Polyamide 6/silica nanocomposites prepared by in situ polymerization

A polyamide 6 (PA 6)/silica nanocomposite was obtained through a novel method, in situ polymerization, by first suspending silica particles in ϵ-caproamide under stirring and then polymerizing this mixture at high temperature under a nitrogen atmosphere. The silicas were premodified with aminobutyric acid prior to the polymerization. The effects of the addition of unmodified and modified silicas on the dispersion, interfacial adhesion, isothermal crystallization, and mechanical properties of PA 6 nanocomposites were investigated by using scanning electron microscopy, dynamic mechanical analysis, differential scanning calorimetry, and mechanical tests, respectively. The results show that the silicas dispersed homogeneously in the PA 6 matrix. The addition of silicas increases the glass transition temperature and crystallization rate of PA 6. The mechanical properties such as impact strength, tensile strength, and elongation at break of the PA 6/modified silica nanocomposites showed a tendency to increase and decrease with increase of the silica content and have maximum values at 5% silica content, whereas those of the PA 6/unmodified silica system decreased gradually. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 355–361, 1998     

Morphology and mechanical properties of polypropylene/polyamide 6 nanocomposites prepared by a two‐step melt‐compounding process

Polypropylene/polyamide 6 blends and their nanocomposites with layered silicates or talc were prepared in a melt‐compounding process to explore their mechanical performance. The thermomechanical behavior, crystallization effects, rheology, and morphology of these materials were studied with a wide range of experimental techniques. In all cases, the inorganic filler was enriched in the polyamide phase and resulted in a phase coarsening of the polypropylene/polyamide nanocomposite in comparison with the nonfilled polypropylene/polyamide blend. The mechanical properties of these nanoblends were consequently only slightly better than those of the pure polymers with respect to the modulus, whereas the impact level was below that of the pure polymers, reflecting the heterogeneity of the nanoblend. Polymer‐specific organic modification of the nanoclays did not result in a better phase distribution, which would be required for better overall performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 283–291, 2006     

Investigation on the melt spinning fibers of PP/organoclay nanocomposites prepared by in‐situ polymerization

Fibers prepared by melt spinning process from the PP (polypropylene)/organoclay nanocomposite were characterized in details with the aid of SEM, FTIR, XRD, DSC, and mechanical measurements. The results suggested that the lower content of organoclay (0.1%) added to the PP matrix increased the crystallinity and mechanical property (tensile strength) of the PP/organoclay nanocomposite fiber. With increasing the content of organoclay (≥ 0.3%), the crystallinity and the tensile strength both a little decreased, and the fiber containing organoclay exhibited multi‐peaks at the same draw ratio during the heating process. Furthermore, the degree of orientation of the fiber increased a little with lower content of organoclay (0.1%) introduction to PP during the infrared dichroism measurement. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of polypropylene–montmorillonite nanocomposites generated by in situ metallocene catalyst polymerization

An ion‐exchange method was applied to replace sodium cations inside the interlamellar space of montmorillonite with positively charged stearyl trimethyl ammonium chloride. The d₀₀₁‐spacing of montmorillonite is larger in toluene than in other solvents. The overexchanged stearyl methyl ammonium chloride in the montmorillonite layers can be completely washed out by ethanol. Polypropylene–montmorillonite nanocomposites were prepared by using the supported rac‐Et(Ind)₂ZrCl₂ catalyst on the montmorillonite. The nanocomposites that were polymerized by the supported catalyst were characterized by infrared spectroscopy, nuclear magnetic resonance, X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, and transmission electron microscopy. Transmission electron microcopy shows that each silicate sheet of montmorillonite is randomly dispersed into the polypropylene matrix following polymerization by using a supported catalyst. The polypropylene nanocomposites had higher crystallinity, hardness, and thermal properties than pure polypropylene. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1228–1236, 2005     

Structural,mechanical and thermal studies of double‐molded isotactic polypropylene nanocomposites with multiwalled carbon nanotubes

