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     

Effect of bentonite on the physical properties and drug‐release behavior of poly(AA‐co‐PEGMEA)/bentonite nanocomposite hydrogels for mucoadhesive

A series of nanocomposite hydrogels for mucoadhesive were prepared from acrylic acid, poly(ethylene glycol) methyl ether acrylate, and intercalated bentonite clay by photopolymerization. The microstructures were identified by X‐ray diffraction (XRD). Results showed that the swelling ratio for the present nanocomposite hydrogels decreased with an increase of bentonite, whereas the gel strength and Young's modulus of the present gels increased with an increase of bentonite. However, the adhesive force of the present gels did not decrease with an increase of bentonite. XRD results indicated that the exfoliation of bentonite was achieved in the xerogels and swollen gels. Finally, the drug‐release behaviors for these gels were also assessed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2934–2941, 2004     

Crystallization,morphology, and mechanical behavior of polylactide/poly(ε‐caprolactone) blends

Optically pure polylactides, poly(L ‐lactide) (PLLA) and poly(D ‐lactide) (PDLA), were blended across the range of compositions with poly(ε‐caprolactone) (PCL) to study their crystallization, morphology, and mechanical behavior. Differential scanning calorimetry and dynamic mechanical analysis (DMA) of the PLA/PCL blends showed two T_gs at positions close to the pure components revealing phase separation. However, a shift in the tan δ peak position by DMA from 64 to 57°C suggests a partial solubility of PCL in the PLA‐rich phase. Scanning electron microscopy reveals phase separation and a transition in the phase morphology from spherical to interconnected domains as the equimolar blend approaches from the outermost compositions. The spherulitic growth of both PLA and PCL in the blends was followed by polarized optical microscopy at 140 and 37°C. From tensile tests at speed of 50 mm/min Young's modulus values between 5.2 and 0.4 GPa, strength values between 56 and 12 MPa, and strain at break values between 1 and 400% were obtained varying the blend composition. The viscoelastic properties (E′ and tan δ) obtained at frequency of 1 Hz by DMA are discussed and are found consistent with composition, phase separation, and crystallization behavior of the blends. POLYM. ENG. SCI., 46:1299–1308, 2006. © 2006 Society of Plastics Engineers     

Cure kinetics of an epoxy/liquid aromatic diamine modified with poly(ether imide)

The cure kinetics and mechanisms of an epoxy oligomer based on diglycidyl ether of bisphenol A (DGEBA), polymerized with a liquid aromatic diamine based on diethyl toluene diamine (DETDA 80), and its blends with poly(ether imide) (PEI) at concentrations of 0–15 wt % were studied with differential scanning calorimetry under dynamic and isothermal conditions. The kinetic analyses were performed with a phenomenological approach. The reaction mechanism of the blends remained the same as that of the neat epoxy. However, the addition of PEI had a marked effect on the cure kinetics in the DGEBA/DETDA 80 system. The rate of reaction decreased with an increase in the thermoplastic content. Diffusion control was incorporated to describe the cure behavior of the blends in the latter stages. Greater diffusion control was observed as the PEI concentration increased and the cure temperature decreased. Polymer blends based on this epoxy/liquid aromatic diamine had not been previously studied from a kinetic viewpoint. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 660–672, 2005     

Preparation of narrowly distributed nanoparticles of poly(n‐butyl methacrylate‐co‐vinyl pyrrolidone) through microemulsion polymerization

Narrowly distributed nanoparticles of poly (n‐butyl methacrylate‐co‐vinyl pyrrolidone) were prepared through microemulsion polymerization with a nonionic surfactant of Tween‐80 as emulsifier (6 wt % of the latex) and n‐butanol as coemulsifier. The polymerizations were initiated with benzoylperoxide (BPO), potassium persulfate (KPS), KPS/ferric sulfate (FeSO₄), and BPO/FeSO₄, respectively, where the initiation in the case of BPO/FeSO₄ took place mainly at the interphase between the oil phase and the reaction media. Namely, this interfacial‐initiated microemulsion polymerization resulted in larger particles with relatively narrower particle size distribution as well as higher limiting monomer conversion but lower polymerization rate compared with the polymerization initiated with KPS/FeSO₄. In this article, the influences of initiation method, monomer ratio, and addition of water‐soluble components on microemulsion polymerization and latex particle size were studied to discuss the mechanism of interfacial‐initiated microemulsion polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2334–2340, 2004     

Pervaporation study of water and tert‐butanol mixtures

The permeation behavior of water/tert‐butanol mixture through Sulzer Pervap2510 hydrophilic poly(vinyl alcohol) membranes was investigated and the effects of feed composition and temperature on separation efficiency of the membranes were studied. The pervaporation experiments were carried out with feed water content varying from 0 to 20 wt % according to the existing industrial needs and with the feed temperature from 60 to 100°C. Over this range, both water flux and separation factor increased with increasing water content and feed temperature. These phenomena may be attributed to (1) the strong interaction between water and the membrane, (2) the decoupling effect of the permeants and the membrane at elevated temperatures, and (3) the steric hindrance effect of branch chain alcohol. The permeability ratio (the ideal separation factor) of water to tert‐butanol across the membrane was calculated and found to follow the same relationship with increasing temperature and water content. Both flux and separation factor obtained from the Pervap2510 membrane in this study were much higher than previous reported values, possible causes for which were analyzed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4082–4090, 2004     

