Application of essential work of fracture concept to toughness characterization of high‐density polyethylene

Deformation and fracture toughness of high‐density polyethylene (HDPE) in plane‐stress tension was studied using the concept of essential work of fracture (EWF). Strain range for necking was determined from uniaxial tensile test, and was used to explain the deformation transition for 2‐staged crack growth in double‐edge‐notched tensile test. Through work‐partitioning, EWF values for HDPE were determined for each stage of the crack growth. Appropriateness of these EWF values to represent the material toughness is discussed. The study concludes that the EWF values for ductile polymers like HDPE may not be constant, but vary with the deformation behaviour involved in the crack growth process. POLYM. ENG. SCI., 47:1327–1337, 2007. © 2007 Society of Plastics Engineers     

Novel nitrogen‐containing epoxy resin. II. Cure kinetics by differential scanning calorimetry

The isothermal and nonisothermal cure behaviors of a novel nitrogen‐containing epoxy resin (XT resin) were studied by differential scanning calorimetry (DSC). Various kinetic parameters and details of cure process were obtained based on the Avrami theory. The results indicated that Avrami method is suitable for calculating the kinetic parameters up to the gel point at least. The apparent activation energy (E_a) for isothermal cure process was in agreement with that for nonisothermal cure process. E_a value in the early stage (78.5–81.0 KJ mol^?1) was about three times than that in the later stage (23.3–26.5 KJ mol^?1). The kinetic results from Avrami theory may present a combined effect of all factors, and which is helpful to understand the cure technique for XT–DDS system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3483–3489, 2006     

Isothermal crystallization kinetics and morphology development of isotactic polypropylene blends with atactic polypropylene

The crystallization kinetics and morphology development of pure isotactic polypropylene (iPP) homopolymer and iPP blended with atactic polypropylene (aPP) at different aPP contents and the isothermal crystallization temperatures were studied with differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. The spherulitic morphologies of pure iPP and larger amounts of aPP for iPP blends showed the negative spherulite, whereas that of smaller amounts of aPP for the iPP blends showed a combination of positive and negative spherulites. This indicated that the morphology transition of the spherulite may have been due to changes the crystal forms of iPP in the iPP blends during crystallization. Therefore, with smaller amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends increased with increasing aPP and presented a lower degree of perfection of the γ form coexisting with the α form of iPP during crystallization. However, with larger amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends decreased and reduced the γ‐form crystals with increasing aPP. These results indicate that the aPP molecules hindered the nucleation rate and promoted the molecular motion and growth rate of iPP with smaller amounts of aPP and hindered both the nucleation rate and growth rate of iPP with larger amounts of aPP during isothermal crystallization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1093–1104, 2007     

Preparation and properties of T300 carbon fiber‐reinforced thermoplastic polyimide composites

In this study, a series of T300 carbon fiber‐reinforced polyimide (CFRPI) composites were prepared by laminating premolding polyimide (PI) films with unidirectional carbon fiber (CF) layers. On the basis of PI systems design, the effect of CF volume fraction, processing conditions, and PI molecular structure on the properties of CFRPI composites was studied in detail. In addition, two kinds of nano‐particles, including carbon nano‐tube (CNT) and SiO₂ were filled into the premolding PI films with different concentrations. And the effect of nano‐particles on the properties of CFRPI composites was also investigated. The surface characteristic of T300 CF was measured by X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The properties of premolding PI film and CFRPI composites were measured by dynamic mechanical analysis (DMTA), SANS testing machine, scanning electron microscopy (SEM), and so forth. These experimental results showed that the properties of CFRPI composites were mainly affected by the premolding PI film and molding condition. The change of CF volume fraction from 55% to 65% took little effect on the mechanical properties of CFRPI composites. In addition, the incorporation of nano‐particle SiO₂ could further improve the properties of CFRPI composites, but CNT hardly improved the properties of CFRPI composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 646–654, 2006     

The kinetics of B‐a and P‐a type copolybenzoxazine via the ring opening process

The structure of benzoxazines is similar to that of phenolic resin through thermal self‐curing of the heterocyclic ring opening reaction that neither requires catalyst nor releases any condensation byproduct. These polybenzoxazine resins have several outstanding properties such as high thermal stability and high glass transition temperature. To better understand the curing kinetics of this copolybenzoxazine thermosetting resin, dynamic and isothermal differential scanning calorimetry measurements were performed. Three models, the Kissinger method, the Flynn–Wall–Osawa method, and the Kamal method, were used to describe the curing process. Dynamic kinetic activation energies based on Kissinger and Flynn–Wall–Osawa methods are 72.11 and 84.06 KJ/mol, respectively. The Kamal method based on an autocatalytic model results in a total order of reaction between 2.66 and 3.03, depending on curing temperature. Its activation energy and Arrhenius preexponential are 50.3 KJ/mol and 7959, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 730–737, 2005     

Phase behavior of ternary polymer blends with favorable interactions

Atactic poly(methyl methacrylate) (aPMMA) and poly(vinyl pyrrolidone) (PVP) with a weight‐average molecular weight of 360,000 g/mol were found to be immiscible on the basis of preliminary studies. Poly(styrene‐co‐vinyl phenol) (MPS) with a certain concentration of vinyl phenol groups is known to be miscible with both aPMMA and PVP. Is it possible to homogenize an immiscible aPMMA/PVP pair by the addition of MPS? For this question to be answered, a ternary blend consisting of aPMMA, PVP, and MPS was prepared and measured calorimetrically. The role of MPS between aPMMA and PVP and the effects of different concentrations of vinyl phenol groups on the miscibility of the ternary blends were investigated. According to experimental results, increasing the vinyl phenol contents of MPS has an adverse effect on the miscibility of the ternary blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2064–2070, 2005     

