Synthesis of thermoplastic polyurethane nanocomposites of reactive nanoclay by bulk polymerization methods

This paper reports synthesis and characterization of thermoplastic polyurethane nanocomposites of reactive silicate clays. Pre-polymer (method I) and chain-extended polymer molecules (method II) with residual -NCO groups participated in tethering reactions with clay during clay-polymer mixing. It was found that both clay-polymer reactions and shear stress of mixing are responsible for clay exfoliation. In method I, more clay-tethered polymer chains were produced, but clay particles did not exfoliate due to low shear stress of mixing. Method II provided an order of magnitude higher shear stress of mixing and yielded exfoliated nanocomposites. Control experiments with high shear stress of mixing and no clay-polymer reactions resulted in only intercalated composites. It was found that clay particles deterred hydrogen bonding among hard segments. The exfoliated nanocomposites exhibited optical clarity and more than 100% increase in tensile strength and tensile modulus over pristine polyurethanes.     

Preparation and characterization of polypropylene/layered silicate nanocomposites using an antioxidant

Polypropylene (PP)/layered silicate nanocomposites were prepared via simple melt mixing of three components, PP, layered silicates modified with octadecylamine (C18-MMT) and antioxidant, to investigate the role of antioxidant. TEM and X-ray scattering results confirmed the intercalated state of silicates in PP/layered silicate nanocomposites with antioxidant. In rheological and mechanical study, the nanocomposites with antioxidant showed higher properties than those of the unfilled PP. The nanocomposite with 5 wt% C18-MMT and 0.5 phr antioxidant exhibited about 1.4 times higher tensile modulus and 1.3 times higher storage modulus than the unfilled PP. However, PP/C18-MMT without antioxidant showed lower rheological values owing to the thermal decomposition of PP and the poor compatibility between PP and C18-MMT. It could be concluded that antioxidants played an important role in enhancing the compatibility between PP and C18-MMT. According to the real time X-ray diffraction, the nanocomposite showed the weak ordering of PP crystals than the unfilled PP in the load-extension plateau region of elongation.     

Preparation and properties of LDHs/epoxy nanocomposites

Layered double hydroxides (LDHs)/epoxy nanocomposites were prepared by mixing the amino laurate intercalated LDHs, EPON 828 resin, and Jeffamine D400 as a curing agent. The organo-modified LDHs with hydrophobic property easily disperse in epoxy resin, and the amino laurate intercalated LDHs with large gallery space allow the epoxy molecules and the curing agents to easily diffuse into the LDHs galleries at elevated temperature. After the thermal curing process, the exfoliated LDHs/epoxy nanocomposites were formed. X-ray diffraction was used to detect the formation process of the exfoliated LDHs/epoxy nanocomposites. TEM was used to observe the dispersed behavior of the LDHs nanolayers, and the LDHs nanolayers were exfoliated and well dispersed in these nanocomposites. Owing to the reaction between the amine groups of the intercalated amino laurate and epoxy groups, the adhesion between the LDHs nanolayers and epoxy molecules makes these LDHs/epoxy nanocomposites more compatible. Consequently, the tensile properties from tensile test and the mechanical properties from DMA were enhanced, and the T_g of these nanocomposites from DMA and TMA were increased. Coefficients of thermal expansion (CTEs, below and above T_g) of these nanocomposites from TMA decreased with the LDHs content. The thermal stability of these nanocomposites was enhanced by the well dispersed LDHs nanolayers.     

Quantitative estimation of the reinforcing effect of layered silicates in PP nanocomposites

Various polypropylene/layered silicate composites were prepared with different silicate contents. Montmorillonites with and without organophilization as well as three maleinated polypropylenes were used to change the extent of exfoliation and hence the properties of the composites. Structure was characterized by X-ray diffraction (XRD), scanning (SEM) as well as transmission electron microscopy (TEM) and tensile properties were also measured. The analysis of the tensile yield stress values of a large number of composites showed a broad range of variation in mechanical properties. XRD and TEM results do not reflect the differences in properties and they usually do not give quantitative information about the extent of exfoliation either. PP/clay composites containing maleinated PP, which do not exhibit a silicate reflection in XRD, may have very poor mechanical properties indicating small extent of exfoliation. The composition dependence of tensile yield stress of these composites may be described and evaluated quantitatively by a simple model developed earlier for particulate filled polymers. The use of a few simple assumptions most of which are supported by previous results allows us to estimate the extent of exfoliation quantitatively. The tensile yield stress of about 40 composites was analyzed with the model. Some of the composites were prepared by us, while results on others were taken from papers published in the literature. The analysis indicated that the extent of exfoliation is very low in most composites; it reaches maximum 8% of the theoretically possible value in the best case. This result is in agreement with our observation that complete exfoliation can be seldom reached in thermoplastic/clay composites; the structure is complex and hierarchical including large particles and individual silicate layers. The results prove that further efforts must be done to increase the extent of exfoliation in order to achieve reinforcement levels forecasted earlier.     

