PVC resin. The outer layer (PMMA) enhanced the dispersibility of MPS‐Si/ACR in the PVC matrix by increasing the interfacial interaction of these composite particles with PVC. The notched impact strengths of the blends were influenced by the weight ratio of MPS to silica, the concentration of emulsifier (SDS), and the MPS‐Si/ACR content. The relationships between the mechanical properties and the core‐shell composite structures were elaborated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

UV‐curing and mechanical properties of polyester–acrylate nanocomposites films with silane‐modified antimony doped tin oxide nanoparticles

Antimony doped tin oxide (ATO) nanoparticles were used as nanofillers to improve mechanical properties of UV‐cured polyester–acrylate films. To improve the dispersion of ATO nanoparticles in the polyester–acrylate resin matrix and to strengthen interfacial interactions between ATO nanoparticles and the resin matrix ATO nanoparticles were first organically modified with 3‐methacryloxypropyltrimethoxysilane (MPS). The modification of ATO nanoparticles with MPS was confirmed by FTIR spectroscopy and thermogravimetric analysis (TGA). UV‐curing behaviors of the nanocomposites films were investigated by FTIR spectroscopy. Compared with the film with neat ATO nanoparticles, the film with the same amount of MPS‐modified ATO nanoparticles showed slightly higher UV‐curing rate and final conversion. The mechanical properties of the nanocomposites films were measured by universal testing machine. The MPS‐modified ATO nanoparticles could improve considerably the mechanical properties of the UV‐cured polyester–acrylate nanocomposites films. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Poly (styrene‐n‐butyl acrylate‐methyl methacrylate)/silica nanocomposites prepared by emulsion polymerization

Poly (styrene‐n‐butyl acrylate‐methyl methacrylate) (PSBM)/silica nanocomposite was prepared by emulsion polymerization in the presence of oleic acid surface modified nanosilica. The structure, morphology, size, and size distribution were characterized by Fourier transform infrared (FTIR), transmission electron microscopy (TEM), and dynamics laser scattering. The chemical bond was formed between PSBM and nanosilica revealed by FTIR and TEM studies. The composite particles with an averaged diameter ranging from 30 to 80 nm have the core‐shell structure. The effect of silica content on the glass transition temperature T_g, pyrolyze temperature, and rheological behavior of PSBM composites was systematically investigated. The results indicated that the addition of nanosilica could effectively inhibit chain movement, and improved the pyrolyze temperature of PSBM. The steady viscosity and dynamic modulus were strongly dependent on the content and distribution of nanosilica in PSBM nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of melt‐mixed metallocene polyethylene/silica nanocomposites

Metallocene polyethylene (mPE)/silica nanocomposites were prepared via melt mixing. Two types of commercial fumed nanosilica, bare silica (A200) and organic modified silica (R974), were incorporated to improve the mechanical properties of the nanocomposites. Transmission electron microscopy, atomic force microscopy, and scanning electron microscopy revealed that the modified silica was dispersed slightly better within the mPE matrix. No distinct effects on the thermal behaviors of the fast‐crystallizing mPE matrix were observed with variations in both the silica dosages and types. Thermal stability was enhanced through the addition of nanosilica, with or without surface treatment. The surface‐modified silica system showed slightly higher tensile strength and Young's modulus compared with the bare silica system, as evidenced by a rheological study using a Cole‐Cole plot to assess enhanced polymer matrix‐dispersed silica interactions, especially for high dosages of organic modified silica. A limited increment in the dynamic storage modulus for modified silica cases, completely opposite of that observed for bare silica cases, was due to the low‐aspect ratio of smaller agglomerates from highly dispersed organic modified silica within the mPE matrix. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Polyethylene nanocomposites by gas‐phase polymerization of ethylene in the presence of a nanosilica‐supported zirconocene catalyst system

