Poly(etherimide)/montmorillonite nanocomposites prepared by melt intercalation

A novel aromatic amine organo‐modifier synthesized in our previous work was used to treat montmorillonite (MMT) and the organo‐modified MMT was used to prepare poly(etherimide) (PEI)/MMT nanocomposites by a melt intercalation method. MMT treated by this amine exhibited large layer‐to‐layer spacing and a high ion‐exchange ratio (>95%). The nanocomposites were characterized with X‐ray diffraction (XRD), transmission electron microscopy (TEM), dynamic mechanical analysis, a universal tester, thermogravimetric analysis, and by differential scanning calorimetry. The results of XRD and TEM showed that the nanocomposites formed exfoliated structures even when the MMT content was 10 wt %. When the MMT content was below 3 wt %, the PEI/MMT nanocomposites were strengthened and toughened at the same time. The nanocomposites also showed marked decreases in coefficient of thermal expansion and solvent uptake. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1857–1863, 2003     

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

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

Polarized confocal Raman microspectroscopy studies of chain orientation on injected poly(propylene)/montmorillonite nanocomposites

Molecular orientation along the depth of poly(propylene) (PP) and PP nanocomposite samples was analyzed by using confocal Raman microspectroscopy. The injection process led to a chain orientation that is higher on the surface of the samples. Residual stresses were relaxed through an annealing treatment, resulting in an increase of the molecular orientation along the injection direction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2377–2382, 2005     

Synthesis and characterization of novel poly(o‐toluidine) montmorillonite nanocomposites: Effect of surfactant on intercalation

The investigation of clay based polymer nanocomposites has opened the door for the development of novel, ecofriendly advanced nano materials that can be safely recycled. Because of their nanometer size dispersion, these nanocomposites often have superior physical and mechanical properties. In this study, novel nanocomposites of poly(o‐toluidine) (POT) and organically modified montmorillonite (MMT) were synthesized using camphor sulfonic acid (CSA), cetyl pyridinum chloride (CPCl), and N‐cetyl‐N,N,N‐trimethyl ammonium bromide (CTAB) to study the role of surfactant modification on the intercalation. The in situ intercalative polymerization of POT within the organically modified MMT layers was analyzed by FTIR, UV–visible, XRD, SEM as well as TEM studies. The average particle size of the nanocomposites was found to be in the range 80–100 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Novel preparation of poly(propylene)–layered silicate nanocomposites

We used a novel approach to prepare poly(propylene)–clay nanocomposite starting from pristine montmorillonite and reactive compatibilizer hexadecyl trimethyl ammonium bromide. The nanocomposite structure was revealed by X‐ray diffraction and high‐resolution electronic microscopy. The thermal properties of the nanocomposite were investigated by thermogravimetric analysis. An increase of thermal stability was observed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2586–2588, 2003     

Electron beam synthesis and characterization of poly(vinyl alcohol)/montmorillonite nanocomposites

Poly(vinyl alcohol) (PVA)/montmorillonite clay (MMT) nanocomposites in the form of films were prepared under the effect of electron beam irradiation. The PVA/MMT nanocomposites gels were characterized by X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and mechanical measurements. The study showed that the appropriate dose of electron beam irradiation to achieve homogeneous nanocomposites films and highest gel formation was 20 kGy. The introduction of MMT (up to 4 wt %) results in improvement in tensile strength, elongation at break, and thermal stability of the PVA matrix. In addition, the intercalation of PVA with the MMT clay leads to an impressive improved water resistance, indicating that the clay is well dispersed within the polymer matrix. Meanwhile, it was proved that the intercalation has no effect on the metal uptake capability of PVA as determined by a method based on the color measurements. XRD patterns and SEM micrographs suggest the coexistence of exfoliated intercalated MMT layers over the studied MMT contents. The DSC thermograms showed clearly that the intercalation of PVA polymer with these levels of MMT has no influence on the melting transitions; however, the glass transition temperature (T_g) for PVA was completely disappeared, even at low levels of MMT clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1129–1138, 2006     

Poly(propylene)–poly(propylene)‐grafted maleic anhydride–organic montmorillonite (PP–PP‐g‐MAH–Org‐MMT) nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of poly(propylene) (PP), PP–organic‐montmorillonite (Org‐MMT) composite, and PP–PP‐grafted maleic anhydride (PP‐g‐MAH)–Org‐MMT nanocomposites were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny and a method developed by Mo well‐described the nonisothermal crystallization process of these samples. The difference in the exponent n between PP and composite (either PP–Org‐MMT or PP–PP‐g‐MAH–Org‐MMT) indicated that nonisothermal kinetic crystallization corresponded to tridimensional growth with heterogeneous nucleation. The values of half‐time, Z_c; and F(T) showed that the crystallization rate increased with the increasing of cooling rates for PP and composites, but the crystallization rate of composites was faster than that of PP at a given cooling rate. The method developed by Ozawa can also be applied to describe the nonisothermal crystallization process of PP, but did not describe that of composites. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The results showed that the activation energy of PP–Org‐MMT was much greater than that of PP, but the activation energy of PP–PP‐g‐MAH–Org‐MMT was close to that of pure PP. Overall, the results indicate that the addition of Org‐MMT and PP‐g‐MAH may accelerate the overall nonisothermal crystallization process of PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3093–3099, 2003     

