Physical gelation of crystallizing metallocene and Ziegler-Natta ethylene-hexene copolymers

The effect of molecular architecture on the evolution of viscoelastic properties during crystallization was investigated using ethylene-hexene copolymers manufactured via metallocene (M-LLDPE) and Ziegler-Natta (ZN-LLDPE) processes. Differences in branching distribution were shown to have a drastic effect on the viscoelastic properties near the gel point. It is shown that the branching distribution rather than branch content is the determining parameter for the evolution of the rheological properties during isothermal and non-isothermal crystallization, and for the width of the solidification interval. We developed a partial melting technique for the preparation of stable critical gels of LLDPE whose viscoelastic properties correspond to the intermediate state between melt and solid. Local molecular conformation and crystallinity in these gels were characterized by Raman spectroscopy, which shows that the transition from melt-like to solid-like rheological behavior (physical gelation) in LLDPE occurs at a very low overall crystallinity of less than 5%.     

Processing, Microstructure, and Wear Behavior of Silicon Nitride Hot-Pressed with Alumina and Yttria

Commercial silicon nitride powder with A1₂O₃ and Y₂O₃ additives was hot-pressed to complete density. The resulting microstructure contained elongated grains with no trace of remaining α-Si₃N₄. The aspect ratio of the elongated grains increased with increasing soak time at a fixed hot-pressing temperature. X-ray diffraction analysis showed that the crystalline phase in the hot-pressed samples was β-sialon (Si_6−zAl_zO_zN_8−z) with z values that increased with soak time. The fracture strength and fracture toughness of the samples increased as the aspect ratio of the grains increased. The Vickers hardness decreased slightly as the soak time was increased, which was attributed to a grain size effect. Wear tests of silicon nitride against silicon nitride were conducted on a reciprocating pin-on-disk apparatus with paraffin oil as a lubricant. Correlation studies of wear with microstructure and mechanical properties were performed. The wear rate increased rapidly with increasing soak time in spite of the increased strength and toughness. This was attributed to increased third-body wear caused by pullout of pieces from the wear surface. The pullout mechanism was not conclusively identified. However, TEM examination showed clear evidence of dislocation motion under the wear scar. Grain boundary microstresses caused by the anisotropic thermal expansion and elastic properties of the elongated grains may have contributed to the observed pullout.     

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     

Isothermal crystallization kinetics and melting behavior of nylon/saponite and nylon/montmorillonite nanocomposites

DSC thermal analysis and X‐ray diffraction have been used to investigate the isothermal crystallization behavior and crystalline structure of nylon 6/clay nanocomposites. Nylon 6/clay has prepared by the intercalation of ε‐caprolactam and then exfoliating the layered silicates by subsequent polymerization. The DSC isothermal results reveal that introducing saponite into the nylon structure causes strongly heterogeneous nucleation induced change of the crystal growth process from a two‐dimensional crystal growth to a three dimensional spherulitic growth. But the crystal growth mechanism of nylon/montmorillonite nanocomposites is a mixed two‐dimensional and three‐dimensional spherulitic growth. The activation energy drastically decreases with the presence of 2.5 wt % clay in nylon/clay nanocomposites and then slightly increases with increasing clay content. The result indicates that the addition of clay into nylon induces the heterogeneous nucleation (a lower ΔE) at lower clay content and then reduces the transportation ability of polymer chains during crystallization processes at higher clay content (a higher ΔE). The correlation among crystallization kinetics, melting behavior, and crystalline structure of nylon/clay nanocomposites is also discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2196–2204, 2004     

Allelochemical resistance of bald cypress,Taxodium distichum,heartwood to the subterranean termite,Coptotermes formosanus

The heartwood of bald cypress,Taxodium distichum (L.) Rich., resisted feeding attack by the Formosan subterranean termite,Coptotermes formosanus Shiraki. Hexane-extracted heartwood, however, was consumed at > 12 times the amount of sound heartwood eaten. A bioassay usingT. distichum sapwood as a feeding substrate was employed to assess the antitermitic activity of successive hexane, acetone, and methanol extracts of heartwood shavings and isolates derived from the active hexane extract. Two fractions, eluted from the crude hexane extract by liquid chromatography, significantly reduced termite feeding compared to the parent extract, while a third fraction was less active than the original hexane extract. Each fraction contained one major component. All three components were structurally related diterpenes. The two most active heartwood constituents were identified by GC-MS and NMR as ferruginol and manool, while the third and least active, but most prevalent, compound in heartwood was identified as nezukol. Results of bioassays suggest that these allelochemicals act principally as feeding deterrents with accompanying termite mortality due to starvation.     

