Preparation and characterization of mesostructured polymer-functionalized sol–gel-derived thin films

The present study attempts to incorporate methacrylate-based polymers into ordered lamellar organic/inorganic nanocomposite films composed of alternating SiO₂/polymer layers. The films are prepared by dip-coating from a solution containing the monomers and silica precursors, thus leading to composite lamellar mesostructured materials through evaporation-induced self-assembly (EISA). A polymerizable coupling agent is added to covalently link the polymers to the silica matrix. The final polymer/SiO₂ hybrid material is obtained by a separate free-radical polymerization step, initiated by UV exposure or thermal treatment. Using trimethoxy(7-octen-1-yl)silane as a coupling agent, a procedure was established that preserved the mesostructure and maintained the swelling properties of the polymers, while acrylate-based coupling agents lead to a significant distortion of the film mesostructure. Structure and composition of the films were studied by X-ray diffraction, NMR and IR.     

FT-IR spectroscopic study of hydrogen bonding in PA6/clay nanocomposites

Fourier transform infrared spectroscopy was used to investigate PA6/clay nanocomposites (PA6CN) with various cooling histories from the melt, including rapid cooling (water-quenched), middle-rate cooling (air-cooling) and slow cooling (mold-cooling). In contrast to pure PA6 dominated by the α-phase, the addition of clay silicate layers favor the formation of the γ-crystalline phase in PA6CN.We focus on the reason why silicate layers favor the formation of γ-phase in PA6. Vaia et al. suggested that the addition of clay layers forces the amide groups of PA6 out of the plane formed by the chains. This results in conformational changes of the chains, which limits the formation of H-bonded sheets so that the γ-phase is favored. If this assumption is correct, PA6CN is expected to show some differences as compared with PA6 with respect to hydrogen bonding.The silicate layers were indeed found to weaken the hydrogen bonding both in the α- and γ-phases. This was also confirmed by X-ray diffraction studies. The γ-phase is most likely concentrated in regions close to the silicate layers, whereas the α-phase is favored in the bulk matrix.     

Preparation of epoxy–clay nanocomposite and investigation on its anti-corrosive behavior in epoxy coating

An epoxy–clay nanocomposite was synthesized using a quaternary ammonium-modified montmorillonite clay and diglycidyl ether of bisphenol A (DGEBA) type epoxy resin, in order to produce anti-corrosive epoxy coating. Anti-corrosive properties of the nanocomposite were investigated using salt spray and electrochemical impedance spectroscopy (EIS) methods. The results showed an improvement in the barrier and anti-corrosive characteristics of epoxy-based nanocomposite coating and a decrease in water uptake in comparison with pure epoxy coating. Wide-angle X-ray diffraction (WAXD) patterns and transmission electron microscopy (TEM) analysis showed that the interlayer spacing of clays increased after addition of epoxy resin along with applying shear force and ultrasound sonicator. The best performance of this coating was achieved at 3 and 5 wt.% clay concentration.     

A comparative study of UV active silane-grafted and ion-exchanged organo-clay for application in photocurable urethane acrylate nano- and micro-composites

A number of urethane acrylate nano- and micro-composites have been developed using both ion exchange and silane grafting chemistry. The organically modified clays which were used contained either methacrylate or acrylate functionalities which were capable of reacting with the acrylate groups in the urethane acrylate matrix. [2-(Acryloyloxy)ethyl]trimethyl-ammonium ion (AOETMA) or [2-(methacryloyloxy)ethyl]trimethylammonium ion (MAOTMA) were exchanged onto montmorillonite (MMT) as shown by an increase in the inter-gallery spacing of the MMT. Silane grafting was undertaken using [3-(acryloxy)propyl]dimethylmethoxysilane (APDMMS) or [3-(methacryloxy)propyl]dimethylmethoxysilane (MAPDMMS) and also showed an increase in inter-gallery spacing. The structures of the resulting urethane acrylate composites were characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM) and showed predominantly intercalated structures with some exfoliation (more evident in the silane-grafted systems). Dynamical mechanical thermal analysis (DMTA) showed a more significant increase in effective crosslink density (as measured from the plateau of the rubbery modulus) in the composites containing the reactive clays as compared to the unmodified clay, supporting the concept that the acrylate and methacrylate functionalities of the modified clays had reacted with the matrix. Other thermal and mechanical properties were also evaluated.     

Interfacial in situ polymerization of single wall carbon nanotube/nylon 6,6 nanocomposites

An interfacial polymerization method for nylon 6,6 was adapted to produce nanocomposites with single wall carbon nanotubes (SWNT) via in situ polymerization. SWNT were incorporated in purified, functionalized or surfactant stabilized forms. The functionalization of SWNT was characterized by FTIR, Raman spectroscopy and TGA and the SWNT dispersion was characterized by optical microscopy before and after the in situ polymerization. SWNT functionalization and surfactant stabilization improved the nanotube dispersion in solvents but only functionalized SWNT showed a good dispersion in composites, whereas purified and surfactant stabilized SWNT resulted in poor dispersion and nanotube agglomeration. Weak shear flow induced SWNT flocculation in these nanocomposites. The electrical and mechanical properties of the SWNT/nylon nanocomposites are briefly discussed in terms of SWNT loading, dispersion, length and type of functionalization.     

