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     

Preparation and characterization of UV‐curable MPS‐modified silica nanocomposite coats

A series of UV‐curable nanocomposites were prepared with 3‐(trimethoxysilyl) propyl methacrylate (MPS) modified nanosilica under the initiation of 2,2‐dimethoxy‐1,2‐diphenylethan‐1‐one. It was found that MPS‐modified nanosilica together with free MPS could form transparent nanocomposite coats. As the particle size of nanosilica increased, the photopolymerization rate, final double bond conversion, and tack‐free time of nanocomposites increased while the surface roughness, glass‐transition temperature, and UV absorbance of nanocomposites decreased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2274–2281, 2005     

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     

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     

Synthesis and thermal characterization of phenolic resin/silica nanocomposites prepared with high shear rate‐mixing technique

In this research the possibility to produce nanosilica/phenolic nanocomposites by means of a simple low labor cost mechanical approach was investigated. A commercial compatibilized nanosilica was selected as a filler and a resol diluted in methanol as a matrix. The morphology of the produced nanocomposites were studied by means of Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), whereas thermogravimetric analysis (TGA) was used to study the thermal stability of the nanocomposites. The post burning morphology of samples was also investigated. A rheological characterization was also carried out. The results of such study showed that it was possible to obtain a good degree of dispersion and distribution of the nanosilica particles, indicating that the proposed process could be successfully adopted as an alternative approach to sol‐gel techniques. Thermogravimetric analyses showed that all the produced nanocomposites exhibited a better thermal stability than the pristine matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

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     

Synthesis and properties of BCDA‐based polyimide–clay nanocomposites

Bicyclo[2.2.2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride (BCDA)‐based polyimide–clay nanocomposites were prepared from their precursor, namely polyamic acid, by a solution‐casting method. The organoclay was prepared by treating sodium montmorillonite (Kunipia F) clay with dodecyltrimethylammonium bromide at 80 °C. Polyamic acid solutions containing various weight percentages of organoclay were prepared from 4,4′‐(4,4′‐isopropylidenediphenyl‐1,1′‐diyldioxy)‐dianiline and BCDA in N‐methyl‐2‐pyrrolidone containing dispersed particles of organoclay at 20 °C. These solutions were cast on a glass plate using a Doctor's blade and then heated subsequently to obtain nanocomposite films. The nanocomposites were characterized using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermal mechanical analysis, dynamic mechanical analysis, polarizing microscopy, scanning electron microscopy, transmission electron microscopy, wide‐angle X‐ray diffraction (WAXD) and thermogravimetric analysis. The glass transition temperature of the nanocomposites was found to be higher than that of pristine polymer. The coefficient of thermal expansion of the nanocomposites decreased with increasing organoclay content. WAXD studies indicated that the extent of silicate layer separation in the nanocomposite films depended upon the organoclay content. Tensile strength and modulus of the nanocomposite containing 1% organoclay were significantly higher when compared to pristine polymer and other nanocomposites. The thermal stability of the nanocomposites was found to be higher than that of pristine polymer in air and nitrogen atmosphere. Copyright © 2007 Society of Chemical Industry     

Kinetic study on the UV‐induced photopolymerization of epoxy acrylate/TiO2 nanocomposites by FTIR spectroscopy

The kinetics of the photopolymerization of epoxy acrylate/TiO₂ nanocomposites, with 2′2‐dimethoxy‐1,2‐diphenylethan‐1‐one (Irgacure 651) or benzophenone/N‐methyl diethanolamine as photoinitiators, were studied by FTIR spectroscopy. It was found that nanocomposites had a decreasing photopolymerization rates in comparison with pure epoxy acrylate. The photopolymerization rate of the nanocomposite could also be influenced by initiator types, oxygen, film thickness, irradiation intensity, dispersing media of TiO₂ slurry, and so forth. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3281–3287, 2006     

Polypropylene/silica nanocomposites prepared by in-situ melt ultrasonication

A novel process using ultrasonic irradiation to enhance nanosilica dispersion in polypropylene-based nanocomposites has been proposed and investigated. The nanocomposites were isotactic polypropylene reinforced with silica nanoparticles at 3 wt% loading level. Ultrasonic processing in the melt state is an effective method for improving nanosilica dispersion. The effectiveness of the proposed ultrasonic processing technique on polypropylene nanocomposites was evaluated by XRD and transmission electron microscopy (TEM). Poly(propylene-g-maleic anhydride) copolymer (PP-g-MAH) containing 5 wt% maleic anhydride content was added to nanocomposites at 0.5 wt% concentration based on silica content. PP-g-MAH plays an important role in nanosilica dispersion in polymer matrix and interface interaction. The reaction of maleic anhydride groups with the hydroxyl groups on the surface of nanosilica was characterized by FTIR spectrum. The final nanocomposites result in a further enhancement of mechanical properties because of silica agglomerate reduction and improving interface combination, even loading level being much lower than that of ordinary fillers in conventional composites. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

