Synthesis and Characterization of in situ Polyethylene and Polypropylene Nanocomposites: Gas Phase Polymerization by Nanosilica Supported <Emphasis Type="Italic">bis</Emphasis> (Cyclopentadienyl) Zirconium (IV) Dichloride Catalyst System

In the present work, in situ polyethylene and polypropylene nanocomposites have been successfully synthesized by gas phase polymerization of ethylene and propylene in presence of surface treated nanofillers with nanosilica-supported-bis (cyclopentadienyl) zirconium (IV) dichloride as a coordination catalyst. The nanofillers used are Cloisite-20A and nanosilica, respectively. These were pre-treated with MAO (Methylaluminoxane) to inhibit their deactivating action on the catalyst because of the presence of either acidic or basic groups on their surfaces; in this way MAO acts as a co-catalyst for the polymerization reactions being discussed. Two in situ Polyethylene (PE) i.e., CFPE and SFPE (Cloisite-20A filled polyethylene and nanosilica filled polyethylene) and two in situ polypropylene (PP) i.e., CFPP and SFPP (Cloisite-20A filled polypropylene and nanosilica filled polypropylene) nanocomposites have been prepared by gas-phase polymerization. The in situ polyethylene and polypropylene nanocomposites were characterized using Fourier transform infrared Spectroscope (FTIR), Thermogravimetric analyzer (TGA), Differential Scanning Calorimeter (DSC) and Scanning electron microscope (SEM). By our approach, it has been observed that the nanofillers are completely encapsulated by a thin layer of polymer chains.     

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     

Effect of electrospun fibers of polyhydroxybutyrate filled with different organoclays on morphology,biodegradation, and thermal stability of poly(ε‐caprolattone)

The properties of nanocomposites of poly(ε‐caprolattone) (PCL) were studied, the pristine PCL was implemented with the introduction of electrospun fibers of polyhydroxybutyrate (PHB), containing a cationic (Cloisite) or an anionic (Perkalite) clay. These multicomponent composites containing a very low amount of clay confined in fibers are different from usual nanocomposite materials containing clay dispersed in the polymer matrix, which are produced by solvent casting or melt extrusion. To analyze the influence of the different fillers on the final composite, a preliminary study on PHB cast films and fibers prepared from the same solution was carried out, and then a thorough analysis was accomplished of the behavior of these particular nanocomposites PCL/PHB fibers/clay to elucidate the effects of the filled electrospun fibers on the PCL matrix. The structure and morphology of the samples were characterized by wide‐angle X‐ray diffraction and small angle X‐ray scattering; differential scanning calorimetry and thermogravimetric analysis were used to understand the influence of the fillers on the thermal behavior and stability; mechanical properties were evaluated and biodegradation studies were carried out. The PHB electrospun fibers and the fractured surface of the final composites were examined by scanning electron microscopy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42342.     

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     

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     

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     

Effects of processing and functionalization methods on nylon‐6,6 nanocomposites with Helical‐ribbon carbon nanofibers

Helical‐ribbon carbon nanofiber‐based nylon‐6,6 nanocomposites were obtained by three processing methods: in situ polymerization, solvent processing through coagulation, and melt compounding. Composites were produced with pristine carbon nanofibers and four functionalization treatments, HNO₃, O₃, air/NH₃, and ethylenediamine, which form sets of two liquid/gas phase treatments and two acidic/basic treatments. Dispersion was monitored at the microscale by optical microscopy, showing clear differences depending on processing and functionalization methods. The best dispersion was obtained by solvent processing, whereas the most appropriate functionalizations were obtained by air/NH₃ and ethylenediamine treatments. It was observed that lower aspect ratio CNFs and stronger CNF‐matrix interaction increased crystallization temperature. Percolation was not detected in the melt‐compounded composites while network formation was observed at concentrations of 2 wt % in the solvent and in situ processing methods, where a high‐aspect ratio was critical for performance. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Quantitative analysis of cloisite 93A infused into linear low‐density polyethylene and maleated linear low‐density polyethylene in a supercritical carbon dioxide medium