Oil absorbents based on styrene–butadiene rubber

Four oil absorbents based on styrene–butadiene (SBR)—pure SBR (PS), 4‐tert‐butylstyrene–SBR (PBS), EPDM–SBR network (PES), and 4‐tert‐butylstyrene‐EPDM‐SBR (PBES)—were produced from crosslinking polymerization of uncured styrene–butadiene rubber (SBR), 4‐tert‐butylstyrene (tBS), and ethylene–propylene–diene terpolymer (EPDM). The reaction took place in toluene using benzoyl peroxide (BPO) as an initiator. Uncured SBR was used as both a prepolymer and a crosslink agent in this work, and the crosslinked polymer was identified by IR spectroscopy. The oil absorbency of the crosslinked polymer was evaluated with ASTM method F726‐81. The order of maximum oil absorbency was PBES > PBS > PES > PS. The maximum values of oil absorbency of PBES and PBS were 74.0 and 69.5 g/g, respectively. Gel fractions and swelling kinetic constants, however, had opposite sequences. The swelling kinetic constant of PS evaluated by an experimental equation was 49.97 × 10^?2 h^?1. The gel strength parameter, S, the relaxation exponent, n, and the fractal dimension, d_f, of the crosslinked polymer at the pseudo‐critical gel state were determined from oscillatory shear measurements by a dynamic rheometer. The morphologies and light resistance properties of the crosslinked polymers were observed, respectively, with a scanning electron microscope (SEM) and a color difference meter.     

Structure and properties of nitrile rubber (NBR)–clay nanocomposites by co‐coagulating NBR latex and clay aqueous suspension

Nitrile rubber (NBR)–clay nanocomposites were prepared by co‐coagulating the NBR latex and clay aqueous suspension. Transmission electron microscopy showed that the silicate layers of clay were dispersed in the NBR matrix at the nano level and had a planar orientation. X‐ray diffraction indicated that there were some nonexfoliated silicate layers in the NBR–clay nanocomposites. Stress–strain curves showed that the silicate layers generated evident reinforcement, modulus, and tensile strength of the NBR–clay nanocomposites, which were significantly improved with an increase in the amount of clay, and strain‐at‐break was higher than that of the gum NBR vulcanizate when the amount of clay was more than 5 phr. The NBR–clay nanocomposites exhibited an excellent gas barrier property; the reduction in gas permeability in the NBR–clay nanocomposites can be described by Nielsen's model. Compared with gum NBR vulcanizate, the oxygen index of the NBR–clay nanocomposites increased slightly. The feasibility of controlling rubber flammability via the nanocomposite approach needs to be evaluated further. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3855–3858, 2003     

Spinning and drawing properties of ultrahigh‐molecular‐weight polyethylene fibers prepared at varying concentrations and temperatures

The concentrations and temperatures of ultrahigh‐molecular‐weight polyethylene (UHMWPE) gel solutions exhibited a significant influence on their rheological and spinning properties. The shear viscosities of UHMWPE solutions increased consistently with increasing concentrations at a constant temperature above 80°C. Tremendously high shear viscosities of UHMWPE gel solutions were found as the temperatures reached 120–140°C, at which their shear viscosity values approached the maximum. The spinnable solutions are those gel solutions with optimum shear viscosities and relatively good homogeneity in nature. Moreover, the gel solution concentrations and spinning temperatures exhibited a significant influence on the drawability and microstructure of the as‐spun fibers. At each spinning temperature, the achievable draw ratios obtained for as‐spun fibers prepared near the optimum concentration are significantly higher than those of as‐spun fibers prepared at other concentrations. The critical draw ratio of the as‐spun fiber prepared at the optimum concentration approached a maximum value, as the spinning temperature reached the optimum value of 150°C. Further investigations indicated that the best orientation of the precursors of shish‐kebab‐like entities, birefringence, crystallinity, thermal and tensile properties were always accompanied with the as‐spun fiber prepared at the optimum concentration and temperature. Similar to those found for the as‐spun fibers, the birefringence and tensile properties of the draw fibers prepared at the optimum condition were always higher than those of drawn fibers prepared at other conditions but stretched to the same draw ratio. Possible mechanisms accounting for these interesting phenomena are proposed.     

Preparation of V doped lanthanum silicate electrolyte ceramics by combustion method and study on conductance mechanism

Vanadium doped La_9.33Si_6−xV_xO_26+0.5x (x = 0.5, 1.0, 1.5) (LSVO) electrolyte powder was prepared by combustion method at 600°C for 5-7 min. The powder was sintered at 1500°C for 3 hours to prepare LSVO ceramics. XPS, IR, XRD, and EIS analysis show that V⁵⁺ doping replaces Si⁴⁺ in [SiO₄] to form [Si(V)O₄] tetrahedron. With the increase in x, the lattice volume increase. When x = 2.0, the LaVO₄ phase was formed, indicating that the limit doping amount of V⁵⁺ replacing Si⁴⁺ is x ≤ 1.5. The conductivity of LSVO increases significantly with the increase in x (x ≤ 1.0), which attributed to the defect reaction caused by V⁵⁺ doping. The addition of the interstitial oxygen Oi* in 6₃ channels and the increase of lattice volume leads to increased conductivity. When x = 1.0, the highest conductivity is 1.46 × 10⁻² S·cm⁻¹ (800°C). The doping enhancement conductivity mechanism is the Interstitial oxygen defect-Lattice volume composite enhancement mechanism.