Preparation and properties of LDHs/polyimide nanocomposites

Layered double hydroxides/polyimide (LDHs/PI) nanocomposites were prepared from solution of polyamic acid (polyimide precursor) and LDH-amino benzoate using N,N-dimethylacetamide as a solvent. LDH-amino benzoate (LDH-AB) was obtained by coprecipitation method. The amino benzoate, grafted on the surface of the Mg/Al nanolayers, as a connector improved the compatibility between the inorganic Mg/Al nanolayers and the organic polyimide molecules. The dispersion behavior of Mg/Al nanolayers was investigated by transmission electron microscopy and X-ray diffraction, indicating that the Mg/Al nanolayers were exfoliated in PI matrix to form LDH-AB/PI nanocomposites. The maximum tensile strength and elongation of the LDH-AB/PI nanocomposites were found with the LDH-AB content of 5 and 4 wt%, respectively. The initial tensile modulus of these nanocomposites was increased with the LDH-AB content. These nanocomposites exhibited higher storage and loss moduli compared to those of pure PI. T_g of these nanocomposites increased with the LDH-AB content. Coefficients of thermal expansion (CTE, below and above T_g) of these nanocomposites deceased with the LDH-AB content. The thermal properties of these nanocomposites were enhanced by the incorporation of Mg/Al nanolayers in PI matrix.     

Properties of polyamide 6/clay nanocomposites processed by low cost bentonite and different organic modifiers

Nanocomposites based on polyamide 6 have been directly prepared by melt compounding, using modified low cost bentonites by three selected quaternary ammonium cations, in particular quaternized octadecylamine (ODA), dimethyl benzyl hydrogenated tallow quaternary ammonium (B2MTH) and dimethyl hydrogenated ditallow quaternary ammonium (2M2TH). Thermal stability of organic modifiers and organoclays has been studied by TGA and results allow evaluating the degree of modifier incorporation into clay galleries. The influence of the organic modifier on the morphology and properties of the obtained nanocomposites has been studied by X-ray diffraction and TEM analysis. Depending on the degree of bentonite modification, different mechanisms were reported to explain the improved mechanical properties of the resulting nanocomposites.     

Morphology, thermal relaxations and mechanical properties of layered silicate nanocomposites based upon high-functionality epoxy resins

This paper investigates the possibility of improving the mechanical properties of high-functionality epoxy resins through dispersion of octadecyl ammonium ion-modified layered silicates within the polymer matrix. The different resins used are bifunctional diglycidyl ether of bisphenol-A (DGEBA), trifunctional triglycidyl p-amino phenol (TGAP) and tetrafunctional tetraglycidyldiamino diphenylmethane (TGDDM). All resins are cured with diethyltoluene diamine (DETDA). The morphology of the final, cured material was probed by wide-angle X-ray scattering, as well as optical and atomic force microscopy. The α- and β-relaxation temperatures of the cured systems were determined using dynamic mechanical thermal analysis. It was found that the presence of organoclay steadily decreased both transition temperatures with increasing filler concentration. Further, the effect of different concentrations of the alkyl ammonium-modified layered silicate on the toughness and stiffness of the different epoxy resins was analyzed. All resin systems have shown improvement in both toughness and stiffness of the materials through the incorporation of layered silicates, despite the fact that it is often found that these two properties cannot be simultaneously achieved.     