Nanocomposites of isotactic polypropylene (iPP) and multiwalled carbon nanotubes (MWCNTs) with various contents of MWCNTs were fabricated by double molding techniques. X‐ray diffraction measurements reveal a development of α‐crystal with lamellar stacks having a long period of 150 Å in the neat iPP that increases to 165 Å in 2 wt % MWCNTs‐loaded composites, indicating that MWCNTs enhance crystallization of iPP as a nucleating factor. Mechanical properties, such as tensile strength, flexural strength, Young's modulus, tangent modulus, and microhardness are found to increase with increasing MWCNTs content. Thermal analyses represent an increase of crystallization and melting temperatures and a decrease of thermal stability of the composites with increasing MWCNTs. Changes in structural, mechanical, and thermal properties of the composites due to the addition of MWCNTs are elaborately discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of nylon 6/carboxylic silica nanocomposites via in situ polymerization

Nylon 6/carboxylic acid‐functionalized silica nanoparticles (SiO₂‐COOH) nanocomposites were prepared by in situ polymerization of caprolactam in the presence of SiO₂‐COOH. The aim of this work was to study the effect of carboxylic silica on the properties of the nylon 6 through the interfacial interactions between the SiO₂‐COOH nanoparticles and the nylon 6 matrix. For comparison, pure nylon 6, nylon 6/SiO₂ (unmodified) and nylon 6/amino‐functionalized SiO₂ (SiO₂‐NH₂) were also prepared via the same method. Fourier transform infrared spectrometer (FTIR) spectroscopy was used to evaluate the structure of SiO₂‐COOH and nylon 6/SiO₂‐COOH. The results from thermal gravimetric analysis (TGA) indicated that decomposition temperatures of nylon 6/SiO₂‐COOH nanocomposites at the 5 wt % of the total weight loss were higher than the pure nylon 6. Differential scanning calorimeter (DSC) studies showed that the melting point (T_m) and degree of crystallinity (X_c) of nylon 6/SiO₂‐COOH were lower than the pure nylon 6. Mechanical properties results of the nanocomposites showed that nylon 6 with incorporation of SiO₂‐COOH had better mechanical properties than that of pure nylon 6, nylon 6/SiO₂, and nylon 6/SiO₂‐NH₂. The morphology of SiO₂, SiO₂‐NH₂, and SiO₂‐COOH nanoparticles in nylon 6 matrix was observed using SEM measurements. The results revealed that the dispersion of SiO₂‐COOH nanoparticles in nylon 6 matrix was better than SiO₂ and SiO₂‐NH₂ nanoparticles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Graphene‐reinforced biodegradable poly(ethylene succinate) nanocomposites prepared by in situ polymerization

In this study, poly(ethylene succinate)(PES)/graphene nanocomposites were facilely prepared by in situ melt polycondensation of succinic acid and ethylene glycol in which contained well dispersed graphene oxide (GO). Fourier transform infrared (FTIR), GPC, TGA, and XRD were used to characterize the composites. The FTIR spectra and TGA measurement confirmed that PES chains had been successfully grafted onto GO sheets along with the thermal reduction of GO to graphene during the polymerization. GPC results indicated that increasing amounts of graphene caused a slight decrease in number average molecular weight of PES matrix when polymerization time was kept constant. The content of grafted PES chains on graphene sheets was also determined by TGA and was to be about 60%, which made the graphene sheets homogeneously dispersed in the PES matrix, as demonstrated by SEM and XRD investigations. Furthermore, the incorporation of thermally reduced graphene improved the thermal stability and mechanical properties of the composites significantly. With the addition of 0.5 wt % graphene, onset decomposition temperature of the composite was increased by 12°C, and a 45% improvement in tensile strength and 60% in elongation at break were also achieved. The enhanced performance of the composites is mainly attributed to the uniform dispersion of graphene in the polymer matrix and the improved interfacial interactions between both components. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3212–3220, 2013     