Linear low‐density polyethylene (LLDPE) is a widely used polymer that can benefit from the enhanced barrier, thermal, and mechanical properties offered by nanoclay fillers. However, optimal property enhancement requires complete exfoliation and uniform dispersion, both of which are difficult to achieve with nanoclay fillers. Supercritical carbon dioxide (scCO₂) processing is an inexpensive and environmentally benign method for exfoliating and dispersing clays into polymers. In a scCO₂ medium under controlled environments, the organically modified clay Cloisite 93A was infused into LLDPE and maleated linear low‐density polyethylene (LLDPE‐g‐MA). Upon microscopic inspection, it was evident that clay infusion was achieved near the surface of the polymer pellet, but no clay found its way into the interior of the pellet. In this article, we describe an analytical method for determining the amount of nanoclay infused into a polymer matrix via Fourier transform infrared analysis. Using this method, we determined the weight percentage of Cloisite 93A infused into LLDPE and LLDPE‐g‐MA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of polyacrylate‐clay nanocomposites by in‐situ polymerization and heterocoagulation

Polyacrylate‐clay nanocomposites were prepared by an in situ polymerization method followed by heterocoagulation. In the heterocoagulation method, a cationic polyacrylate emulsion was prepared by emulsion polymerization using a cationic initiator in the presence/absence of free surfactant, cetyl trimethylammonium bromide (CTABr), followed by mixing with an aqueous clay slurry. WAXD results and TEM images suggest that morphologies of these nanocomposites depend on preparation method, mixing method, and the amount of free surfactant. TG‐DTG analyses demonstrate the improvement in thermal stability of these nanocomposites, while DSC results indicate no significant changes in glass transition temperature of these nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3850–3855, 2006     

Enhancement of mechanical and tribological properties in ring‐opening metathesis polymerization functionalized molybdenum disulfide/polydicyclopentadiene nanocomposites

This study focuses on the possibility of improving performance properties of polydicyclopentadiene (PDCPD) nanocomposites for engineering applications using nanoparticles. In this article, molybdenum disulfide/polydicyclopentadiene (MoS₂/PDCPD) nanocomposites have been prepared by in situ ring‐opening metathesis polymerization using reaction injecting molding (RIM) process. To enhance the interfacial adhesion between the fillers and PDCPD matrix, the surface modified MoS₂ nanoparticles hybridized with dialkyldithiophosphate (PyDDP) were successfully prepared by in situ surface grafting method. The effect of low MoS₂ loadings (<3 wt %) on the mechanical and tribological behaviors of PDCPD was evaluated. The results indicated that the friction coefficient of the MoS₂/PDCPD nanocomposites was obviously decreased and the wear resistance of nanocomposites was greatly improved by the addition of PyDDP‐hybridized MoS₂ nanoparticles; meanwhile, the mechanical properties were also enhanced. The MoS₂/PDCPD nanocomposites filled with 1 wt % PyDDP‐hybridized MoS₂ exhibited the best mechanical and anti‐wear properties. The friction coefficient was shown to decrease by more than 40% compared to pure PDCPD by incorporating just 1 wt % hybridized MoS₂ nanoparticles, and modest increase in modulus and strength was also observed. The reinforcing and wear‐resistant mechanisms of MoS₂/PDCPD nanocomposites were investigated and discussed by scanning electron microscopy. The well interfacial compatibility between the particle/matrix interfaces played an important role for the improved mechanical and tribological properties of MoS₂/PDCPD nanocomposites in very low MoS₂ loadings. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers by atom‐transfer radical polymerization

Well‐defined polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐PS triblock copolymers were synthesized by atom‐transfer radical polymerization (ATRP), using C—X‐end‐group PEO as macroinitiators. The triblock copolymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The experimental results showed that the polymerization was controlled/living. It was found that when the number‐average molecular weight of the macroinititors increased from 2000 to 10,000, the molecular weight distribution of the triblock copolymers decreased roughly from 1.49 to 1.07 and the rate of polymerization became much slower. The possible polymerization mechanism is discussed. According to the Cu content measured with atomic absorption spectrometry, the removal of catalysts, with CHCl₃ as the solvent and kaolin as the in situ absorption agent, was effective. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2882–2888, 2000     

In Situ synthesis of inorganic filler‐filled polyethylene using polyethersulfone‐supported TiCl4 catalyst system