BACKGROUND: Much of the current research related to the development of in situ nanocomposites of olefins by polymerizing them with metallocenes in the presence of surface‐treated fillers is carried out in the slurry phase. In slurry‐phase methods a large amount of solvent is required and there is always a need of purification of the final product due to the possibility of traces of solvents present in the product. To overcome these drawbacks, to perform solvent‐free metallocene‐catalysed polymerizations with in situ incorporation of inorganic nanoparticles, we have used a gas‐phase polymerization technique as this does not require solvents and also utilizes monomer feed stocks efficiently. RESULTS: The catalyst used for the synthesis of in situ polyethylene nanocomposites by gas‐phase polymerization was nanosilica‐supported zirconocene. The fillers used were Cloisite‐20A, kaolin and nanosilica. Three different in situ polyethylene nanocomposites, i.e. Cloisite‐20A‐filled polyethylene (CFPE), kaolin‐filled polyethylene (KFPE) and nanosilica‐filled polyethylene (SFPE), were prepared by gas‐phase polymerization. The nanocomposites were obtained in the form of fine powder. The polyethylene content in the developed nanocomposites is in the orthorhombic crystalline phase. Using our approach, it is observed that the nanofillers are completely encapsulated by a thin layer of polyethylene. Significantly higher molecular weight polyethylene was formed in the case of KFPE in comparison to CFPE and SFPE. The thermal decomposition temperature, melting temperature and enthalpy are also observed to be higher for KFPE. CONCLUSIONS: The gas‐phase polymerization technique has been successfully carried out for the synthesis of in situ polyethylene nanocomposites. Copyright © 2007 Society of Chemical Industry     

Ionic‐liquid‐assisted three‐dimensional caged silica ablative nanocomposites

In this study, we demonstrated a novel three‐dimensional network of thermally stable fumed silica (FS)–resorcinol formaldehyde (RF) nanocomposites via an ionic‐liquid (IL)‐assisted in situ polycondensation process. The study involved subjecting the tailored nanocomposites to thermogravimetric analysis and oxyacetylene flame environment as per ASTM test standards for thermal ablative performance. X‐ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, high‐resolution transmission electron microscopy, Raman spectroscopy, and wettability studies were undertaken to underline the improvement correlation in the microstructure and material properties. Significant reductions in the linear ablation rate (66%) and mass ablation rate (26.6%), along with lower back‐face temperature profiles, marked enhanced ablative properties. The increased char yield (33.3%) and higher temperatures for weight losses evinced the improved thermal stability of the modified RF resin. The uniformly dispersed fused nanosilica with a glassy coating morphology on the ablative surface acted as barrier to oxidation. The results signify that the IL‐assisted modification of the RF resin with FS significantly enhanced ablative performance. A viable replacement to the conventional phenolic nanocomposites for thermal ablative applications to buy critical time for the containment and suppression of thermal‐heat‐flux threats is of paramount importance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45328.     

Preparation of silica/polyurethane nanocomposites by UV‐induced polymerization from surfaces of silica

UV‐curable nanocomposites were prepared by the in situ photopolymerizaton with nanosilica obtained from sol–gel process. The photoinitiator 2‐hydroxy‐2‐methyl‐1‐phenylpropane‐1‐one (1173) was anchored onto the surface of the nanosilica with or without methacryloxypropyltrimethoxysilane (MAPS) modification. The photopolymerization kinetics was studied by real‐time Fourier transform IR (RTIR), and the microstructure and properties of the nanocomposite were investigated using transmission electron microscopy and UV–visible (UV–vis) transmistance spectra. RTIR analysis indicated that the nanocomposites without MAPS had higher curing rates and final conversion than those with MAPS. The nanocomposites with an uniformal dispersion of nanosilica had high UV–vis transmittance. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polypropylene–nanosilica‐filled composites: Effects of epoxy‐resin‐grafted nanosilica on the structural,thermal, and dynamic mechanical properties

This article reports a comparative study of polypropylene (PP) nanocomposites synthesized with nanosilica (NS) and diglycidyl ether of bisphenol A, an epoxy‐resin‐grafted nanosilica (ENS), as nanofillers. These nanocomposites were prepared with the melt‐mixing method at a constant loading level of 2.5 wt %; this loading level was much lower than that used for fillers in conventional composites. The effects of pure NS and ENS on the thermal, structural, mechanical, and dynamic mechanical properties of PP were analyzed with wide‐angle X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and scanning electron microscopy. The transmission electron microscopy studies showed a better dispersion of ENS in the PP matrix, that is, in the polypropylene‐epoxy‐resin‐grafted nanosilica (PP–ENS) nanocomposite, in comparison with NS in the PP matrix, that is, in the polypropylene–nanosilica (PP–NS) nanocomposite. Also, the thermogravimetric analysis results showed a higher thermal stability for PP–ENS than PP–NS. Furthermore, the dynamic mechanical analysis studies showed an increase in the elastic modulus and glass‐transition temperature for PP–ENS with respect to PP–NS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2117–2124, 2006     

Effects of preparation method on microstructure and properties of UV‐curable nanocomposite coatings containing silica