Poly(vinyl chloride‐co‐vinyl acetate‐co‐maleic anhydride)/silica nanocomposites derived from in situ suspension polymerization

Poly(vinyl chloride‐co‐vinyl acetate‐co‐maleic anhydride) (PVVM)/silica nanocomposites were prepared by the suspension radical copolymerization of the monomers in the presence of fumed silica premodified with γ‐methylacryloxypropl trimethoxy siliane. Morphological observation showed that the silica particles of nanometer scale were well dispersed in the copolymer matrix of the nanocomposites films, whereas silica particles tended to agglomerate in the composites films prepared by the solution blending of PVVM with silica. The experimental results show that the thermal stability, glass‐transition temperature, tensile strength, and Young's modulus were significantly enhanced by the incorporation of silica nanoparticles. The enhancement of properties was related to the better dispersion of silica particles in polymer matrix and the interaction between the polymer chains and the surfaces of the silica particles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of bimodal polypropylene in two‐step polymerization

Polymerization of propylene was carried out by using MgCl₂.EtOH.TiCl₄.DIBP.TEA.cHMDMS catalyst system in n‐heptane, where MgCl₂, EtOH, TiCl₄, DIBP (diisobutyl phthalate), TEA (triethyl aluminum), and cHMDMS (cyclohexyl methyl dimethoxy silane) were support, ethanol for alcoholation, catalyst, external donor, cocatalyst (activator), and internal donor, respectively. The catalyst activity and polymer isotacticity were studied by measuring the produced polymer and its solubility in boiling n‐heptane, respectively. The molecular weight and molecular weight distribution of the polymers were evaluated by gel permeation chromatography. Hydrogen was used for controlling the molecular weight. For producing the bimodal polypropylene, the polymerization was carried out in two steps (i.e., in the presence and absence of hydrogen). It was found that the catalyst showed high activity and stereoselectivity, on the other hand, bimodal polymer could simply be produced in two‐step polymerization by using MgCl₂.EtOH.TiCl₄.DIBP.TEA.cHMDMS catalyst system. Meanwhile, the effect of the step of the hydrogen adding on propylene polymerization was investigated. It was shown that the addition of hydrogen in the second step was more suitable. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1456–1462, 2006     

Polyethylene‐montmorillonite nanocomposites obtained by in situ polymerization of ethylene with nickel‐diimine catalysts

Nanocomposites of exfoliated montmorillonite in polyethylene were obtained using a combination of 1,4‐bis(2,6‐diisopropylphenyl)‐acenaphthenediimine‐dichloro‐nickel(II), montmorillonite, and methylalumoxane (MAO) or trimethylaluminum (TMA) to polymerize ethylene. The properties of the polymers were strongly influenced by the amount of clay they contained. The addition of 2.5% commercial montmorillonite (KSF or Cloisite 15A) enhanced the storage modulus from 5 to 878 MPa. Transmission electron microscopy (TEM) analyses provided evidence of exfoliation of the montmorillonite with the formation of a polyethylene nanocomposite. The enhanced mechanical properties were explained as a consequence of the reinforcement due to the presence of nanoscale layers formed from exfoliation of the clay included in the polyethylene matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Property investigation of polypropylene/multiwall carbon nanotube nanocomposites prepared via in situ polymerization

In this study, polypropylene/carbon nanotube nanocomposites were prepared via in situ polymerization using a bi‐supported Ziegler ? Natta catalytic system. In this system, magnesium ethoxide and multiwall carbon nanotubes (MWCNTs) are jointly used as catalyst supports. SEM images reveal the distribution and quite good dispersion of MWCNTs throughout the polypropylene (PP) matrix. The thermal properties of the samples were examined using DSC and TGA tests. The results show that the crystallization temperature of the nanocomposites significantly increases while the melting point is not markedly affected. In addition, the thermal stability is improved. The melt rheological properties of PP/MWCNT nanocomposites in the linear and nonlinear viscoelastic response regions were studied. An increment of the complex viscosity (η^*), storage modulus (G′) and loss modulus (G′′) and a decrement of the loss factor (tan δ) compared with neat PP are observed. Steady shear flow experiments show an increase in shear viscosity with increasing the MWCNT content. © 2013 Society of Chemical Industry     