In situ ethylene polymerizations with inorganic fillers were performed using catalyst based on titanium tetrachloride supported on polyethersulfone. The inorganic fillers used were MgO, TiO₂, and CaCO₃, which were pretreated with cocatalyst (methylaluminoxine) for better dispersion onto the polymer matrix. The formation of polyethylene (PE) within the whole matrix was confirmed by Fourier transform infrared studies. The wide‐angle X‐ray diffraction profile of the synthesized PEs indicated the presence of crystalline region. It was found that the nature of inorganic filler did not have any remarkable effect on the melting characteristics of the polymer, but the degree of crystallinity of PE was found to be higher for TiO₂‐filled PE. The amount of filler incorporated into the matrix was also evaluated through thermogravimetric analysis, where TiO₂‐filled PE showed ～ 49% of filler material, which was also reflected in the higher productivity obtained by this system. The morphology of the filler‐filled PEs was different, whereas the elemental dispersion was found to be uniform on the surface as elucidated through energy‐dispersive X‐ray spectroscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of elastomeric polyurethane and PU/clay nanocomposites based on an aliphatic diisocyanate

This investigation reports preparation of polyurethane and polyurethane/clay nanocomposites based on polyethylene glycol, isophorone diisocyanate (IPDI), an aliphatic diisocyanate and 1,4‐ Butanediol as chain extender by solution polymerization. In this case PU/clay nanocomposites were prepared via ex‐situ method using 1, 3, and 5 wt % of Cloisite 30B. Thermogravimetric analysis showed that the maximum decomposition temperature (T_max) of the PU/clay nanocomposite is much higher than the pristine PU. The tensile properties improved upon increasing the organoclay (Cloisite 30B) content upto 3 wt %, and then decreased to some extent upon further increasing the nanoparticle loading to 5 wt %. Optical properties of the nanocomposites were studied by UV‐vis spectrophotometer. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) were used to study the morphology of the nanocomposites. It was observed that with the incorporation of 3 wt % nanoclay the crystallinity in PU nanocomposite increases, then diminishes with further loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3328–3334, 2013     

Preparation of different dendritic‐layered silicate nanocomposites

Several dendrimer–clay nanocomposites have been prepared. Firstly, the dendrimer (DE₁)/clay nanocomposite was obtained via an in situ free radical polymerization of a double bond‐ended dendrimer (DE₁), derived from Behera's amine by using 2,2′‐azobisisobutyronitrile (AIBN), as initiator, and Cloisite 30 B, as nanofiller. Further free radical in situ copolymerization processes were conducted between DE₁, methyl methacrylate (MMA), and styrene (St). Two other dendrimer/clay nanocomposites were prepared by the reaction of second generation (G₂)–36‐acid dendrimer (DE₂) and N,N′,N′,N′‐tetrakis[2‐hydroxy‐1,1‐bis(hydroxylmethyl) ethyl]‐α,α,ω,ω‐alkane‐tetracarboxamide [6]‐10‐[6] Arborols (DE₃) with montmorillonite clay (MMT). POLYM. ENG. SCI., 53:2166–2174, 2013. © 2013 Society of Plastics Engineers     

Silver‐coated copper nanowires with improved anti‐oxidation property as conductive fillers in low‐density polyethylene

Silver‐coated copper nanowires (AgCuNWs) are prepared by chemical plating method with copper nanowires (CuNWs) and Ag‐amine reagent. The prepared AgCuNWs with silver content of 66.52 wt.%, diameter 28–33 nm exhibited improved anti‐oxidation behaviour. The silver coating on AgCuNWs can effectively reduce the formation of copper oxide under room temperature. The temperature at which nanowires begin to gain weight can be improved from 85 to 230°C and the maximum weight gain can be decreased from 20.3% to 3.2% by applying silver coating. The volume electrical resistivity of the AgCuNWs filled low‐density polyethylene nanocomposites is lower than that of the CuNWs filled low‐density polyethylene nanocomposites with same volume percentage of fillers because the silver content in the AgCuNWs is not oxidised during compression moulding. © 2012 Canadian Society for Chemical Engineering     

Crystallization behavior and UV‐protection property of PET‐ZnO nanocomposites prepared by in situ polymerization

