MWCNT‐based composites have been successfully synthesized via layer‐by‐layer self‐assembly of crosslinked polyphosphazene nanoparticles on the surface of MWCNTs. The amino‐terminated CNTs were characterized by XPS, FT‐IR spectroscopy, EDS, XRD and TEM. The degree of functionalization could be controlled by simply changing the mass of hexachlorocyclotriphosphazene with 4,4′‐diaminodiphenyl ether. The activity of the surface amino groups was confirmed by the reaction of these groups with HAuCl4. In addition, the effects of the mass of HCCP and ODA ratios on the content of the surface amino groups was also investigated.
We report a ternary system of poly(styrene‐co‐acrylonitrile) (SAN), poly(vinyl chloride) (PVC), and multi‐walled carbon nanotube (MWCNT) composites prepared by both a solution blending method and the SOAM. The MWCNT content in the composites was optimized by both TGA and mechanical characterization of binary mixtures of SAN/MWCNT and PVC/MWCNT composites. The dispersion of MWCNTs in the miscible SAN/PVC blends was characterized by FT‐Raman spectroscopy, FE‐SEM, and FE‐TEM. The distribution of MWCNTs in the SAN/PVC blends was examined in terms of their wetting coefficients and minimization of the interfacial energy. Composites prepared using the SOAM method showed superior physical properties to the SAN/PVC blends and SAN/PVC/MWCNT composites prepared using the solution blending method.
Temperature‐responsive PVCL homopolymers and functional PVCL polymers containing carboxylic acids are prepared in organic and aqueous solutions. PVCL bulk polymers are characterized using 1H NMR, photometry, ATR‐FTIR, and thermal analysis. A finite phase transition at 37–40 °C occurs in aqueous solutions of PVCL and PVCL‐COOH. PVCL and PVCL‐COOH polymers are electrospun into fibers ranging from 100 to 2300 nm in diameter. PVCL/cellulose bi‐component films are obtained by electrospinning of CA and PVCL followed by alkaline hydrolysis. These tunable thermo‐responsive PVCL/cellulose nanofibers have potential applications in developing affinity membranes.
An effective approach is presented for designing and tailoring diffusion‐controlled systems for targeted release rate profiles. The diffusion‐controlled system consists of PBA networks with precisely controlled crosslink densities via RAFT copolymerization of BA with ethylene glycol dimethacrylate, which gives a desired diffusivity. One‐dimensional releases in the crosslinked PBA matrix (CPM) slabs are evaluated with a hydrophobic dye. Fick's second law is used to model the transient mass transfers in the CPMs with a mixed Newton‐Tikhonov regularization method for determination of their diffusion coefficients. A two‐layer CPM (CPM‐2) with controlled crosslink densities is constructed. The dye release results from the CPM‐2 agreed well with theoretical predictions.
A robust method to prepare hydrogels with high mechanical strength is presented. Core/shell nanospheres with derivatizable allyl groups in the shell were first prepared. Starch‐based nanospheres were used as crosslinker to prepare polyacrylamide hydrogels. The starch‐based nanospheres were bridged by acrylamide to form crosslink points in the hydrogel network. They possess an extremely high mechanical strength. The results show that starch‐based nanosphere hydrogels can sustain strengths of 10.34 MPa, which is 60 times greater than for a normal hydrogel. The mechanical properties of SNH can be tailored by varying the content of SN. This approach offered a new way of making functional hydrogel with biodegradable component as a substitute for tissue.
A systematic study of the effects of , flow rate, voltage, and composition on the morphology of electrospun PLGA nanofibers is reported. It is shown that changes of voltage and flow rate do not appreciably affect the morphology. However, the of PLGA predominantly determines the formation of bead structures. Uniform electrospun PLGA nanofibers with controllable diameters can be formed through optimization. Further, multi‐walled carbon nanotubes can be incorporated into the PLGA nanofibers, significantly enhancing their tensile strength and elasticity without compromising the uniform morphology. The variable size, porosity, and composition of the nanofibers are essential for their applications in regenerative medicine.
