Phase morphology and clay distribution of poly(trimethylene terephthalate)/polypropylene/montmorillonite nanocomposites

Poly(trimethylene terephthalate) (PTT)/polypropylene (PP) blend nanocomposites were prepared by melt mixing of PTT, PP, and organically modified clay. The phase morphologies of the PTT/PP nanocomposites and the distribution of the clay in the nanocomposites were investigated using scanning electron microscopy, transmission electron microscopy (TEM), and wide angle X‐ray diffraction. When PP is the dispersed phase, the domain size of the PP phase is decreased significantly with increasing the clay content from 0 to 5 wt %. In contrast, when PTT is the dispersed phase, the dimension of the PTT phase is a little larger in the presence of 2 wt % clay compared with the case of without clay. TEM observations indicate that the clay is mainly distributed at the phase interfaces along the phase borderlines. In addition, some intercalated clay tactoids (multilayer particles) are observed in the PTT matrix whereas no discernable clay particles can be found in the PP phase, indicating that the affinity of clay with PTT is higher than with PP. In the presence of 5 wt % PP‐graft‐maleic anhydride, the phase morphology is much finer, and most clay is exfoliated and distributed at the phase interfaces forming phase borderlines in polygonal shape. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of clay on immiscible morphology of poly(butylene terephthalate)/polyethylene blend nanocomposites

Polymer blend nanocomposites containing poly(butylene terephthalate) (PBT), polyethylene (PE), and organoclay were prepared by direct melt compounding. Their immiscible morphologies weree investigated using electronmicroscopy, X‐ray diffraction, and parallel plate rheometry. The PE domain sizes were reduced when the polar PBT phase was continuous (PBT/PE = 60/40) because the clay tactoids effectively prevented the coalescence of the dispersed PE domains. However, when the PBT component presented domains dispersed in the rich PE matrix (PBT/PE = 40/60), the addition of clay (>2 wt %) changed the phase morphology into a novel cocontinuous one, which was further confirmed by rheological measurements. The existence of clay tactoids led to a sharp enhancement in the viscosity of the PBT phase, changing the viscosity ratio between the PBT and PE phases remarkably, which may have promoted the phase inversion. As a result, clay had significant effects on the morphology of the polymer blend. © 2006 Wiley Periodicals Inc. J Appl Polym Sci 102: 3628–3633, 2006     

Nonisothermal crystallization kinetics of poly(butylene terephthalate)/montmorillonite nanocomposites

The melt intercalation method was employed to prepare poly(butylene terephthalate) (PBT)/montmorillonite (MMT) nanocomposites, and the microstructures were characterized with X‐ray diffraction and transmission electron microscopy. Then, the nonisothermal crystallization behavior of the nanocomposites was studied with differential scanning calorimetry (DSC). The DSC results showed that the exothermic peaks for the nanocomposites distinctly shifted to lower temperatures at various cooling rates in comparison with that for pure PBT, and with increasing MMT content, the peak crystallization temperature of the PBT/MMT hybrids declined gradually. The nonisothermal crystallization kinetics were analyzed by the Avrami, Jeziorny, Ozawa, and Mo methods on the basis of the DSC data. The results revealed that very small amounts of clay (1 wt %) could accelerate the crystallization process, whereas higher clay loadings reduced the rate of crystallization. In addition, the activation energy for the transport of the macromolecular segments to the growing surface was determined by the Kissinger method. The results clearly indicated that the hybrids with small amounts of clay presented lower activation energy than PBT, whereas those with higher clay loadings showed higher activation energy. The MMT content and the crystallization conditions as well as the nature of the matrix itself affected the crystallization behavior of the hybrids. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3257–3265, 2006     

Crystal morphology and crystallization kinetics of polyamide‐11/clay nanocomposites

Polyamide‐11 (PA11)/clay nanocomposites were prepared by in situ intercalative polymerization. The crystal morphology and crystallization kinetics of these nanocomposites were investigated via polarized light microscopy (PLM), small‐angle laser scattering (SALS) and differential scanning calorimetry (DSC). PA‐11 can crystallize into well‐formed spherulites, while only very tiny crystallites were observed by PLM and SALS for the nanocomposites. Both isothermal and non‐isothermal crystallization methods were employed to investigate the crystallization kinetics by DSC. Both techniques showed an increased crystallization rate with the addition of clay. However, the Avrami exponent decreased with the addition of clay in isothermal crystallization but showed a wide range of values depending on the cooling rate in the non‐isothermal crystallization. The changes in crystal morphology and crystallization kinetics can be understood as being due to the ‘supernucleating’ effect of the nanodispersed clay layers. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of poly(ethylene terephthalate)/attapulgite nanocomposites

