Morphology,thermal, and mechanical properties of polyamide 66/clay nanocomposites with epoxy‐modified organoclay

A new kind of organophilic clay, cotreated by methyl tallow bis‐2‐hydroxyethyl quaternary ammonium and epoxy resin into sodium montmorillonite (to form a strong interaction with polyamide 66 matrix), was prepared and used in preparing PA66/clay nanocomposites (PA66CN) via melt‐compounding method. Three different types of organic clays, CL30B–E00, CL30B–E12, and CL30B–E23, were used to study the effect of epoxy resin in PA66CN. The morphological, mechanical, and thermal properties have been studied using X‐ray diffraction, transmission electron microscopy (TEM), mechanical, and thermal analysis, respectively. TEM analysis of the nanocomposites shows that most of the silicate layers were exfoliated to individual layers and to some thin stacks containing a few layers. PA66CX–E00 and PA66CX–E12 had nearly exfoliated structures in agreement with the SAXS results, while PA66CX–E23 shows a coexistence of intercalated and exfoliated structures. The storage modulus of PA66 nanocomposites was higher than that of the neat PA66 in the whole range of tested temperature. On the other hand, the magnitude of the loss tangent peak in α‐ or β‐transition region decreased gradually with the increase in the clay loading. Multiple melting behavior in PA66 was also observed. Thermal stability more or less decreased with an increasing inorganic content. Young's modulus and tensile strength were enhanced by introducing organoclay. Among the three types of nanocomposites prepared, PA66CX–E12 showed the highest improvement in properties, while PA66CX–E23 showed properties inferior to that of PA66CX–E00 without epoxy resin. In conclusion, an optimum amount of epoxy resin is required to form the strong interaction with the amide group of PA66. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1711–1722, 2006     

Thermal and mechanical properties of a polypropylene nanocomposite

An experimental polypropylene (PP) nanocomposite, containing approximately 4 wt % of an organophilic montmorillonite clay, was prepared and characterized, and its properties were compared with those of talc‐filled (20–40 wt %) compositions. Weight reduction, with maintained or even improved flexural and tensile moduli, especially at temperatures up to 70°C, was a major driving force behind this work. By a comparison with the analytical data from a nylon 6 (PA‐6) nanocomposite, it was found that the PP nanocomposite contained well‐dispersed, intercalated clay particles; however, X‐ray diffraction, transmission electron microscopy, dynamic mechanical analysis, and permeability measurements confirmed that exfoliation of the clay in PP was largely absent. The increased glass‐transition temperature (T_g) of a PA‐6 nanocomposite, which possessed fully exfoliated particles, indicated the molecular character of the matrix–particle interaction, whereas the PP nanocomposite exhibited simple matrix–filler interactions with no increase in T_g. The PP nanocomposite exhibited a weight reduction of approximately 12% in comparison with the 20% talc‐filled PP, while maintaining comparable stiffness. Undoubtedly, considerable advantages may be available if a fully exfoliated PP nanocomposite is fabricated; however, with the materials available, a combination of talc, or alternative reinforcements, and nanocomposite filler particles may provide optimum performance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1639–1647, 2003     

Melt‐compounded natural rubber nanocomposites with pristine and organophilic layered silicates of natural and synthetic origin

Composites based on natural rubber (NR) and containing organophilic and pristine layered silicates of natural and synthetic origin were produced by melt compounding and sulfur curing. The curing, thermomechanical, and mechanical properties of the mixes, which contained 10 phr (parts per hundred parts of rubber) silicates, were determined. The dispersion of the silicates was studied by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Organophilic clays accelerated the sulfur curing of NR, which was believed to occur because of a complexation reaction in which the amine groups of the clay intercalants participated. The property improvements caused by the fillers were ranked as follows: organophilic clays > pristine synthetic layered silicate (sodium fluorohectorite) > pristine natural clay (purified sodium bentonite) > precipitated nonlayered silica (used as a reference). This was attributed to partial intercalation of the organophilic clay by NR on the basis of XRD and TEM results and to the high aspect ratio of the fluorohectorite. Apart from intercalation, severe confinement (i.e., the collapse of the interlayer distance) of the organoclays was observed. This peculiar feature was traced to the formation of a zinc coordination complex, which extracted the amine intercalant of the organoclays, thus causing the collapse of the layers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 813–819, 2004     

Rubber–clay nanocomposite by solution blending

Ethylene vinyl acetate rubber (45% vinyl acetate content, EVA‐45) and organomodified clay (12Me‐MMT) composites were prepared by solution blending of the rubber and the clay. A combination of X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy studies showed that the composites obtained are on the nanometer scale. The measurements of the dynamic mechanical properties for different compositions over a temperature range (?100 to +100°C) showed that the storage moduli of these rubber–clay nanocomposites are higher above the glass to rubber transition temperature compared to the neat rubber. The tensile strength of the nanocomposites is about 1.6 times higher than that of the EVA‐45. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2216–2220, 2003     

Crystallization behavior and mechanical properties of polypropylene copolymer by in situ copolymerization with a nucleating agent and/or nano‐calcium carbonate