Rheology of poly(propylene)/clay nanocomposites

The linear and nonlinear shear rheological behaviors of poly(propylene) (PP)/clay (organophilic‐montmorillonite) nanocomposites (PP/org‐MMT) were investigated by an ARES rheometer. The materials were prepared by melt intercalation with maleic anhydride functionalized PP as a compatibilizer. The storage moduli (G′), loss moduli (G″), and dynamic viscosities of polymer/clay nanocomposites (PPCNs) increase monotonically with org‐MMT content. The presence of org‐MMT leads to pseudo‐solid‐like behaviors and slower relaxation behaviors of PPCN melts. For all samples, the dependence of G′ and G″ on ω shows nonterminal behaviors. At lower frequency, the steady shear viscosities of PPCNs increase with org‐MMT content. However, the PPCN melts show a greater shear thinning tendency than pure PP melt because of the preferential orientation of the MMT layers. Therefore, PPCNs have higher moduli but better processibility compared with pure PP.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2427–2434,2004     

Preparation and characterization of maleic anhydride‐g‐polypropylene/diamine‐modified clay nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by compounding maleic anhydride‐g‐polypropylene (MAPP) with MMT modified with α,ω‐diaminododecane. Structural characterization confirmed the formation of characteristic amide linkages and the intercalation of MAPP between the silicate layers. In particular, X‐ray diffraction patterns of the modified clay and MAPP/MMT composites showed 001 basal spacing enlargement as much as 1.49 nm. Thermogravimetric analysis revealed that the thermal decomposition of the composite took place at a slightly higher temperature than that of MAPP. The heat of fusion of the MAPP phase decreased, indicating that the crystallization of MAPP was suppressed by the clay layers. PP/MAPP/MMT composites showed a 20–35% higher tensile modulus and tensile strength compared to those corresponding to PP/MAPP. However, the elongation at break decreased drastically, even when the content of MMT was as low as 1.25–5 wt %. The relatively short chain length and loop structure of MAPP bound to the clay layers made the penetration of MAPP molecules into the PP homopolymer phase implausible and is thought to be responsible for the decreased elongation at break. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 307–311, 2005     

Mechanical property and morphology comparison between the two blends poly(propylene)/ethylene‐propylene‐diene monomer elastomer and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer

The comparison of the mechanical properties between poly(propylene)/ethylene‐propylene‐diene monomer elastomer (PP/EPDM) and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer [PP/MEPDM (MAH‐g‐EPDM)] showed that the latter blend has noticeably higher Izod impact strength but lower Young's modulus than the former one. Phase morphology of the two blends was examined by dynamic mechanical thermal analysis, indicating that the miscibility of PP/MEPDM was inferior to PP/EPDM. The poor miscibility of PP/MEPDM degrades the nucleation effectiveness of the elastomer on PP. The observations of the impact fracture mode of the two blends and the dispersion state of the elastomers, determined by scanning electron microscopy, showed that PP/EPDM fractured in a brittle mode, whereas PP/MEPDM in a ductile one, and that a finer dispersion of MEPDM was found in the blend PP/MEPDM. These observations indicate that the difference in the dispersion state of elastomer between PP/EPDM and PP/MEPDM results in different fracture modes, and thereby affects the toughness of the two blends. The finer dispersion of MEPDM in the blend of PP/MEPDM was attributed to the part cross‐linking of MEPDM resulting from the grafting reaction of EPDM with maleic anhydride (MAH) in the presence of dicumyl peroxide (DCP). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2486–2491, 2002     

Investigation on the microstructure and the electric property of poly(propylene)/chlorinated poly(propylene)/poly(aniline) composites