Structure and properties of tailor‐made poly(ethyl acrylate)/clay nanocomposites prepared by in situ atom transfer radical polymerization

An in‐depth study was carried out on the structure and properties of a series of poly(ethyl acrylate)/clay nanocomposites prepared by in situ atom transfer radical polymerization (PNCIs) with well‐defined molecular weights and narrow molecular weight distributions. Wide‐angle X‐ray diffraction and transmission electron microscopy studies revealed an exfoliated clay morphology, whereas conventional solution blending generated an intercalated structure. The storage moduli of the PNCIs showed a moderate increase over that of the neat polymer [poly(ethyl acrylate)]. The sample containing 4 wt % clay (PNCI4, where the number following PNCI indicates the weight percentage of clay) exhibited the highest improvement (31.9% at 25°C). In PNCIs, the β‐transition temperature showed a remarkable decrease (by 175% in PNCI4) along with a shift toward higher temperatures. This indicated the probability of the anchoring of the ? OH group of the clay layers to the >C?O group of the pendant acrylate moiety, which was also confirmed by Fourier transform infrared analysis. Rheological measurements indicated a significant increase in the shear viscosity [by 9% in PNCI2, 15% in PNCI4, and 6% in the poly(ethyl acrylate)/clay nanocomposite with 2 wt % clay prepared by solution blending]. The PNCIs registered enhanced thermal stability, as indicated by the shift in the peak maximum temperature (388 and 392°C for the neat polymer and PNCI4, respectively) and a decrease in the rate of degradation (by 3.5% in PNCI2, 10.2% in PNCI4, and 49.3% in PNCI6). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and crystallization of poly(ethylene terephthalate)/SiO2 nanocomposites by in‐situ polymerization

Poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites were prepared by in situ polymerization. The dispersion and crystallization behaviors of PET/SiO₂ nanocomposites were characterized by means of transmission electron microscope (TEM), differential scanning calorimeter (DSC), and polarizing light microscope (PLM). TEM measurements show that SiO₂ nanoparticles were well dispersed in the PET matrix at a size of 10–20 nm. The results of DSC and PLM, such as melt‐crystalline temperature, half‐time of crystallization and crystallization kinetic constant, suggest that SiO₂ nanoparticles exhibited strong nucleating effects. It was found that SiO₂ nanoparticles could effectively promote the nucleation and crystallization of PET, which may be due to reducing the specific surface free energy for nuclei formation during crystallization and consequently increase the crystallization rate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 655–662, 2006     

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     

Preparation by melt mixing and characterization of isotactic polypropylene/SiO2 nanocomposites containing untreated and surface‐treated nanoparticles

In the present study two series of isotactic polypropylene (iPP)/SiO₂ nanocomposites containing 1, 2.5, 5, 7.5, and 10 wt % SiO₂ nanoparticles were prepared by melt‐mixing on a twin‐screw corotating extruder. In the first series untreated fumed silica nanoparticles were used, whereas in the second nanoparticles were surface‐treated with dimethyldichlorosilane. In both cases, the average size of the primary nanoparticles was 12 nm. Tensile and impact strength were found to increase and to be affected mainly by the type and content of silica nanoparticles. A maximum was observed, corresponding to samples containing 2.5 wt % SiO₂. These findings are discussed in light of the SEM and TEM observations. By increasing the amount of nanoparticles, large aggregates of fumed silica could be formed, which may explain the reduction of mechanical properties with higher concentrations of SiO₂. However, it was found that surface‐treated nanoparticles produced larger aggregates than did those derived from untreated nanoparticles, despite the increased adhesion of the iPP matrix, as was postulated from yield strength. This behavior negatively affected mechanical properties. In addition, an effort was made to determine if toughening theories, mainly the critical interparticle distance for rubber toughening or composites, also might be applicable in nanocomposites. From DSC measurements it was demonstrated that silica nanoparticles acted as effective nucleating agents, increasing the crystallization rate and the degree of crystallinity of iPP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2684–2696, 2006     

