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     

Synthesis of polystyrene/poly(butyl acrylate) core–shell latex and its surface morphology

A polystyrene (PS)/poly(butyl acrylate) (PBA) composite emulsion was produced by seeded emulsion polymerization of butyl acrylate (BA) with PS seed particles which were prepared by emulsifier‐free polymerization of styrene with potassium persulfate (KPS) under a nitrogen atmosphere at 70°C for 24 h with stirring at 60 rpm and swelled with the BA monomer in an ethanol/water medium. The structure of the PS/PBA composite particles was confirmed by the presence of the characteristic absorption band attributed to PS and PBA from FTIR spectra. The particles for pure PS and PS/PBA with a low content of the BA monomer were almost spherical and regular. As the BA monomer content was increased, the particle size of the PS/PBA composite particles became larger, and more golf ball‐like particles were produced. The surface morphology of the PS/PBA composite particles was investigated by AFM and SEM. The T_g's attributed to PS and PBA in the PS/PBA composite particles were found at 110 and ?49°C, respectively. The thermal degradation of the pure PS and PS/PBA composite particles occurred in one and two steps, respectively. With an increasing amount of PBA, the initial thermal decomposition temperature increased. On the contrary the residual weight at 450°C decreased with an increasing amount of PBA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 595–601, 2003     

Preparation and swelling behavior of biodegradable hydrogels based on α,β‐poly(N‐2‐hydroxyethyl‐DL‐aspartamide)

Biodegradable polymers and the hydrogels have been increasingly applied in a variety of biomedical fields and pharmaceutics. α,β‐Poly(N‐2‐hydroxyethyl‐DL ‐aspartamide), PHEA, one of poly(amino acid)s with hydroxyethyl pendants, are known to be biodegradable and biocompatible, and has been studied as an useful biomaterial, especially for drug delivery, via appropriate structural modification. In this work, hydrogels based on PHEA were prepared by two‐step reaction, that is, the crosslinking of polysuccinimide, the precursor polymer, with oligomeric PEG or PEI‐diamines and the following nucleophilic ring‐opening reaction by ethanolamine. Soft hydrogels possessing varying degrees of gel strength could be prepared easily, depending on the amount of different crosslinking reagents. The swelling degrees, which were in the range of 10–40 g–water/dry gel, increased somewhat at higher temperature, and also at alkaline pH of aqueous solution. A typical hydrogel remained almost unchanged for 1 week, at 37°C in phosphate buffer of pH 7.4, and then seemed to degrade slowly as time. A porous scaffold could be fabricated by the freeze drying of water‐swollen gel. The PHEA‐based hydrogels have potential for useful biomaterial applications including current drug delivery system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3741–3746, 2003     

Influence of post‐extrusion parameters on the final morphology of polystyrene/high density polyethylene blends

The deformation of the dispersed phase in polystyrene/high density polyethylene (PS/HDPE) blends produced by ribbon extrusion was studied numerically and experimentally. A mathematical model for the deformation of the dispersed phase in ribbon extrusion processing of polymer blends was developed assuming uniaxial deformation of the ribbon and the equilibrium shapes of the dispersed particles with a pressure balance over a drop. Simulated morphologies as function of the post‐extrusion parameters were obtained and compared with experiments. The analysis of the ribbon extrusion process showed that parameters such as draw ratio (DR) and ribbon‐water contact length (X) significantly influence the ribbon dimensions, the extensional stress, and the stretching force. The results also showed that deformation and coalescence of the dispersed phase in the ribbon extrusion processing of polymer blends increase at higher DR and/or lower X values. The comparison between the model and the experimental morphologies of PS/HDPE produced a good agreement.     