UV‐curable nanocomposites were prepared by the blending method or the in situ method with nanosilica obtained from a sol–gel process. The microstructure and properties of the nanocomposite coatings were investigated using ²⁹Si‐NMR cross‐polarization/magic‐angle spinning, transmission electron microscopy (TEM), Fourier transform IR (FTIR), differential scanning calorimetry (DSC), and UV–visible (UV–vis) spectra, respectively. The NMR and TEM showed that during the blending method, tetraethyl orthosilicate (TEOS) completely hydrolyzed to form nanosilica particles, which were evenly dispersed in the polymer matrix. However, for the in situ method, TEOS partially hydrolyzed to form some kind of microstructure and morphology of inorganic phases intertwisted with organic molecules. FTIR analysis indicated that the nanocomposites prepared from the in situ method had much higher curing rates than those from the blending method. DSC and UV–vis measurements showed that the blending method caused higher glass‐transition temperatures and UV absorbance than the in situ method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1119–1124, 2005     

Surface‐activated nanosilica treated with silane coupling agents/polypropylene composites: Mechanical,morphological, and thermal studies

This work reports the mechanical, morphological, and thermal properties of the polypropylene (PP) nanocomposites containing nanosilica (nano‐SiO₂) which were treated by different functional group silane coupling agents. Four types of silane coupling agents namely aminopropyltriethoxy silane (APTES), glycidyloxypropyltrimethoxy silane (GPTMS), trimethoxysilylpropyl methacrylate (TMPM), and dichlorodimethyl silane (DCMS) were used to modify the surface‐activated nanosilica. To enhance the effectiveness of the coupling, nanosilica was chemically activated and analyzed through FTIR and X‐ray photo electron spectroscopy (XPS). The highest tensile strength was recorded by the activated nanocomposites treated with APTES followed by nanocomposite treated with GPTMS, TMPM, and DCMS, respectively. The addition of silane coupling agents into nano‐SiO₂/PP system further improved the tensile modulus of the PP nanocomposites. From the transmission electron microscopy (TEM) analysis, activated nanosilica treated with APTES showed better nanosilica dispersion in the PP matrix and lesser agglomeration occurred when compared with the other silane coupling agents which were used in this study. Surface activation process does not effectively increase the degree of crystallinity and thermal stability on the PP nanocomposites. However, with the assistance of the surface treatment, it was found that the thermal behavior of the PP nanocomposites had been enhanced. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Photo‐curable highly water‐repellent nanocomposite coatings

Modification and use of natural products have gained a lot of interest in recent years due to their environmental friendliness and their availability from different sources. In this study, (castor oil)‐based photo‐curable highly hydrophobic coatings were prepared and characterized. Castor oil was first modified with 3‐isocyanatopropyltriethoxysilane and then hydrolyzed prior to the coating preparation. The resulting precursor was mixed with norbornyl acrylate and hexanediol diacrylate, and highly roughened hydrophobic coatings were prepared with the aid of fluorinated/nonfluorinated alkoxysilane coupling agents and hydrophobic fumed nanosilica particles. The coatings were applied on borofloat glass. The addition of fluorine and nanosilica showed a significant impact on the properties of the coatings. As the fluorine and nanosilica contents were increased in the formulations, flame retardancy and the contact angle values of the coatings increased. The surface roughness of the coatings increased with the addition of hydrophobic fumed nanosilica particles. Also, the relation between the surface energy and the contact angle values of the coatings was investigated. J. VINYL ADDIT. TECHNOL., 19:31–38, 2013. © 2013 Society of Plastics Engineers     

Effect of functionalized nanosilica on the mechanical,dynamic‐mechanical,and morphological performance of polycarbonate/nanosilica nanocomposites

Polycarbonate (PC)/nanosilica (nSiO₂) nanocomposites were prepared by melt‐blending technique, in which surfactants are used to enhance the interfacial adhesion between nSiO₂ and polymer matrix. Mechanical properties demonstrate increased Young's modulus and yield strength of modified PC/nSiO₂ nanocomposites when compared with PC. Increased compatibility further indicates an effective increase in thermal stability as observed from thermogravimetric analysis. Dynamic mechanical analysis point out a reduction in T_g value with increased storage modulus. The flammability characteristics of PC/nSiO₂ nanocomposites were evaluated using limiting oxygen index, whereas the morphological properties are characterized by wide‐angle X‐ray diffraction and scanning electron microscopy. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Characterization of nanosilica‐filled epoxy composites for electrical and insulation applications