Synthesis and characterization of polymer–nanoclay conductive nanocomposites

Polymer–clay nanocomposites based on poly(3,4‐ethylenedioxythiophene)/polystyrene sulfonate (PEDOT) : PSS and nanoclay montmorillonite were synthesized and characterized. The doping of PEDOT with polystyrene sulfonate made it water dispersible (PEDOT–PSS). Sodium dodecyl benzene sulfonate (SDBS) and ionic liquid were used to increase the interlayer spacing and the conductivity of the nanocomposites, respectively. The nanocomposite was characterized by various techniques, such as X‐ray diffraction (XRD), TEM, surface resistivity, and thermogravimetric measurement analysis. Interlayer spacing increased as a result of the addition of SDBS, and this was confirmed by the 2θ shift observed via XRD analysis. The surface morphology of the conductive coated clay was examined by TEM analysis. Good electrical surface conductivity, interlayer spacing, and polymer coating were observed for the material prepared using the surfactant and conductive ionic liquid. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of poly(vinyl chloride)/layered double hydroxide nanocomposites with enhanced thermal stability

Poly(vinyl chloride)/layered double hydroxide (PVC/LDH) nanocomposite has been prepared via solution intercalation process using dodecyl sulfate (DS⁻) or stearate anion modified LDH. XRD and TEM results give evidence that the inorganic LDH particles were dramatically exfoliated into nanoscale and homogeneously dispersed in PVC matrix. The enhanced thermal stability was confirmed by conventional Congo Red test. The nanocomposite containing Mg₃Al-LDH-stearate had the maximum of increased dehydrochlorination time, 15 times of that of neat PVC, and more than twice of that of PVC/LDH-NO₃ composite and PVC/LDH-DS nanocomposite at 5 wt% loading. Furthermore, its thermal stability time increased with the LDH content. At 10 wt% loading of Mg₃Al-LDH-stearate, it reached 20 times of that of PVC, and obviously larger than that of the previously reported nanocomposite using alkyl phosphonate (AP) grafted LDH. The reason may lie on the absorption of the released HCl during degradation by both nanoscale dispersed LDH particles and stearate anions.     

Possible mechanism of interaction among the components in MAPP modified layered silicate PP nanocomposites

Model reactions were carried out with components frequently used for the preparation of intercalated or exfoliated polypropylene (PP) nanocomposites. The results prove that maleinated polypropylene (MAPP) can react chemically with the surfactant applied for the organophilization of the filler, if this latter contains active hydrogen groups. The reaction of hexadecylamine (HDA) and MAPP was detected by MALDI-TOF spectroscopy, DSC measurements and FTIR spectroscopy. Anhydride groups are consumed and mainly amide groups form in the reaction. The formation of cyclic imides could not be proved by the techniques used. MAPP reacts also with the surfactant adsorbed on the surface of the silicate in ionic form. On the other hand, N-cetylpyridinium chloride (CPCl) not containing active hydrogen atoms does not react with maleinated PP. Intercalated or exfoliated composites could be prepared from the silicate organophilized with HDA, while microcomposites formed from the filler treated with CPCl. Chemical reactions remove the surfactant from the surface of MMT and hydrogenated silicate sites are left behind. The high energy surface interacts either with the anhydride or the amide groups by dipole-dipole interactions. Even the unmodified polypropylene chains may be attached much stronger to the surface by London dispersion forces than to the silicate covered with aliphatic chains. Although the effect of competitive adsorption (MAPP, HDA) and mutual solubility of the components (PP, MAPP, surfactant, reaction products) cannot be neglected, chemical reactions play a crucial role in structure formation in PP nanocomposites containing a functionalized polymer. Direct interaction of the silicate surface and the functionalized polymer as well as the formation of hydrogen bridges seem to play a lesser role, but the relative influence of processes may change with the type of surfactant, functionalized polymer, surface coverage and processing conditions.     

Poly lactic acid nanocomposites containing modified nanoclay with synergistic barrier to water vapor for coated paper

The binary nanocomposites of poly lactic acid (PLA) with the montmorillonite modified with trisilanol polyhedral oligomeric silsesquioxanes (Trisilanolisooctyl POSS^®) were prepared via a solution‐blending process and coated on paper by bar coating and compress hot melt coating methods. The resulting components were characterized with Fourier transform infrared spectroscopy, and X‐ray diffraction (XRD) techniques. Moreover, the water vapor transmission rates (WVTR) for the coated writing paper were determined using an IGA‐003. The results indicated that the modified clay PLA nanocomposites enhanced the water vapor barrier properties of coated paper significantly. The permeability of PLA nanocomposites to water vapor decreased by 74% [26.0 g/(m² day)], respectively, as compared to those of the paper coated with pure PLA. The dispersion and phase behavior of the modified montmorillonite in PLA matrix was revealed by Transmission electron microscope. The intercalation of montmorillonite with PLA was further demonstrated using XRD. WVTR results indicated that the compress hot melt coating of the nanocomposites is an effective method to improve the water vapor resistance of coated paper. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40952.     