The aim of this study was to investigate the crystallization behavior and UV‐protection property of polyethylene terephthalate (PET)‐ZnO nanocomposits. PET‐ZnO nanocomposites containing 0.5–3.0 wt % of ZnO were successfully synthesized by in situ polymerization. The Fourier transformed infrared (FTIR) spectroscopy indicated the silane coupling agent was anchored onto the surface of ZnO. Scanning electron microscope (SEM) images showed ZnO particles were dispersed homogeneously in PET matrix with amount of 0.5–1.0 wt %. Differential scanning calorimetry (DSC) results exhibited that the incorporation of ZnO into PET resulted in increase of the melting transition temperature (T_m) and crystallization temperature (T_c) of PET‐ZnO nanocomposites. The crystallization behavior of PET and PET‐ZnO nanocomposites was strongly affected by cooling rate. ZnO nanoparticles can act as an efficient nucleating agent to facilitate PET crystallization. UV–vis spectrophotometry showed that UV‐ray transmittance of PET‐ZnO nanocomposites decreased remarkably and reached the minimum value of 14.3% with 1.5 wt % of ZnO, compared with pure PET whose UV‐ray transmittance was 84.5%. PET‐ZnO nanocomposites exhibited better UV‐protection property than pure PET, especially in the range of UVA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

In situ fast polymerization of graphene nanosheets‐filled poly(methyl methacrylate) nanocomposites

A series of graphene nanosheets‐filled poly(methyl methacrylate) nanocomposites (GNS/PMMA) is successfully prepared by an in situ fast polymerization method with graphene weight fractions from 0.1 to 2.0 wt %. In situ polymerization is effective in well dispersing of GNS in matrixes and suitable for both low and high content of GNS. The synthesis processes of polymer composites could be simplified and fast by using industrial grade graphene. The GNS fillers are found to disperse homogeneously in the PMMA matrix. The maximum electrical conductivity of the composites achieves 0.57 S m^?1, with an extremely low percolation threshold of 0.3 wt %. The electrical conductivities are further predicted by percolation theory and found to agree well with the experimental results. The results indicate that the microstructures, thermal, electrical, and mechanical properties of PMMA polymer are significantly improved by adding a low amount of graphene nanosheets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43423.     

Development of biodegradable cellulose‐g‐poly(butyl acrylate)/kaolin nanocomposite with improved fire retardancy and mechanical properties

The main aim of the work is to convert a low cost renewable biopolymer to a high performance fire‐retardant biomaterial by modification via grafting. Cellulose, a linear and most abundant biomacromolecule, has gained increasing attention for its interesting properties and potential applications in the synthesis of polymer nanocomposites. Cellulose has been grafted with butyl acrylate via emulsifier free emulsion polymerization using in situ developed transition metal complex initiating system: CuSO₄/glycine/ammonium persulfate with and without additive kaolin to prepare nanocomposites and copolymer, respectively. The morphology of so‐prepared grafted nanocomposites was characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, and field emission scanning electron microscopy. The enhancement in thermal behavior and mechanical properties of nanocomposites over copolymer were outstanding. The fire‐retardant properties were evaluated by limiting oxygen index and cone calorimetry test. The biodegradation and water absorbency of the fire‐retardant nanocomposites have been carried out for better commercialization and environmental concern. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45968.     

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     

Novel in situ carbon nanofiber/polydimethylsiloxane nanocomposites: Synthesis,morphology, and physico‐mechanical properties

A series of carbon nanofiber (CNF)/polydimethylsiloxane (PDMS)‐based nanocomposites was prepared by anionic ring opening polymerization of octamethylcyclotetrasiloxane (D₄) in presence of pristine CNF and amine‐modified CNF. A detailed study of morphology–property relationship of the nanocomposites was carried out in order to understand the effect of chemical modification and loading of filler on property enhancement of the nanocomposites. An elaborate comparison of structure and properties was carried out for the nanocomposites prepared by in situ and conventional ex situ methods. Pronounced improvement in degree of dispersion of the fillers in the matrix on amine modification of CNFs was reflected in mechanical properties of the modified nanocomposites. Maximum upliftment in mechanical properties was observed for in situ prepared amine modified CNF/hydroxyl PDMS nanocomposites. For 8 phr filler loading, tensile strength increased by 370%, while tensile modulus showed an increase of 515% compared with the virgin elastomer. Furthermore, in situ prepared unmodified CNF/hydroxyl PDMS nanocomposites showed an increase of 141°C in temperature of maximum degradation (T_max) for 8 phr CNF loading. These results were correlated with the morphological analysis through transmission electron microscopic studies. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012