Synthesis of syndiotacticity‐rich high molecular weight poly(vinyl alcohol) by suspension polymerization of vinyl pivalate and saponification

Vinyl pivalate (VPi) was suspension‐polymerized to synthesize high molecular weight (HMW) poly(vinyl pivalate) (PVPi) with a high conversion above 95% for a precursor of syndiotacticity‐rich HMW poly(vinyl alcohol) (PVA). Also, the effects of the polymerization conditions on the conversion, molecular weight, and degree of branching (DB) of PVPi and PVA prepared by the saponification of PVPi were investigated. Bulk polymerization was slightly superior to suspension polymerization in increasing the molecular weight of PVA. On the other hand, the latter was absolutely superior to the former in increasing the conversion of the polymer, indicating that the suspension polymerization rate of VPi was faster than that of the bulk one. These effects could be explained by a kinetic order of a 2,2′‐azobis(2,4‐dimethylvaleronitrile) concentration calculated by the initial rate method. Suspension polymerization of VPi at 55°C by controlling various polymerization factors proved to be successful in preparing PVA of HMW [number‐average degree of polymerization (P_n): 8200–10,500], high syndiotactic diad content (58%), and very high yield (ultimate conversion of VPi into PVPi: 94–98%). In the case of the bulk polymerization of VPi at the same conditions, the maximum P_n and conversion of 10,700–11,800 and 32–43% were obtained, respectively. The DB was lower and the P_n was higher with PVA prepared from PVPi polymerized at lower initiator concentrations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 832–839, 2003     

Preparation and properties of nadic‐end‐capped cyclotriphosphazene‐containing polyimide/carbon fiber composites

New novel fire‐resistant and heat‐resistant cyclotriphosphazene‐containing polyimide resins were prepared in situ by the polymerization of (p‐aminophenoxy)(phenoxy)cyclotriphosphazenes with 3,3′,4,4′‐benzophenonetetracarboxylic acid or 3,3′,4,4′‐diphenylsulfonetetracarboxylic acid and a crosslink agent, 5‐norbornene‐2,3‐dicarboxylic acid and were used as polymer matrix compositing with a woven carbon fiber to prepare nadic‐end‐capped cyclotriphosphazene‐containing polyimide/carbon fiber composites. The thermal stability, flame retardance, morphology of the surface fracture, and some physical properties of the composites were investigated by thermogravimetric analysis, scanning electron microscopy, and a material testing system, respectively. The composites had good thermal stability, flame retardance, and mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 810–818, 2003     

Nanoscratch testing to assess the fiber adhesion of short‐carbon‐fiber composites

In a composite material, the degree of adhesion between the fiber and the matrix plays an important role in the overall performance of the material. Because the load between the fiber and the matrix is realized throughout the interphase region material, a lot of effort has gone into characterizing the strength of the interphase. In this study, nanoscratch tests on the composite samples were used to provide a relative measure of adhesion in different composite materials. Carbon‐filled nylon 6,6 and polycarbonate resins were evaluated with this method. The carbon fillers we used were polyacrylonitrile‐based carbon fibers sized and surface‐treated for the respective matrix and pitch‐based carbon fibers without any sizing or surface treatment. Tensile and X‐ray photoelectron spectroscopy data for the composites we considered are also presented to compare to the nanoscratch results. It is shown that nanoscratch testing on the composites, with the proposed data analysis, can be an effective tool for determining the relative degree of adhesion between different composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 328–335, 2007     

Characterization and comparison of diblock and triblock amphiphilic copolymers of poly(δ‐valerolactone)

Three types of pegylated amphiphilic copolymers of poly(δ‐valerolactone) (PVL) were copolymerized with methoxy poly(ethylene glycol) (MePEG) and poly(ethylene glycol) (PEG₄₀₀₀ and PEG_10,000), respectively. Pegylation of PVL allowed copolymers possessing amphiphilic property and efficiently self‐assembled to form micelles with a low critical micelle concentration (CMC) in the range of 10^?7–10^?8M. The average molecular weight of copolymers was in the range of 10,000–20,000 Da, and the polydispersity of copolymers was about 1.7–1.8. Higher mobility of low molecular weight PEG (i.e., MePEG and PEG₄₀₀₀) than high molecular weight PEG_10,000 allowed valerolactone ring opening more efficient in terms of PVL/MePEG and PVL/PEG₄₀₀₀ copolymers possessing longer chain length in hydrophobic domain. Pegylated PVL with low CMC and triblock structure was preferred to encapsulate drug during micelle formation. Although all of these amphiphilic copolymers exhibited controlled release character, the micelles formed by triblock copolymer possessed a more stable core‐shell conformation than that by diblock copolymer, and resulted in the release of drug from triblock micelles slower than that from diblock micelles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1836–1841, 2006