The crystallization behavior of polypropylene (PP) copolymer obtained by in situ reactor copolymerization with or without a nucleating agent and/or nano‐CaCO₃ particles was investigated both by thermal analysis and by polarized light microscopy. The Avrami model is successfully used to describe the crystallization kinetics of the studied copolymer. The results of the investigation show that a dramatic decrease of the half‐time of crystallization t_1/2, as well as a significant increase of the overall crystallization rate, are observed in the presence of the nucleating agent. These effects are further promoted in the presence of the nano‐CaCO₃ particles. The incorporation of the nucleating agent and nano‐CaCO₃ particles into PP copolymer remarkably improved the mechanical properties and heat distortion temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 431–438, 2004     

Characterization of poly(vinyl pyrrolidone‐co‐isobutylstyryl polyhedral oligomeric silsesquioxane) nanocomposites

Poly(vinyl pyrrolidone‐co‐isobutyl styryl polyhedral oligomeric silsesquioxane)s (PVP–POSS) were synthesized by one‐step polymerization and characterized using FTIR, high‐resolution ¹H‐NMR, solid‐state ¹³C‐NMR, ²⁹Si‐NMR, GPC, and DSC. The POSS content can be controlled by varying the POSS feed ratio. The T_g of the PVP–POSS hybrid is influenced by three main factors: (1) a diluent role of the POSS in reducing the self‐association of the PVP; (2) a strong interaction between the POSS siloxane and the PVP carbonyl, and (3) physical aggregation of nanosized POSS. At a relatively low POSS content, the role as diluent dominates, resulting in a decrease in T_g. At a relatively high POSS content, the last two factors dominate and result in T_g increase of the PVP–POSS hybrid. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2208–2215, 2004     

Preparation and properties of (BATB–ODPA) polyimide–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials consisting of 1,4‐bis(4‐aminophenoxy)‐2‐tert‐butylbenzene–4,4′‐oxydiphthalic anhydride (BATB–ODPA) polyimide (PI) and layered montmorillonite (MMT) clay were successfully prepared by an in situ polymerization reaction through thermal imidization up to 300°C. The synthesized PCN materials were subsequently characterized by Fourier‐Transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of material composition on thermal stability, mechanical strength, molecular permeability and optical clarity of bulk PI and PCN materials in the form of membranes were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), molecular permeability analysis (GPA) and ultraviolet‐visible (UV/VIS) transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1072–1079, 2004     

Morphology,crystallinity, and electrochemical properties of in situ formed poly(ethylene oxide)/TiO2 nanocomposite polymer electrolytes

A method to produce nanocomposite polymer electrolytes consisting of poly(ethylene oxide) (PEO) as the polymer matrix, lithium tetrafluoroborate (LiBF₄) as the lithium salt, and TiO₂ as the inert ceramic filler is described. The ceramic filler, TiO₂, was synthesized in situ by a sol–gel process. The morphology and crystallinity of the nanocomposite polymer electrolytes were examined by scanning electron microscopy and differential scanning calorimetry, respectively. The electrochemical properties of interest to battery applications, such as ionic conductivity, Li⁺ transference number, and stability window were investigated. The room‐temperature ionic conductivity of these polymer electrolytes was an order of magnitude higher than that of the TiO₂ free sample. A high Li⁺ transference number of 0.51 was recorded, and the nanocomposite electrolyte was found to be electrochemically stable up to 4.5 V versus Li⁺/Li. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2815–2822, 2003     

无机纳米复合技术在热塑性弹性体研究中的应用

综述了热塑性弹性性/无机物纳米复合的研究进展,并展望其技术发展趋势。     

Poly(trimethylene terephthalate) nanocomposite fibers comprising different organoclays: Thermomechanical properties and morphology

Poly(trimethylene terephthalate) (PTT) nano composites were synthesized by in situ polymerization at high temperature with two thermally stable organoclays: 1,2‐dimethylhexadecylimidazolium‐montmorillonite (IMD‐MMT) and dodecyltriphenyl phosphonium‐MMT (C₁₂PPh‐MMT). PTT hybrid fibers with various organoclay contents were melt‐spun at various draw ratios (DRs) to produce monofilaments. The thermomechanical properties and morphologies of the PTT hybrid fibers were characterized using differential scanning calorimetry, thermogravimetric analysis, wide‐angle X‐ray diffraction, electron microscopy, and mechanical tensile properties analysis. The nanostructure of the hybrid fibers was observed by both scanning and transmission electron microscopy, which showed that the clay layers were well dispersed into the matrix polymer, although some clusters or agglomerated particles were also detected. Unlike the hybrids containing IMD‐MMT, the clay layers of the C₁₂PPh‐MMT hybrid fiber were more dispersed into the matrix polymer. The thermal stability and tensile properties of the hybrid fibers increased with increasing clay content for DR = 1. However, as DR increased from 1 to 9 the ultimate strength and initial modulus of the hybrid fibers with IMD‐MMT increased slightly whereas those of C₁₂PPh‐MMT hybrid fibers decreased slightly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4535–4545, 2006