Preparation and characterization of maleic anhydride‐g‐polypropylene/diamine‐modified clay nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by compounding maleic anhydride‐g‐polypropylene (MAPP) with MMT modified with α,ω‐diaminododecane. Structural characterization confirmed the formation of characteristic amide linkages and the intercalation of MAPP between the silicate layers. In particular, X‐ray diffraction patterns of the modified clay and MAPP/MMT composites showed 001 basal spacing enlargement as much as 1.49 nm. Thermogravimetric analysis revealed that the thermal decomposition of the composite took place at a slightly higher temperature than that of MAPP. The heat of fusion of the MAPP phase decreased, indicating that the crystallization of MAPP was suppressed by the clay layers. PP/MAPP/MMT composites showed a 20–35% higher tensile modulus and tensile strength compared to those corresponding to PP/MAPP. However, the elongation at break decreased drastically, even when the content of MMT was as low as 1.25–5 wt %. The relatively short chain length and loop structure of MAPP bound to the clay layers made the penetration of MAPP molecules into the PP homopolymer phase implausible and is thought to be responsible for the decreased elongation at break. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 307–311, 2005     

Change in the Surface Microstructure of Ti(C0.5N0.5)–20WC–10Ni–10Co Cermets During Sintering in a Nitrogen Atmosphere

Experiments were carried out to determine the effects of introducing nitrogen during sintering on the formation of the surface gradient zone for Ti(C,N)-based cermets. WC was used as a secondary carbide in a Ti(C,N)–Ni/Co system, and processing was carried out in vacuum, and under various nitrogen conditions (at 1torr). Nitrogen was introduced during various stages of the sintering (above 1300°C). The introduction of nitrogen during the heating stage facilitated the formation of a (Ti,W)(C,N)-enriched layer to a greater extent than the vacuum conditions. A thermodynamic calculation revealed that denitrification occurs during sintering, even when nitrogen pressure is applied. A nitrogen atmosphere during the heating stage is effective in retarding the dissolution of WC in the cermet matrix. The introduction of nitrogen during the holding or cooling stages also led to an enrichment in the binder phase near the surface. The thickness of the stratified binder layer was strongly related to the cooling rate.     

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     

Morphology and mechanical properties of blends of thermoplastic polyurethane and polyolefins

Polyolefins (PO) were melt mixed with thermoplastic polyurethane (TPU) in a 20 : 80 weight ratio with or without compatibilizer containing 0.5 wt % of maleic anhydride. Effects of component viscosities on morphology and on mechanical properties of the blend were studied by scanning electron microscope (SEM), tensile property analysis, and dynamic mechanical analysis (DMA). It was found that the disperse particle size of compatibilizer‐free blends decreased with the decreasing viscosity ratio of the disperse phase to TPU. The efficiency of the compatibilizer in reducing the particle size varied with viscosity ratios of the disperse phase to compatibilizer. However, the particle size did not decrease with the decreasing viscosity ratio monotonically. With lower viscosity ratio, addition of 5 wt % compatibilizer resulted in a greater reduction of particle size and less loss in the tensile properties as compared to the TPU matrix. For the polyethene (PE) that has the lowest viscosity value among all the POs, its size in the blend was stabilized with the addition of compatibilizer and no compatibilization was detected by DMA and by tensile property analysis. The mobility of the disperse phase and compatibilizer and the dispersion competition between them seemed important. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 875–883, 2006     

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     

Encapsulation of titanium dioxide in styrene/n‐butyl acrylate copolymer by miniemulsion polymerization

Miniemulsion copolymerization of styrene/n‐butyl acrylate was investigated as a means of encapsulating hydrophilic titanium dioxide (TiO₂) in a film‐forming polymer. Dispersion studies of the TiO₂ were first carried out to determine the choice of stabilizer, its concentration, and the dispersion process conditions for obtaining stable TiO₂ particles with minimum particle size. Through screening studies of various functional stabilizers and shelf‐life stability studies at both room and polymerization temperatures, Solsperse 32,000 was selected to give relatively small and stable TiO₂ particles at 1 wt % stabilizer and with 20–25 min sonification. The subsequent encapsulation of the dispersed TiO₂ particles in styrene/n‐butyl acrylate copolymer (St/BA) via miniemulsion polymerization was carried out and compared with a control study using styrene monomer alone. The lattices resulting from the miniemulsion encapsulation polymerizations were characterized in terms of the encapsulation efficiencies (via density gradient column separations; DGC) and particle size (via dynamic light scattering). Encapsulation efficiencies revealed that complete encapsulation of all of the TiO₂ by all of the polymer was not achieved. The maximum encapsulation efficiencies were 79.1% TiO₂ inside 61.7% polystyrene and 63.6% TiO₂ inside 38.5% St/BA copolymer. As the density of the particles collected from the DGC increased from one layer to another, both the average particle size and the number of the TiO₂ particles contained in each latex particle increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3479–3486, 2006