The article presents results of studies on composites made from poly(propylene) (PP) modified with poly(aniline) (PANI) doped with dodecylbenzene sulfonic acid (DBSA) and chlorinated poly(propylene) (CPP). The volume resistivity of PP/CPP/PANI composites was detected, and the results show that the volume resistivity decreases with increasing CPP content, and there exists a minimum volume resistivity. Effects of CPP on the microstructure and crystalline structure of the PP/CPP/PANI composites and the relationship between the effects and the electric property were carefully analyzed by scanning electron microscope (SEM) and wide angle X‐ray diffraction (WAXD). The method that the specimens of SEM are polished is appropriate to investigate the morphology of conducting polymer composites. The obtained results illuminate that the area of conducting parts and insulating parts obtained from the digital analysis of the SEM image is obviously influenced by the CPP content, the parameters of the lamellar‐like structure are immediately related to CPP content and denote the dispersion of PANI‐DBSA, and the percent crystallinity and mean crystal size of PP are directly correlated with the CPP content. The increasing area of conducting parts, the increasement of layer distance, the decreasement of size and layer number of the lamellar‐like structure of PANI‐DBSA, and the increasement of the percent crystallinity and mean crystal size of PP are beneficial to the improvement of the conductive property of PP/CPP/PANI composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical,rheological, thermal,and morphological properties of blends based on poly(propylene)/poly(propylene‐co‐1‐octene)/poly(ethylene‐co‐1‐octene)

The effect of addition of propylene copolymer, produced by metallocene catalysts, on the mechanical, rheological, and morphological properties of blends based on poly(propylene) (PP) and ethylene–1‐octene copolymer (EOC) was evaluated. It was observed that the addition of 2 wt % propylene–1‐octene copolymer (POC) improved the impact strength of the EOC/PP blends. The rheological analysis indicated that the addition of propylene copolymer produced materials with improved processability. Thermal and morphological analysis showed that the POC acts as a compatibilizer on the EOC/PP blends. © 2003 Wiley Periodicals, J Appl Polym Sci 89: 1690–1695, 2003     

Preparation and characterization of polypropylene/clay nanocomposites with polypropylene‐graft‐maleic anhydride

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by the esterification of propylene‐g‐maleic anhydride (MAPP) with MMT modified with α,ω‐hydroxyamines. The structural characterization confirmed the formation of ester linkages and the interaction between the silicate layers. In particular, X‐ray diffraction patterns of the modified clays and MAPP/MMT composites showed 001 basal spacing enlargement as great as 0.14–0.62 nm according to the type of α,ω‐hydroxyamine. Thermal characterization by thermogravimetric analysis for the composites revealed increased onset temperatures of thermal decomposition. The melting peak temperature decreased, and the crystallization peak temperature increased; this indicated that MMT retarded the crystallization of MAPP. Compounding PP with MAPP/MMT composites enhanced the tensile modulus and tensile strength of PP. However, the elongation at break decreased drastically even when the MMT content was as low as 0.4–2.0 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1229–1234, 2005     

Preparation of polypropylene–clay nanocomposites by the co‐intercalation of modified polypropylene and short‐chain amide molecules

The effect of short‐chain amide (AM) molecules on the intercalation of montmorillonite clay has been investigated by the melt blending of polypropylene (PP) with clay in the presence of AM molecules such as 13‐cis‐docosenamide (erucamide). Polypropylene–clay nanocomposites (PPCNs) were prepared by the co‐intercalation of maleic anhydride grafted polypropylene (PP–MA) and an AM compound. The resulting nanocomposite structures were characterized with X‐ray diffraction (XRD) and transmission electron microscopy, whereas the thermal characterization of the PPCNs was conducted by thermogravimetric analysis. XRD results showed that the AM molecules intercalated into clay galleries and increased the interlayer spacing, a result confirmed by surface energy (contact angle) and melt flow index measurements. This additive allowed the formation of an intercalated nanocomposite structure, but an exfoliated PPCN structure was also formed with the use of AM with a PP–MA‐based compatibilizer. A new preparation method for PPCNs was, therefore, developed by the co‐intercalation of AM and PP–MA; this resulted in a significantly improved degree of intercalation and dispersion. The enhanced thermal stability of PPCN, relative to pure PP, further demonstrated the improved clay dispersion in the nanocomposite structures prepared by this method. A possible mechanism for the co‐intercalation of AM and PP–MA into the clay galleries is proposed, based on hydrogen bonding between these additives and the silicate layers. Consideration is also given to possible chemical reactions and physical interactions in this rather complex system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Study on poly(propylene)/ammonium polyphosphate composites modified by ethylene‐1‐octene copolymer grafted with glycidyl methacrylate