有机／无机纳米复合材料的制备方法

综述了近年来国内外有机/无机纳米复合材料的制备方法及其最新进展情况。     

An improved technique for exfoliating and dispersing nanoclay particles into polymer matrices using supercritical carbon dioxide

An environmentally benign process, which uses supercritical carbon dioxide (sc-CO₂) as a processing aid, is developed in this work to help exfoliate and disperse nanoclay into the polymer matrices. The process relies on rapid expansion of the clay followed by direct injection into the extruder where the mixture is dispersed into the polymer melt. Results from the mechanical properties, rheological studies, and X-ray diffraction (XRD) show that this method represents a significant improvement relative to direct melt blending in single or twin-screw extruders or other methods using sc-CO₂. The greatest mechanical property response was a result of directly injecting pre-mixed sc-CO₂ and nanoclay into the polypropylene melt during extrusion. It was observed that for concentrations as high as 6.6 wt% (limited only by present process capabilities), XRD peaks were eliminated, suggesting a high degree of exfoliation. Mechanical properties such as modulus increased by as much as 54%. The terminal region of the dynamic mechanical spectrum was similar to that of the base polymer, contrary to what is frequently reported in the literature.     

改性黏土填充PP/PA6复合材料制备与性能研究进展

分别从制备方法,力学性能,流变性能,微观形态和其他性能5个方面综述了近年来有机改性黏土填充PP/PA6复合材料的研究概况,从而得出结论:要提高有机改性黏土填充PP/PA6纳米复合材料的宏观性能,关键在于微观相容性的提高。     

Impact of nanoclay on physicomechanical and thermal analysis of polyvinyl alcohol/fumed silica/clay nanocomposites

Polyvinyl alcohol (PVA)/fumed silica/clay nanocomposites are prepared via solution intercalation by exploiting phase separation based on the bridging of particles by polymer chains. PVA/fumed silica/clay nanocomposites are characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy, and thermogravimetric analysis. Mechanical properties are determined by universal testing machine. From FTIR results, it indicates that IR spectrum for PVA/fumed silica/clay nanocomposites, especially PVA/fumed silica/clay (1.30E) nanocomposites, is much broader than pure PVA and other clay nanocomposites. The better interfacial bonding between PVA/fumed silica/clay (1.30E) nanocomposites are reflected in the improvement of the mechanical properties as well as thermal stability. The surface area analysis result proves that the PVA/fumed silica/clay (1.30E) nanocomposites have higher surface area and pore volume with less pore size. With the addition of 1.30E clay to the composite system, the tensile strength and modulus had shown the highest values as well as higher activation energy for thermal decomposition. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41843.     

Structure and photocatalytic performance of TiO2/clay nanocomposites for the degradation of dimethachlor

In the present study TiO₂/clay composites were synthesized by dispersion of TiO₂ on the surfaces of a natural montmorillonite and a synthetic hectorite in order to increase the sorption ability of TiO₂ and therefore its photocatalytic action. Six materials with different loading in TiO₂ (15, 30 and 55 wt%) were prepared and characterized by several analytical techniques including XRD, BET and SEM analysis. The synthetic procedure allows the development of delaminated layers for hectorite–TiO₂ samples, while in the case of montmorillonite–TiO₂ composites we have the formation of a more lamellar-like aggregation. It was found that, the greater the percentage of TiO₂, the greater the pore volume and the specific surface area of the montmorillonite–TiO₂ samples. On the contrary, in the case of hectorite–TiO₂ samples, as the content of TiO₂ increases, the surface area and pore volume decreases. The photocatalytic efficiency of the nanocomposite catalysts was evaluated using a chloroacetanilide herbicide (dimethachlor) in water as model compound. The primary degradation of dimethachlor followed pseudo-first-order kinetics according to the Langmuir–Hinshelwood model. All supported catalysts exhibit good photodegradation efficiency and their overall removal efficiency per mass of TiO₂ was better than that of bare TiO₂ produced by the sol–gel method. In conclusion, together with their good sedimentation ability the composite materials could be considered as a promising alternative for the removal of organic water contaminants.     