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     

Enhancement of dynamic mechanical properties and flame resistance of nanocomposites based on epoxy and nanosilica modified with KR-12 coupling agent

The epoxy/silica nanocomposites containing a wide range of isopropyltri[di(octyl) phosphate] titanate coupling agent (KR-12) modified nanosilica (m-nanosilica) loading (0–7 wt%) cured with tetrabutyl titanate hardener were prepared. Their morphology, thermal stability, thermal expansion, and mechanical properties including hardness, abrasion resistance were investigated. The wetting ability of epoxy-nanosilica systems on glass surface was assessed based on static contact angle. The obtained results showed that the contact angle of the nanocomposites containing m-nanosilica is slightly changed as compared to the contact angle of pure epoxy resin and lower than that of the nanocomposite containing unmodified nanosilica. The data of dynamic mechanical analysis of the nanocomposites using different nanosilica content indicated that the presence of m-nanosilica lowered the recovery energy of the nanocomposites to 41.62% as compared to neat epoxy. The limiting oxygen index (LOI) of the nanocomposites confirmed that the m-nanosilica increased the flame retardance of epoxy matrix. When using 7 wt% of m-nanosilca, the LOI value of the nanocomposite was 27.4 while this index of neat epoxy was 21.6. The scanning electron microscopic images of residual char combustion of the nanocompsites indicated a formation of nanosilica layer contributed to restrain combustion of the material.     

Dielectric properties of EVA/LDPE TPE system: Effect of nanosilica and controlled irradiation

The pristine nanosilica particles were melt‐blended with a model low‐density polyethylene–ethylene vinyl acetate thermoplastic elastomers (TPE) system by varying the sequence of addition and nanosilica contents. Bis‐[3‐(triethoxysilyl)propyl] tetrasulfide (Si‐69) was used to improve the state of dispersion of nanosilica particles in one of the compositions. The dielectric properties of the TPE systems are influenced remarkably by loadings of silica, variation of sequence of addition of ingredients during mixing, addition of Si‐69, and controlled electron beam irradiation. The effects of interfacial and orientation polarization on the permittivity and the loss tangent were studied by dielectric analyses. These were correlated with the structures of various nanocomposites. An attempt has also been made to support the dielectric results by volume resistivity measurements, measurements of breakdown voltage, and swelling–deswelling kinetic results. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Effect of multiwall carbon nanotube and au nanoparticle on the structure–property relationship of poly(N‐isopropyl acrylamide)

Temperature‐sensitive poly(N‐isopropyl acrylamide) (PNIPAAm) was synthesized both in the presence and absence of nanomaterials like allyl mercaptan decorated gold nanoparticle and allyalcohol‐conjugated multiwall carbon nanotube. The influence of the nanomaterials on the structure–property relationship of PNIPAAm was analyzed and critically compared to the pristine PNIPAAm. During the in situ polymerization, the nanosphere shape of Au nanoparticle was converted into Au nanorod shape, which was confirmed through UV–vis spectroscopy. The glass transition temperature (T_g) of polymer/nanocomposites was greater than that of the pristine polymer. Thermogravimetric analysis declared that the polymer/nanocomposites exhibited higher thermal stability than the homopolymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of PLA nanocomposites containing nanosilica modified with different organosilanes II: Effect of the organosilanes on the properties of nanocomposites: Thermal characterization

Thermal behavior of polylactic acid (PLA)/nanosilica nanocomposites prepared via bulk ring opening polymerization from lactide was investigated by differential scanning calorimetry and thermogravimetric analysis (TGA). Both unmodified nanosilica and modified by surface treatments with different amounts of two distinct silanes were used. Samples containing pure silica show enhanced crystallization processes; with silane‐modified silica this effect is magnified, especially in the case of materials with high loadings of epoxy silane. Nonisothermal crystallization temperatures become higher and isothermal crystallization kinetics show a marked increase of Kinetic constant (K_c). TGA analyses show that, when pure nanosilica is present, nanocomposites have a thermal stability far greater than the one of standard PLA, starting their degradation at temperatures up to 70°C higher than the ones of pure PLA. When silanes are present, thermal stability lowers as silane content increases, but it is anyway higher than the one of the pure polymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation,crystallization, and spinnability of poly(ethylene terephthalate)/silica nanocomposites