The compatibilization effect of ethylene‐1‐octene copolymer grafted with glycidyl methacrylate (POE‐g‐GMA) as an interface compatibilizer on the mechanical and combustion properties, and the morphology and structures of the cross sections of ammonium polyphosphate (APP)–filled poly(propylene) (PP) were investigated by thermogravimetry, dynamic mechanical analysis, and differential scanning calorimetry. The results indicated that the toughness of the PP/APP composites increased rapidly with adding POE‐g‐GMA; the dynamic mechanical spectra revealed that the increase of the toughness was closely related to the peaks of loss modulus (E″) and mechanical loss (tan δ). The improvement of the dispersion of APP in the PP matrix was attributed to the addition of POE‐g‐GMA; it was found that the interfacial adhesion between the filler and matrix was enhanced when the grafting material was added to the composites. Under such circumstances, the ratio of char formation was increased when the PP composites were heated, although the content of flame retardant was not changed, so the flame retardance of the material was improved. The addition of POE‐g‐GMA increased the rate of crystallization. At the same time, the degree of crystallinity and the temperature at the beginning of crystallization were decreased, although exerting little influence on the melt behavior of the crystallization of the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 412–419, 2004     

Investigation Into Poly(propylene)/Montmorillonite/Calcium Carbonate Nanocomposites

Summary: A novel method was used to prepare poly(propylene)/montmorillonite/calcium carbonate nanocomposites by melt‐mixing, using pristine montmorillonite (MMT), hexadecyltrimethylammonium bromide (C16), calcium carbonate (CaCO₃) and a matrix in a twin‐screw extruder. Two different sizes of calcium carbonate were used (nanosized CaCO₃ and micron‐sized CaCO₃, the average sizes being 60 nm and 12 μm respectively). The nanocomposite structure was evidenced using X‐ray diffraction (XRD), transmission electron microscopy (TEM) and high resolution electronic microscopy (HREM). Tensile tests and Izod notch impact tests suggested that the incorporation of nanosized CaCO₃ into PP/montmorillonite nanocomposites increased the mechanical properties of the composites, but the improvement in the micro‐sized CaCO₃‐filled PP/montmorillonite nanocomposites was found to be minimal. The thermal stability and flammability properties were characterized by thermogravimetric analysis (TGA) and a cone calorimeter respectively.

     

Poly(propylene)/Clay Nanocomposites Prepared by Reactive Compounding with an Epoxy Based Masterbatch

Summary: Poly(propylene) (PP)/clay nanocomposites have been prepared via a novel reactive compounding approach, in which an epoxy based masterbatch consisting of 20 wt.‐% clay was introduced to poly(propylene) with the aid of a maleic anhydride grafted PP (MAPP). The masterbatch was prepared using a recently developed “slurry compounding” technique. After melt compounding, most clay particles have been exfoliated and dispersed into small stacks with several clay layers. WAXD data shows that the dispersion of clay is better at low clay content or high MAPP content. Due to the novelty of the preparation process and complication of the system, the tensile properties of nanocomposites exhibit some unique tendencies with varying the content of MAPP or masterbatch. It is believed that the yield strength and Young's modulus can be dramatically improved after minimizing the excess of unreacted epoxy and optimizing the dispersion of clay.

TEM micrograph of PP/clay nanocomposites prepared with epoxy based masterbatch.     

Synthesis and characterization of sulfonated poly(ethylene terephthalate)/montmorillonite nanocomposites

Sulfonated poly(ethylene terephthalate) (SPET)/montmorillonite nanocomposites were prepared by in situ intercalative polymerization. The microstructure, morphology, and properties of the nanocomposites were studied with wide‐angle X‐ray diffraction, transmission electron microscopy, atomic force microscopy, differential scanning calorimetry, and thermogravimetric analysis. The results indicated that an increase in the ? SO₃Na content improved the dispersion of organically modified montmorillonite in the SPET ionomer matrix, and the dispersed layered silicates in the SPET matrix acted as nucleating agents in SPET crystallization processes and improved the thermal stability of SPET. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1150–1156, 2005     

Preparation of poly(divinylbenzene) microspheres with controllable pore structure using poly(propylene)/toluene as coporogen

Poly(divinylbenzene) (poly(DVB)) microspheres with controllable pore structure were synthesized by suspension polymerization in the presence of toluene and low‐molecular weight poly(propylene) (PP) as coporogen. The weight fraction of PP in toluene varied from 0 to 20 wt %, and the feed ratio of coporogen and DVB was kept at 1/1 (vol/vol). Effects of PP weight fraction in coporogen on the specific surface area, the average pore size, the pore size distribution and the total pore volume of final microspheres were examined. As expected, poly(DVB) microspheres prepared with toluene as sole porogen had a high specific surface area (558 m²/g). Using mixtures of toluene and PP as coporogen, it was found that the specific surface area shifted higher values when low levels of PP (2.0–6.0 wt %) in toluene were used as coporogen. However, further increase of PP weight fraction in toluene resulted in progressive decline of the specific surface area. Hg intrusion/extrusion curves and N₂ sorption isotherms implied caged pore structure with some small entrances. Furthermore, most of pore connectivity limitations may be eliminated when the weight fraction of PP in toluene exceeded 10.0 wt %. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009