The effect of hydrophilic and hydrophobic nanosilica on the morphological, mechanical and thermal properties of polyamide 6 (PA) and poly(propylene) (PP) blends is investigated by extrusion compounding. Depending on the difference between the polymer/nanoparticle interfacial tensions, different morphologies are obtained as highlighted by TEM and SEM. Hydrophobic nanosilica migrates mainly at the PA/PP interface, which leads to a clear refinement of PP droplet size. The macroscopic properties of the hybrid blends are discussed and interpreted in relation with the blend morphology and melt‐mixing procedure. The control over coalescence allows a morphology refinement of the blends and improves mechanical properties.
A new melt‐processable PTFE material is presented and characterized that provides new and economical solutions in polymer technology while bridging the gap between perfluorinated PTFE and fluorothermoplastic materials such as perfluoroalkoxy resins. Thermal transitions, MW and MWD, and microstructures of the melt‐processable PTFE materials are investigated and compared to standard PTFE, modified PTFE, and PFA materials. The influence of the polymerization type used for the preparation of the melt‐processable PTFE (emulsion and suspension polymerization) on the MWD and the comonomer distribution are discussed.
Electroactive macroporous poly[(vinylidene fluoride)‐co‐trifluoroethylene] membranes have been produced by solvent evaporation at room temperature, starting with a diluted solution of the copolymer in dimethylformamide. The pore architecture consists of interconnected spherical pores. This architecture is independent of the membrane thickness. The thickness of the membranes ranges from a few to several hundred µm, using spin coating and evaporation in static conditions, respectively. The pore structure is explained by a spinodal decomposition of the liquid/liquid phase separation and crystallization in the copolymer‐rich phase.
A novel method is described to functionalize nanofibers to form a nanocomposite with core/shell particles in order to control protein release. The nanocomposite is produced by electrically neutralizing negatively charged poly(lactic acid) nanofibers with positively charged poly[(lactic acid)‐co‐(glycolic acid)] particles via a one‐step electrohydrodynamic jetting process. The protein‐encapsulated core/shell particles exhibited no significant initial burst release or denaturation. The protein release profile was controlled by porosity and protein/polymer interactions. The method may be promising to engineer intelligent scaffolds that can fulfill the needs of biomimetic materials.
Nanocomposites based on poly(vinyl alcohol) and silver nanoparticles were efficiently prepared by sun‐ and thermal‐promoted reduction processes. Uniaxial drawing of the Ag/PVA nanocomposites favoured the anisotropic distribution of silver particles, providing oriented films with polarisation‐dependent tunable optical properties. These dichroic properties were more pronounced for nanocomposites produced by sun exposition, which provided more compact and interacting metal clusters. The results obtained suggest the nanocomposite films could find potential applications as colour polarising filters, radiation responsive polymeric objects and smart flexible films in packaging applications.
The influence of electron beam (EB) irradiation on the mechanical properties of biopolymers from modified linseed oil is studied. The thermoset is prepared by copolymerizing norbornenyl‐functionalized linseed oil and dicyclopentadiene (DCPD) by ring‐opening metathesis polymerization (ROMP). EB irradiation of the bulk polymer results in a substantial increase in the crosslinking density. The residual carbon‐carbon double bonds remaining after ROMP are expected to act as further crosslinking sites upon exposure to the high‐energy electrons. The increase in the crosslinking density is studied by DMA and sol/gel fraction measurements from Soxhlet extraction. Tensile testing reveals that Young's modulus and tensile strength are enhanced after EB irradiation.
We report a novel rubber film made by a simple mixing method, which realizes a steep temperature dependence of the contact angle of water at a critical temperature of 41 °C. We mixed a common SBR with a known temperature‐responsive PNIPA to make a thermo‐responsive rubber. This rubber film distinctly showed a switch of surface wettability between hydrophilic below 41 °C and hydrophobic above 41 °C. The switching property is possibly controlled by the mixing ratio of PNIPA to SBR, preparation method, added chemicals, and so on. This mixing technique will be applied for the control of surface wetting properties by temperature on various SBR‐like rubber materials, such as wet‐brake performance of automobile tires on a rainy day.