Polymer nanocomposites using zinc aluminum and magnesium aluminum oleate layered double hydroxides: Effects of LDH divalent metals on dispersion, thermal, mechanical and fire performance in various polymers

Oleate-containing layered double hydroxides of zinc aluminum (ZnAl) and magnesium aluminum (MgAl) were used to prepare nanocomposites of polyethylene, poly(ethylene-co-butyl acrylate) and poly(methyl methacrylate). The additives and/or their polymer composites were characterized by X-ray diffraction, FTIR, elemental analysis, thermogravimetric analysis, mechanical testing, and cone calorimetry. The unusual packing of the monounsaturated oleate anions in the gallery of these LDHs facilitates the dispersion of these nanomaterials. The inorganic LDH protects the polymer from thermal oxidation, shown by enhancement of the thermal and fire properties of the corresponding polymer nanocomposites. There is a qualitative difference in the morphology of the two LDHs in PE and PMMA. ZnAl is better dispersed in PE while MgAl is better dispersed in PMMA. The zinc-containing material led to a large reduction in the peak heat release rate in polyethylene, while the magnesium-containing material led to enhancement of the fire properties of the more polar poly(methyl methacrylate). These fire properties are consistent with the morphological differences. Neither of these LDHs shows efficacy with poly(ethylene-co-butyl acrylate), which indicates a selective interaction between the LDH and the various polymers.     

Synthesis, structure, thermal and mechanical properties of nanocomposites based on linear polymers and layered silicates modified by polymeric quaternary ammonium salts (ionenes)

Polymer–clay composites has been prepared by melt blending an organo-bentonite with linear polymers (polyamide, polysterene and polypropylene) in a disk-screw extruder. In first time organo-clay was prepared by surface treatment of Na-forms bentonite with polymeric quaternary ammonium salts (PQAS). XRD indicated that organo-bentonite layers were exfoliated and dispersed into polyamide and polystyrene. Addition of 2 wt% organo-bentonites (optimal concentration) to polyamide increased tensile strength by 53% and Sharpy impact by 140%. With the incorporation of 2 wt% organo-bentonites (optimal concentration) into polystyrene the tensile strength increased to 28% and the Sharpy impact increased to 25%. For polypropylyne–organo-bentonites composites we did not observe delamination of layered structure, and as result absence of reinforcements. TGA showed that the polyamide and polystyrene nanocomposites have higher decomposition temperature in comparison with the original polymers.     

Preparation and properties of layered double hydroxide/poly(ethylene terephthalate) nanocomposites by direct melt compounding

Thermal, rheological and mechanical properties of layered double hydroxide (LDHs)/PET nanocomposites were investigated. To enhance the compatibility between PET matrix and LDHs, organic modification of parent LDH having carbonate anion was carried out using various anionic surfactants such as dodecylsulfate (DS), dodecylbenzenesulfonate (DBS), and octylsulfate(OS) by rehydration process. Then, PET nanocomposites with LDH content of 0, 1.0, and 2.0 wt% were prepared by direct melt-compounding. The dispersion morphologies were observed by transmission electron microscopy and X-ray diffraction, indicating that LDH-DS were exfoliated in PET matrix. From the rheology study, there are some network structures owing to filler-filler and/or filler-matrix interactions in nanocomposite systems. Consequently, DS intercalated LDH provided good compatibility with PET molecules, resulting in exfoliated LDH-DS/PET nanocomposites having enhanced thermal and mechanical properties as compared to other nanocomposites as well as homo PET.     

Transport properties of organic vapors in nanocomposites of organophilic layered silicate and syndiotactic polypropylene

Syndiotactic polypropylene (sPP) nanocomposites were obtained by melt blending synthetic fluorohectorite modified octadecyl ammmonium ions (OLS), and maleic-anhydride-grafted isotactic polypropylene (iPP-g-MA) as compatibilizer. The composition of the inorganic material was varied between 5 and 20 w/w%. Films of the composites were obtained by hot press molding the pellets. Melt-direct polymer intercalation of sPP into the OLS gave rise to nanocomposites in which the silicate layers were delaminated at low clay contents, and ordered to intercalated structures at the highest clay content. The elastic modulus was higher than for the pure polymer in a wide temperature range and increased with the inorganic content. The transport properties were measured for dichloromethane and n-pentane. The sorption was reduced compared to pure sPP. There were not significative differences between the samples having different inorganic contents. The diffusion coefficient decreased with increasing clay content. Permeability (P) showed a strong decreasing dependence on the clay content. The improvement of the barrier properties was largely caused by the reduced diffusion.