We report in this article the results of nanosilica (SiO₂)‐filled epoxy composites with different loadings and their electrical, thermal, mechanical, and free‐volume properties characterized with different techniques. The morphological features were studied by transmission electron microscopy, and differential scanning calorimetry was used to investigate the glass‐transition temperature (T_g) of the nanocomposites. The properties of the nanocomposites showed that the electrical resistivity (ρ), ultimate tensile strength, and hardness of the composites increased with SiO₂ weight fraction up to 10 wt % and decreased thereafter; this suggested that the beneficial properties occurred up to this weight fraction. The temperature and seawater aging had a negative influence on ρ; that is, ρ decreased with increases in the temperature and aging. The free‐volume changes (microstructural) in the composite systems correlated with seawater aging but did not correlate so well with the mechanical properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Structure–property correlation of polyurethane nanocomposites: Influence of loading and nature of nanosilica and microstructure of hyperbranched polyol

New generation polyurethane nanocomposites based on toluene diisocyanate, poly(propylene glycol), hyperbranched polymers (HBPs), and nanosilica were synthesized with the aim of determining the effect of the loading and nature of nanosilica and the functionality of HBP on the structure and properties of polyurethane nanocomposites. Good dispersion of nanosilica at 4 wt % loading in the polymer was confirmed from atomic force microscopy. The properties of the polyurethane nanocomposites were a function of content and nature of the nanosilica in the matrix. The optimum silica loading was 4 wt %. At this loading, tensile strength and storage modulus at 25°C of the nanocomposites increased by 52 and 40%, respectively over the pristine polyurethane. Organo‐treated nanosilica exhibited higher physico‐mechanical properties than the untreated one. With the increase of functionality in the hyperbranched polyol, the tensile strength, thermal stability, and dynamic mechanical properties of the nanocomposites improved. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nanosilica‐reinforced Epoxidized natural rubber nanocomposites: Effect of Epoxidation level on morphological and mechanical properties

Epoxidized natural rubbers (ENRs) with three different epoxide contents (i.e., 20, 35, and 50 mol% indicated as ENR20, ENR35, and ENR50, respectively) were prepared. They were then reinforced with 3‐methyacryloxypropyl trimethoxysilane‐modified nanosilica (MPTS‐SiO₂). Influence of epoxide level in ENR molecules on morphological, mechanical, and dynamic mechanical properties of the ENR nanocomposites was investigated. The scanning electron microscopy results revealed larger agglomerates of SiO₂ were found in the ENR composites with higher epoxide content. Furthermore, the strength and moduli of the ENR nanocomposites increased with increasing epoxide content. However, the optimal tensile strength and elongation at break were observed in the nanocomposites with the intermediate level of epoxide contents. The correlation between the strength properties and the interfacial silica‐matrix adhesion indicated that the maximum interfacial adhesion of the nanocomposites was observed in the nanocomposite with ENR35. Also, DMA results indicated stronger interaction between ENR35 and MPTS‐SiO₂ due to higher storage modulus. POLYM. COMPOS., 38:1151–1157, 2017. © 2015 Society of Plastics Engineers     

Preparation and properties of thermosensitive organic‐inorganic hybrid gels containing modified nanosilica

A series of thermosensitive organic–inorganic hybrid gels containing nanosilica or modified nanosilica were prepared from N‐isopropylacrylamide (NIPAAm), and N,N′‐methylene‐bis‐acrylamide (NMBA) and nanosilica (AE200) or modified AE200 (mAE200); and NIPAAm, NMBA, 3‐(trimethoxysilyl) propyl methacrylate (TMSPMA) as coupling agent and AE200 or mAE200 in this study. The effect of inorganic nanosilica on the swelling behaviors and mechanical properties were investigated by adding different amount of nanosilica and modified nanosilica. Results showed that the swelling ratios of the hybrid gels decrease with increasing nanosilica content. Existence of silane coupling agent would also reduce the swelling ratios of the hybrid gels. Adding coupling agent or nanosilica would improve the gel strength. Modification of nanosilica by grafting amino‐silane via sol–gel process was carried out and the effect of addition of modified silica on gel properties was also investigated. Results showed that the hybrid gels containing modified silica would have higher swelling ratios and moduli than those containing unmodified silica. Gels containing both silane coupling agent and silica would have higher crosslinking density because the silica would be better crosslinked with coupling agent. POLYM. COMPOS., 31:1712–1721, 2010. © 2010 Society of Plastics Engineers.