The influence of talc loading on phase morphology of PLA/PCL/talc composites and improvement in resulting properties are reported. Talc‐based composites of PLA/PCL blends were prepared by melt blending. SEM analysis demonstrates that PLA appears as discrete domain phase, while PCL acts as a bulk phase in the blend. Talc addition decreases PLA domain sizes and voids in the matrix. This results in significant improvement of oxygen and water vapor barrier properties of composite by 33 and 25%, respectively, at 3 wt.‐% talc loading. DSC shows that talc acted as nucleating agent for PCL phase in the composite and improves its crystallinity. Various theoretical models based on dispersion and filler geometry are used to predict the tensile modulus and oxygen permeability.
Fully exfoliated PS/clay nanocomposites were prepared via FRP in dispersion. Na‐MMT clay was pre‐modified using MPTMS before being used in a dispersion polymerization process. The objective of this study was to determine the impact of the clay concentrations on the monomer conversion, the polymer molecular weight, and the morphology and thermal stability of the nanocomposites prepared via dispersion polymerization. DLS and SEM revealed that the particle size decreased and became more uniformly distributed with increasing clay loading. XRD and TEM revealed that nanocomposites at low clay loading yielded exfoliated structures, while intercalated structures were obtained at higher clay loading.
Novel nanocomposites prepared by melt mixing of MWCNTs in a hot‐melt adhesive PCL‐based polyurethane are investigated. The nucleating effect of MWCNTs and the confinement they cause to polymer chains are considered. The broadening of the glass transition is indicative of a growth of the immobilized amorphous fraction adhered to MWCNTs. In the molten state the formation of a combined polymer/MWCNT network is observed. Practical requisites of hot melt adhesives, such as adequate melting temperature, crystallization degree, and viscosity are preserved when MWCNTs are added. Improvement of strength at room temperature and welding rate during cooling, are observed.
A series of hydrogels based on poly(ethylenglycol) methyl ether methacrylate (PEGMEMA) is synthesized using macromonomers of three different molecular weights, in combination with varied degrees of chemical crosslinking. The effects of PEGMEMA, initiator, and crosslinker concentrations on gel yield and swelling properties are studied. In addition, the chemical structure of the gels is characterized by FTIR and solid‐state NMR spectra. The swelling and rheological behaviors of hydrogels as well as protein partitioning into the gels are discussed in terms of the network mesh size. Low protein sorption and bacteria deposition tendencies indicate that PEGMEMA‐based hydrogels could be highly beneficial for uses as fouling‐resistant materials, for instance, as protective coatings for desalination membranes.
PCL‐based nanoclay (layered silicate) nanocomposites are prepared using a small scale intermeshing co‐rotating twin‐screw extruder. Improving the level of nanoclay dispersion in PCL nanocomposites is obtained by changing the extrusion parameters. Increasing the screw speed and decreasing the throughput leads to an improved dispersion quality, as observed from the improved mechanical properties of the nanocomposites as well as from their clearly affected rheological and crystallization behavior. Furthermore, a commercially available software that simulates the twin‐screw extrusion process (LUDOVIC) is used to asses the processing parameters applied for making the nanocomposites.
A simple process is described for preparing transparent composite sheets from soy‐oil‐based biopolyurethane (BioPU) with microcrystalline cellulose (MCC). The sheets are prepared by the reaction of a mixture of soy‐oil‐based polyol and petrochemical polyol with polymeric methyldiphenyl diisocyanate (pMDI) in the presence and absence of MCC reinforcement by compression molding. MCC is well dispersed in the PU matrix, and characteristic peaks for MCC and BioPU are shown by the FTIR spectra. Mechanical properties are substantially improved with increasing MCC content. DMA and TGA results show better thermal stability in comparison to the neat BioPU sheets.
Spherical silica particles with pseudo‐inverse opal structure are synthesized by using pomegranate‐like polymer microparticles as templates. A micro‐dispersion polymerization occurring in the suspended monomer droplets in the presence of a silica precursor leads to the formation of nearly monodisperse polymer sub‐particles of about 1 µm size, randomly‐packed within a 30–100 µm polymer particle. The polymerization is followed by an acid‐catalyzed reaction that induces formation of silica in the interstices between the sub‐particles within a polymer particle. Spherical PIOS particles are eventually produced by selectively removing the polymer template by pyrolysis. The PIOS particles show large specific surface areas with unique pore geometry and pore size distribution.