A kind of clay with fibrous morphology, attapulgite (AT), was used to prepare poly (ethylene terephthalate) (PET)/AT nanocomposites via in situ polymerization. Attapulgite was modified with Hexadecyltriphenylphosphonium bromide and silane coupling agent (3‐glycidoxypropltrimethoxysilane) to increase the dispersion of clay particles in polymer matrix and the interaction between clay particles and polymer matrix. FTIR and TGA test of the organic‐AT particles investigated the thermal stability and the loading quantity of organic reagents. XRD patterns and SEM micrographs showed that the organic modification was processed on the surface of rod‐like crystals and did not shift the crystal structure of silicate. For PET/AT nanocomposites, it was revealed in TEM that the fibrous clay can be well dispersed in polymer matrix with the rod‐like crystals in the range of nanometer scale. The diameter of rod‐like crystal is about 20 nm and the length is near to 500 nm. The addition of the clay particles can enhance the thermal stability and crystallization rate of PET. With the addition of AT in PET matrix, the flexural modulus of those composites was also increased markedly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1279–1286, 2007     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate)/clay nanocomposites prepared by melt processing

In this study, cold and melt crystallization behaviors of amorphous poly(ethylene terephthalate) (PET)/clay nanocomposites were investigated. Two nanocomposite samples with the same amount of inorganic content were prepared by melt processing using natural montmorillonite (Na‐MMT) and organo‐modified montmorillonite (org‐MMT). Depending on the clay structure, clay dispersion into PET and crystallization behavior of the samples were studied using X‐ray diffraction and differential scanning calorimetry methods, respectively. Effects of clay structure and organic groups between clay layers in org‐MMT on the melt crystallization kinetics of the samples were analyzed with various kinetic models, namely, the Ozawa, Avrami modified by Jeziorny, and Liu‐Mo. Crystallization activation energies of the samples were also determined by the Kissinger and Augis–Bennett models. Exfoliated structures were obtained in the nanocomposite samples prepared with both the Na‐MMT and org‐MMT. From the kinetics study, it was found that the melt‐crystallization rate of the sample prepared with the Na‐MMT was higher than that prepared with the org‐MMT at a given cooling rate. It can be concluded that organic ammonium groups in the org‐MMT decelerate the crystallization rate of PET chains possibly by affecting the chain diffusion and folding. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Nonisothermal melt crystallization kinetics of poly(ethylene terephthalate)/Barite nanocomposites

Poly(ethylene terephthalate) (PET)/Barite nanocomposites were prepared by direct melt compounding. The nonisothermal melt crystallization kinetics of pure PET and PET/Barite nanocomposites, containing unmodified Barite and surface‐modified Barite (SABarite), was investigated by differential scanning calorimetry (DSC) under different cooling rates. With the addition of barite nanoparticles, the crystallization peak became wider and shifted to higher temperature and the crystallization rate increased. Several analysis methods were used to describe the nonisothermal crystallization behavior of pure PET and its nanocomposites. The Jeziorny modification of the Avrami analysis was only valid for describing the early stage of crystallization but was not able to describe the later stage of PET crystallization. Also, the Ozawa method failed to describe the nonisothermal crystallization behavior of PET. A combined Avrami and Ozawa equation, developed by Liu, was used to more accurately model the nonisothermal crystallization kinetics of PET. The crystallization activation energies calculated by Kissinger, Takhor, and Augis‐Bennett models were comparable. The results reveal that the different interfacial interactions between matrix and nanoparticles are responsible for the disparate effect on the crystallization ability of PET. POLYM. COMPOS., 31:1504–1514, 2010. © 2009 Society of Plastics Engineers     

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     

Interface structure of poly(ethylene terephthalate)/silica nanocomposites

The interface structure of the poly(ethylene terephthalate) (PET)/silica nanocomposites was characterized by Fourier transform infrared and solid-state nuclear magnetic resonance. Our study reveals that PET chains are grafted onto the surface of silica nanoparticles, and they form branched and lightly crosslinking structures during the polycondensation. Gel permeation chromatography measurements indicate that the grafted PET chains have a lower molecular weight and broader distribution. Furthermore, a model has been developed to elucidate the interaction of an entanglement network between silica and PET chains that lead to enhancements of G′, G″ and η* values of PET/2 wt% silica nanocomposites.     