Synthesis and characterization of a positive‐working,aqueous‐base‐developable photosensitive polyimide precursor

A positive‐working, aqueous‐base‐developable photosensitive polyimide precursor based on poly(amic ester)‐bearing phenolic hydroxyl groups and a diazonaphthoquinone photosensitive compound was developed. The poly(amic ester) was prepared from a direct polymerization of 2,2′‐bis‐(3‐amino‐4‐hydroxyphenyl)hexafluoropropane and bis(n‐butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. Subsequently, the thermal imidization of the poly(amic ester) precursor at 300°C produced the corresponding polyimide. The inherent viscosity of the precursor polymer was 0.23 dL/g. The cyclized polyimide showed a glass‐transition temperature at 356°C and a 5% weight loss at 474°C in nitrogen. The structures of the precursor polymer and the fully cyclized polymer were characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. The photosensitive polyimide precursor containing 25 wt % diazonaphthoquinone photoactive compound showed a sensitivity of 150 mJ/cm² and a contrast of 1.65 in a 3 μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 10 μm was obtained from this composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 352–358, 2002     

On the oxidation kinetics and mechanisms of various SiC-coated carbon-carbon composites

SiC coatings on the surface of C-C were produced by either silicone resin impregnation/ pyrolysis or reaction sintering. Cycles of resin impregnation/pyrolysis produced an SiC coating, on the walls of fine open pores, which was effective in reducing the oxidation rate of C-C and in shifting the transition temperature to a higher value. Unless it is pre-coated with a pyrocarbon layer before sintering, plain reaction sintered SiC has oxidation behaviors similar to those of the above-mentioned SiC. The dense pyrocarbon film deposition on the surface of C-C could form a better SiC film than others. The carbon film homogenized the surface of C-C and a dense SiC film was established. The oxidation of the coated C-C can be modelled by a set of “oxidation resistors” in series and/or in parallel, with each resistor corresponding to an oxidation element. The controlling mechanism can be resolved from the activation energy. A combined resistant layer, consisting of resin impregnation, pyrocarbon film and reaction sintering SiC, showed the best oxidation resistance of any single-layer coated C-C composite.     

Free radical solution oligomerization of styrene in a continuous-stirred tank reactor train

For free radical oligomerization of styrene, a scheme for calculating the molecular weight distribution and conversion in a continuous-stirred tank reactor (CSTR) train is developed, which also allows the calculation of molecular weight distribution (MWD) for batch reaction. Calculations show that under conventional or near dead-end condition: (1) increasing initial initiator concentration, reaction time and reaction temperature, and decreasing initial monomer concentration cause P?_n and P?_w to decrease and MWD to narrow; (2) increasing initial initiator concentration, reaction time and reaction temperature, and increasing monomer concentration cause monomer conversion to increase; (3) a single CSTR gives a lower rate of oligomer production, but a narrower MWD than does a batch reactor.     

应力作用下的相变

水静压抑制Fe-C和钢中体积膨胀型相变，如铁素体、珠光体、贝氏体和马氏体相变。单向应力促发铁素体和珠光体相变，拉应力的效果尤为显著。0．38C-Cr-Mo钢中，铁素体、珠光体和贝氏体相变在应力下的动力学，可由Johnson-Mehl-Avrami方程中加入应力因子经修正来描述。由于铁素体和珠光体的化学驱动力小，应力所作膨胀功使形核率(J^*)增高和孕育期τ缩短。而贝氏体相变中，可能由于应力下碳自奥氏体贫化，或减少相界面能，从而使τ增高和τ缩短，待试验予以证明。水静压对Ms温度影响的定量描述因不同材料而异。列出Patel-Cohen所建立的dMs／dσ方程，及本文作者提出的应力影响Ms的方程。应力诱发马氏体会改变其晶体学及形态，提出以形核率的数值来判定其形态。奥氏体的力学稳定化在马氏体相变中主要由于奥氏体强化所导致，在贝氏体相变中却主要由于晶体学阻碍长大所造成的。     

Coalescence of tungsten grains around molybdenum grains in the presence of a liquid phase

The microstructural evolution of W–22.4Mo–7.8Ni–3.4Fe was investigated in this study. A first liquid phase primarily composed of Ni, Fe, and Mo resulted in the coexistence of large W–Mo grains having Mo-rich cores and small W grains.