Morphological, mechanical and gas-transport characteristics of crosslinked poly(propylene glycol): homopolymers, nanocomposites and blends

Linear polyethers possess unusually high CO₂ solubility and, hence, selectivity due to the presence of accessible ether linkages that can interact with the quadrupolar moment of CO₂ molecules. In this work, membranes derived from crosslinked poly(propylene glycol) diacrylate (PPGda) oligomers differing in molecular weight (M), as well as PPGda nanocomposites containing either an organically-modified montmorillonite clay or a methacrylate-terminated fumed silica are investigated and compared with highly CO₂-selective poly(ethylene glycol) diacrylate (PEGda) homopolymer and nanocomposite membranes previously reported. The rheological and permeation properties of PPGda depend sensitively on M, with the elastic modulus decreasing, but CO₂ permeability and CO₂/H₂ selectivity increasing, with increasing M. Incorporation of either nanofiller into PPGda enhances the elastic modulus and reduces the gas permeability in the resultant nanocomposites without strongly affecting CO₂/H₂ selectivity. Blending PPGda and PEGda prior to chemical crosslinking yields binary membranes that exhibit intermediate gas-transport properties accurately described by a linear rule of mixtures.     

Constitutive modeling of HDPE polymer/clay nanocomposite foams

A constitutive model for tensile behavior of high density polyethylene (HDPE)/clay nanocomposite foams was proposed. The elastic modulus of HDPE/clay nanocomposite was developed using micromechanics theory, and the modulus for foams was obtained by using representative volume element (RVE) concept. In order to describe the tensile behavior of the foams, a constitutive equation obtained from a viscoelastic model was proposed. The constitutive model was expressed in terms of microstructural properties of polymer, and physical properties of the foams. The effects of the material parameters and processing conditions on the foam morphologies and mechanical properties of HDPE/clay nanocomposite foams were investigated. Microcellular closed-cell nanocomposite foams were manufactured with HDPE, where the nanoclay loadings of 0.5, 1.0, and 2.0 wt% were used. The effect of clay loading and foaming conditions on the volume expansion ratio, elastic modulus, tensile strength, and elongation at break was investigated. Except for the elongation at break, the mechanical properties were improved with nanoclay loading. The tensile experimental data of the foams were compared with the prediction by the theoretical model. It was demonstrated that the tensile behaviors of HDPE/clay nanocomposite foams were well described by the constitutive model.     

Unusual swelling behavior of polymer-clay nanocomposite hydrogels

The swelling behavior and the elastic properties of nanocomposite hydrogels have been investigated. The hydrogels were prepared by free-radical polymerization of the monomers acrylamide (AAm), N,N-dimethylacrylamide (DMA), and N-isopropylacrylamide (NIPA) in aqueous clay suspensions at 21 °C. Laponite with a radius of gyration in distilled water of 20 nm was used as clay particles in the hydrogel preparation. The reactions with AAm monomer were carried out in the presence of the chemical crosslinker N,N′-methylenebis(acrylamide) (BAAm). It was found that the volume of nanocomposite hydrogels immersed in water rapidly increases and attains a maximum value after about one day. Surprisingly, further increase in the swelling time results in the deswelling of the gels until they reach a limiting swelling ratio after about 5 days. This unusual swelling behavior is observable only when the clay concentration in the hydrogel is above the overlap threshold c^∗. Swelling measurements combined with the elasticity tests show that the effective crosslink density first decreases, but then increases with increasing time of swelling of the hydrogels. The results were explained in terms of the rearrangements of the highly entangled polymer chains and clay particles during the gel volume change.     

Comparatively electrochemical studies at different operational temperatures for the effect of nanoclay platelets on the anticorrosion efficiency of DBSA-doped polyaniline/Na-MMT clay nanocomposite coatings

In this paper, DBSA-doped polyaniline (PANI)/Na⁺-montmorillonite (MMT) clay nanocomposite (PCN) materials have been successfully prepared with dodecylbenzenesulfonic acid (DBSA) as emulsifier and dopant for the emulsion polymerization of aniline. The as-prepared DBSA-doped samples were subsequently characterized by FTIR spectroscopy, WAXRD patterns and TEM. It should be noted that the nanocomposite coating containing 1 wt.% of clay loading was found to exhibit an observable enhanced corrosion protection on cold-rolled steel (CRS) electrode at higher operational temperature of 50 °C, which was even better than that of uncoated and electrode-coated with PANI alone at room temperature of 30 °C based on the electrochemical parameter evaluations (e.g., E_corr, R_p, I_corr, R_corr and impedance). In this work, all electrochemical measurements were performed at a double-wall jacketed cell, covered with a glass plate, through which water was circulated from a thermostat to maintain a constant operational temperature of 30, 40 and 50 ± 0.5 °C. Moreover, a series of electrochemical parameters shown in Tafel, Nyquist and Bode plots were all used to evaluate PCN coatings at three different operational temperatures in 5 wt.% aqueous NaCl electrolyte. Effect of material composition on the molecular weight and optical properties of neat PANI and PCN materials, in the form of solution, were studied by gel permeation chromatography (GPC) and UV-vis spectra, respectively. Finally, electrical conductivity at three different operational temperatures of PANI and PCN powder-pressed pellets doped with different inorganic acids such as HCl, HNO₃ and H₂SO₄ was also investigated through the measurements of standard four-point-probe technique.     

配位插层法制备三聚氰胺-甲醛树脂/Cu2+ -蒙脱石纳米复合材料

采用微波加热溶液交换法分两步将提纯后的天然膨润土转变为Cu2 -膨润土(铜基土),通过三聚氰胺单体与Cu2 -蒙脱石层间Cu2 的配位作用,把三聚氰胺单体引入蒙脱石层间,然后加入甲醛经插层原位聚合制备三聚氰胺-甲醛树脂/Cu2 -蒙脱石纳米复合材料。X-射线衍射结果表明蒙脱石的层间距由1.25 nm增加到1.58 nm,所得产物为三聚氰胺-甲醛树脂/Cu2 -蒙脱石插层型纳米复合材料。