Isothermal crystallization of poly(ethylene‐co‐glycidyl methacrylate)/clay nanocomposites

Poly(ethylene‐co‐glycidyl methacrylate) (PEGMA)/clay nanocomposites with clay concentrations of 1, 3, or 5 wt % were prepared via y melt blending in a twin‐screw extruder. Wide‐angle X‐ray diffraction showed that the clay layers were intercalated by PEGMA. Differential scanning calorimetry was used to analyze the isothermal crystallization, and the equilibrium melting temperature was determined with the Hoffman–Weeks method. The Avrami, Tobin, Malkin, and Urbanovici–Segal models were applied to describe the kinetics of crystallization from the melt state under isothermal conditions. The crystallization kinetics showed that the addition of clay facilitated the crystallization of PEGMA, with the clay functioning as a heterophase nucleating agent; at higher concentrations, however, the physical hindrance of the clay layers to the motion of PEGMA chains retarded the crystallization process. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1051–1064, 2005     

Synthesis and characterization of poly(ethylene terephthalate) nanocomposites with organoclay

Poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation method. The clay was organo‐modified with the intercalation agent cetylpyridinium chloride (CPC). Wide‐angle X‐ray diffraction (XRD) showed that the layers of MMT were intercalated by CPC. Four nanocomposites with organoclay contents of 1, 5, 10, and 15 wt % were prepared by solution blending. XRD showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay present. According to the results of differential scanning calorimetry (DSC) analysis, clay behaves as a nucleating agent and enhances the crystallization rate of PET. The maximum enhancement of crystallization rate for the nanocomposites was observed in those containing about 10 wt % organoclay within the studied range of 1–15 wt %. From thermogravimetric analysis (TGA), we found that the thermal stability of the nanocomposites was enhanced by the addition of 1–15 wt % organoclay. These nanocomposites showed high levels of dispersion without agglomeration of particles at low organoclay content (5 wt %). An agglomerated structure did form in the PET matrix at 15 wt % organoclay. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 140–145, 2004     

Thermal stability of surfactants with amino and imido groups in poly(ethylene terephthalate)/clay composites

Effects of thermal stability of surfactants with amino and imido groups on thermal properties of poly(ethylene terephthalate) (PET)/clay composites were studied. The imidosilane surfactant was synthesized successfully from the imide reaction between amino silane and phthalic anhydride. TGA shows that imidosilane decomposition behaviors have two major stages according to the degradations of different functional groups. After melt extrusion, the decomposition of amino functional groups in amino surfactants decreases the thermal stability of organoclay and accelerates the degradation behaviors of PET composites. Because of the enhanced thermal stability of imidosilane surfactants, PET/imido‐palygorskite (PT) composites represent enhanced thermal stability, good dispersion and low thermal expansion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Suspension polymerization of poly(methyl methacrylate)/clay nanocomposites

Polymer/clay nanocomposites (PCNs) of poly(methyl methacrylate) and an organically modified clay, Cloisite 15a, were synthesized in situ with a suspension polymerization technique. The amount of clay present in the PCNs was varied to provide a better understanding of the effect of the clay on the properties of the polymer matrix. However, unexpectedly, we found that the concentration of clay had a dramatic impact on the molecular weight of the polymer matrix, and a relationship between the clay concentration and polymer molecular weight was determined. The PCNs were characterized with size exclusion chromatography (SEC), X‐ray diffraction, transmission electron microscopy, and oscillatory shear rheology. From oscillatory shear rheology, the full master curves for the PCNs were obtained by application of the time–temperature superposition principle. To enable the effect of the clay on the rheology to be quantified, the experimental data was compared to the time‐dependent diffusion model of des Cloizeaux for polydisperse polymer melts, which enabled the polydispersity to be incorporated through the use of the molecular weight distribution obtained via SEC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Melting behaviors and isothermal crystallization kinetics of poly(ethylene terephthalate)/mesoporous molecular sieve composite

Isothermal crystallization and subsequent melting behavior of mesoporous molecular sieve (MMS) filled poly(ethylene terephthalate) (PET) composites have been investigated at the designated temperature by using differential scanning calorimeter (DSC). The commonly used Avrami equation was used to fit the primary stage of the isothermal crystallization. The Avrami exponents n were evaluated to be 2<n<3 for the neat PET and composites. MMS particles acting as nucleating agent in composite accelerated the crystallization rate with decreasing the half-time of crystallization. The crystallization activation energy calculated from the Arrhenius' formula was reduced as MMS content increased. It is shown that the MMS particles made the molecular chains of PET easier to crystallize during the isothermal crystallization process. Subsequent differential scanning calorimeter scans of the isothermally crystallized samples exhibited different melting endotherms. It is found that much smaller or less perfect crystals formed in composites due to the interaction between molecular chains and the MMS particles. The crystallinity of composites was enhanced by increasing MMS content.     