Poly(ethylene terephthalate) (PET)/silica nanocomposites were successfully prepared by in situ polymerization. Silica nanoparticles were uniformly dispersed in the process of polymerization. By means of hot‐stage polarization microscope and DSC, the influence of nanosilica on the crystallization of PET/silica nanocomposites has been clarified. The results show that nanosilica does not behave as a nucleating agent in PET but postpones the appearance of crystallite. This phenomenon is very favor to improve spinnability. The investigation on melt spinning of PET/silica nanocomposites also shows that it is advantageous to spinning with descending the spinning temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2564–2568, 2007     

Synthesis of poly(butyl acrylate‐co‐methyl methacrylate)/montmorillonite waterborne nanocomposite via semibatch emulsion polymerization

Poly(butyl acrylate‐co‐methyl methacrylate)‐montmorillonite (MMT) waterborne nanocomposites were successfully synthesized by semibatch emulsion polymerization. The syntheses of the nanocomposites were performed in presence of sodium montmorillonite (Na‐MMT) and organically modified montmorillonite (O‐MMT). O‐MMT was used directly after the modification of Na‐MMT with dimethyl dioctadecyl ammonium chloride. Both Na‐MMT and O‐MMT were sonified to obtain nanocomposites with 47 wt % solids and 3 wt % Na‐MMT or O‐MMT content. Average particle sizes of Na‐MMT nanocomposites were measured as 110–150 nm while O‐MMT nanocomposites were measured as 200–350 nm. Both Na‐MMT and O‐MMT increased thermal, mechanical, and barrier properties (water vapor and oxygen permeability) of the pristine copolymer explicitly. X‐ray diffraction and transmission electron microscope studies show that exfoliated morphology was obtained. The gloss values of O‐MMT nanocomposites were found to be higher than that of the pristine copolymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42373.     

Synthesis and characterization of UV-cured epoxy acrylate/POSS nanocomposites

In this study, epoxy acrylate (EA)/vinyl-polyhedral oligomeric silsesquioxane (POSS) nanocomposites were prepared through in situ polymerization and by UV-curing technique. The vinyl-POSS monomers were added to EA matrix by physically blending at loadings between 0 wt.% and 15 wt.%. The microstructure of the EA/vinyl-POSS composites was studied by X-ray diffraction (XRD) measurements, and the result indicated that the separate POSS domains were present in EA/POSS composites. Aggregates were observed in the nanocomposites by SEM and the EDS results indicated that there were vinyl-POSS molecules existing in the EA matrix. TEM images further proved there were both POSS aggregates and monomers dispersed in the EA matrix. The kinetics of the photopolymerization was investigated by real time FTIR spectroscopy. The DSC analysis showed that the increasing POSS content caused a decrease on the composite's glass transition temperature. TGA measures confirmed that the degradation mechanism of EA was not affected by POSS and the nanocomposites thermal stability was slightly improved with the increasing of POSS loadings. It can be seen that the degradation rate slowed down with the increasing of POSS content and the 50% mass loss temperature of EA/POSS hybrids all increased conspicuously relative to plain EA.     

Preparation and characterization of light‐cured methacrylate/montmorillonite nanocomposites

Polymer/clay nanocomposites were prepared from dimethacrylate monomers, commonly used in dental restorative resins, and an organically modified silicate (montmorillonite). The photopolymerization process was hardly affected by the presence of the silicate filler, and thus 2 mm thick samples containing 3 wt% clay were extensively cured. Transmission electron microscopy revealed that the montmorillonite platelets were either intercalated or exfoliated. Nevertheless, for all formulations, intermediate‐sized aggregates of about 1 µm were present and their fraction increased as the amount of filler increased. The presence of the clay was found to have no major effect on the flexural modulus and compressive yield strength of the nanocomposites. Moreover, the water uptake of nanocomposites containing 3 wt% clay was about 10–15% higher than that of unfilled monomers. Modification of the clay surface with alternative organic cations is certainly necessary in order to achieve an optimal dispersion of the clay in the polymer matrix. Copyright © 2010 Society of Chemical Industry     

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