Synthesis and characterization of chlorine‐containing flame‐retardant polyurethane nanocomposites via in situ polymerization

We have developed flame‐retardant polyurethanes (FRPUs) and polyurethane (PU) nanocomposites via in situ polymerization. Three series of thermoplastic elastomeric PUs were synthesized to investigate the effect of incorporating 3‐chloro‐1,2‐propanediol (CPD) and nanoclay on mechanical, thermal properties, and also resistance to burning. PU soft segments were based on poly(propylene glycol). Hard segments were based on either CPD or 1,4‐buthane diol (BDO) in combination with methyl phenyl di‐isocyanate named PU or FRPU, respectively. In the third series, CPD was used as chain extender also nanoclay (1% wt) and incorporated and named as flame‐retardant polyurethane nanocomposites (FRPUN). Mechanical properties and LOI of PUs and nanocomposites have been evaluated. Results showed that increasing the hard segment (chlorine content) leads to the increase in flame retardancy and burning time. Addition of nanoclay to CPD‐containing PUs leads to obtain self‐extinguish PUs using lower CPD contents, higher Young's modulus, and strength without any noticeable decrease in elongation at break. Investigation of the TGA results showed that copresence of nanoclay and chlorine structure in the PU backbone can change thermal degradation pattern and improve nanocomposite thermal stability. X‐ray diffraction and transmission electron microscopy studies confirmed that exfoliation and intercalation have been well done. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of polystyrene/layered double‐hydroxide nanocomposites via in situ emulsion and suspension polymerization

Polystyrene (PS)/ZnAl layered double‐hydroxide (LDH) nanocomposites were synthesized via in situ emulsion and suspension polymerization in the presence of N‐lauroyl‐glutamate surfactant and long‐chain spacer and characterized with elemental analysis, Fourier transform infrared spectrum, X‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis. The XRD and TEM results demonstrate that the exfoliated ZnAl–LDH layers were well dispersed at molecular level in the PS matrix. The completely exfoliated PS/LDH nanocomposites were obtained even at the 20 and 10 wt % LDH loadings prepared by emulsion polymerization and suspension polymerization, respectively. The PS/LDH nanocomposites with a suitable amount of LDH showed apparently enhanced thermal stability. When the 50% weight loss was selected as a comparison point, the decomposition temperature of the exfoliated PS/LDH sample prepared by emulsion polymerization with a 5 wt % LDH loading was about 28°C higher than that of pure PS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3758–3766, 2006     

Study of polypropylene/montmorillonite nanocomposites prepared by solid‐state shear compounding (S3C) using pan‐mill equipment: the morphology of montmorillonite and thermal properties of the nanocomposites

In this paper, polypropylene (PP)/organophilic montmorillonite (OMMT) nanocomposites were successfully prepared without any compatibilizers by solid‐state shear compounding (S³C) using pan‐mill equipment. X‐ray diffraction (XRD) patterns show that the OMMT characteristic (001) peak at 2θ equal to 4.59 degrees disappeared for the milled OMMT and corresponding composites. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) photographs show that the thickness of pan‐milled OMMT decreased from ca 100–200 nm to ca 30–50 nm, and OMMT was partly exfoliated in the PP matrix because the pan‐type mill can exert fairly strong squeezing force in the normal direction and shearing force in both radial and tangential directions on milled materials. PP/OMMT nanocomposites at low OMMT loading have higher melting point, crystallization temperature, thermal degradation temperature and heat distortion temperature than those of neat PP. Moreover, addition of OMMT accelerates crystallization of PP significantly. S³C is a novel approach to prepare polymer/layered silicate nanocomposites with high performances at low filler loading. Copyright © 2004 Society of Chemical Industry     

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

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

Synthesis and 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