Antimicrobial activity and biodegradation behavior of poly(butylene adipate‐co‐terephthalate)/clay nanocomposites

Poly(butylene adipate‐co‐terephthalate) (PBAT) nanocomposites films are prepared by a solution intercalation process using natural montmorillonite (MMT) and cetyltrimethylammonium bromide (CTAB)‐modified montmorillonite (CMMT). Cation exchange technique has been used for modification of MMT by CTAB and characterized by Fourier transform infrared analysis, thermo‐gravimetric analysis, and X‐ray diffraction (XRD) studies. CMMT gives better dispersion in the PBAT matrix than MMT and is confirmed by XRD and transmission electron microscopy. Because of better compatibility of CMMT, water vapor transmission rate of PBAT decreases more in the presence of CMMT than MMT. The biodegradability of PBAT and its nanocomposite films are studied in compost and from the morphological analysis it is apparent that the PBAT/CMMT shows a lower biodegradation rate in comparison to the PBAT/MMT. The antimicrobial activity of PBAT and its nanocomposite films is tested by an inhibition zone method. Because of the presence of the quaternary ammonium group of CTAB‐modified MMT, PBAT/CMMT nanocomposites show adequate antimicrobial activity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40079.     

Preparation and properties of poly(ethylene terephthalate)/ATO nanocomposites

Antimony doped tin oxide (ATO) nanoparticles modified poly(ethylene terephthalate) (PET) composites used for manufacturing antistatic PET fiber were synthesized by in situ polymerization. The crystallization and multiple melting behavior of the nanocomposites were systemically investigated by means of Differential Scanning Calorimeter (DSC), Fourier Transform Infrared (FTIR), X‐ray Diffraction (XRD) techniques. The degree of crystallinity in nanocomposites increased with increasing ATO content. Smaller and more incomplete crystals are presented in the crystalline regions of the nanocomposites with increasing the content of ATO, which could be attributed to heterogeneous nucleation effects of ATO nanoparticles. Dynamic Mechanical Analysis (DMA) measurements showed that the storage moduli of the nanocomposites increased with increasing the content of ATO, due to formation of immobilized layer between polymer and filler. The interactions between ATO and PET molecules result in high tan δ for the PET/ATO nanocomposites. Percolation threshold of PET/ATO hybrid fibers prepared by the nanocomposites at room temperature was as low as 1.05 wt %, much lower than that of the composites filled with conventional conductive particles. Adding ATO nanoparticles obviously improves the conductivity of PET. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Nonisothermal crystallization kinetics of poly(butylene terephthalate)/poly(ethylene terephthalate)/glass fiber composites

The influences of the glass fiber (GF) content and the cooling rate for nonisothermal crystallization process of poly(butylene terephthalate)/poly(ethylene terephthalate) (PBT/PET) blends were investigated. The nonisothermal crystallization kinetics of samples were detected by differential scanning calorimetry (DSC) at cooling rates of 5°C/min, 10°C/min, 15°C/min, 20°C/min, 25°C/min, respectively. The Jeziony and Mozhishen methods were used to analyze the DSC data. The crystalline morphology of samples was observed with polarized light microscope. Results showed that the Jeziony and Mozhishen methods were available for the analysis of the nonisothermal crystallization process. The peaks of crystallization temperature (T_p) move to low temperature with the cooling rate increasing, crystallization half‐time (t_1/2) decrease accordingly. The crystallization rate of PBT/PET blends increase with the lower GF contents while it is baffled by higher GF contents. POLYM. COMPOS. 36:510–516, 2015. © 2014 Society of Plastics Engineers     

Properties and morphology of poly(L‐lactide)/clay composites according to the clay modification

Montmorillonite (MMT) was modified with dodecylamine, 1,12‐diaminododecane, and 1,11‐aminoundecanoic acid to prepare CHMMT, NHMMT, and COMMT, respectively. The three clays were mixed with poly(L ‐lactide) (PLLA) with the aid of chloroform. Depending on the modifiers, PLLA/MMT composites exhibited different mechanical properties and morphology. A completely exfoliated morphology was observed in the PLLA/COMMT composite (PLACO). The PLACO exhibited the best tensile properties among the tested composites because of the finest dispersion of the clay layers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4983–4988, 2006