Slow stable crack growth in high density polyethylenes

The phenomenon of slow stable crack growth in polyethylene is investigated using notched specimens subject to constant load and the concepts of fracture mechanics. The effect of specimen geometry and dimension, the loading and the mode of loading on the applied stress intensity factor versus crack speed ($\text{K}{}_{\mathrm{c}}\text{-}\text{a}\text{?}$) curves has been studied to demonstrate that K_c is the controlling stress parameter for crack growth under suitable conditions. $\text{K}{}_{\mathrm{c}}\text{-}\text{a}\text{?}$ curves are obtained for a high density polyethylene homopolymer in distilled water and in a diluted detergent solution at four different temperatures. Results are also obtained for a much tougher medium density polyethylene copolymer whenever possible. Several mechanisms can be identified from the form of the $\text{K}{}_{\mathrm{c}}\text{-}\text{a}\text{?}$ curves. Two, in particular, have been observed but not explained before: (i) crack growth with a time dependence of 0.25, and (ii) the high $\text{K}{}_{\mathrm{c}}\text{-}\text{a}\text{?}$ slopes for crack growth in a tough copolymer. With the help of scanning electron microscopic studies of the fracture surfaces, (i) is postulated to be due to diffusion controlled void growth process and (ii) is considered to be the result of crack tip blunting effects. From the temperature dependence of crack growth, the activation energy of the diffusion controlled crack growth process is found to coincide with that of the x-relaxation process in polyethylene implying that diffusion controlled crack growth may be related to the motion of main chains in the polymer.     

The SMSI between supported platinum and CeO2–ZrO2–La2O3 mixed oxides in oxidative atmosphere

CeO₂–ZrO₂–La₂O₃ (CZL) mixed oxides were prepared by citric acid sol–gel method. The as-received gel was calcined at 500, 700, 900 and 1050 °C to obtain the so-called C5, C7, C9 and CK, respectively. The C5, C7 and C9 powders were impregnated with H₂PtCl₆ and then calcined at 500 °C to prepare P5C5, P5C7 and P5C9, respectively. The impregnated CK powders were calcined at 500, 700 and 900 °C to prepare P5CK, P7CK and P9CK, respectively. The XRD and XPS analyses show that the surface distribution of Pt is evidently influenced by the structural and textural properties of the support. The CO adsorption followed by FTIR reveals that the dispersion and the chemisorption sites of Pt are reduced as the calcination temperature of CZL support increases. The chemisorption ability of the CK samples is even completely deactivated. The encapsulation mechanism, which has been applied to explain the so-called strong metal–support interaction (SMSI) after reductive treatment, is introduced here to demonstrate the abnormal observations though the samples were prepared in oxidative atmosphere. The HRTEM results also confirm this explanation. The effects of oxygen vacancies, the chemisorption sites on the Pt surface and Pt/Ce interfacial sites on the three-way catalytic activities are discussed.     

Micromechanical properties on the surface of PVC/SBR blends spatially resolved by a nanoindentation technique

The microhardness and micromodulus on the surface of poly(vinyl chloride) (PVC)/styrene‐butadiene rubber (SBR) blends were determined using a nanoindenter. A flat surface was obtained by microtoming the sample at ?100°C in liquid nitrogen. Dozens of indents along a line with a spatial interval of 0.5 μm were performed. From the loading and unloading curves of each indentation, the stiffnesses of the unloading curve and the contact area between the sample and the indenter were evaluated, and the local modulus and hardness were calculated. Profiles of the local hardness and modulus were obtained from the lines of indents. Pure PVC and a miscible PVC/acrylonitrile‐butadiene rubber (NBR) (40/10) blend showed constant modulus and hardness values. In the case of an immiscible PVC/SBR (50/50) blend, which has a morphology of elongated PVC droplets in the SBR matrix, the hardness and modulus profiles showed regions of the different phases. At the interface between the SBR and PVC phases, a step change in the modulus and hardness profiles was observed. The force required to deform the material at the same displacement increased systematically across the interface from the SBR to the PVC phase because of the increasing contribution of the PVC phase. Polym. Eng. Sci. 44:609–614, 2004. © 2004 Society of Plastics Engineers.     

氯化聚乙烯接枝氯乙烯聚合速率及传热

本文用气相色谱技术研究氯化聚乙烯(CPE)-接枝(g)-氯乙烯(VC)聚合动力学,对不同引发剂体系分析热负荷分布,并对7 m~3聚合釜传热面进行校核。     

Isotopic Oxygen Exchange and EPR Studies of Superoxide Species on the SrF2/La2O3 Catalyst

By using the in situ IR spectroscopy, the superoxide species (O₂⁻), characterized by the O–O stretching peak at 1130 cm⁻¹, was detected on the SrF₂/La₂O₃ catalyst at temperatures up to 973 K. The introduction of ¹⁸O₂ isotope caused the 1130 cm⁻¹ peak to shift to lower wavenumbers (1095 and 1064 cm⁻¹), consistent with the assignment of the spectra to the superoxide species. A good correlation between the rate of the disappearance of the O₂⁻ species and that of the formation of C₂H₄ was observed, suggesting that O₂⁻ was the active oxygen species responsible for the oxidative coupling of methane (OCM) on the SrF₂/La₂O₃ catalyst. This conclusion was reinforced by the EPR experiments (g_xx = 2.0001, g_yy = 2.0045, g_zz = 2.0685), showing that O₂⁻ was the only paramagnetic oxygen species detectable on the O₂-preadsorbed SrF₂/La₂O₃ catalyst. These results suggest that superoxide O₂⁻ can be a stable active oxygen species, whose role in the OCM reaction cannot be overlooked.     

MICROSCOPIC SPREADING CHARACTERISTICS OF NONPOLAR PERFLUOROPOLYETHER FILMS

The surface diffusion characteristics of nonpolar perfluoropolyether (PFPE) Z on carbon surfaces are investigated in two regimes, submonolayer and multilayer, for nano-thin films. For the submonolayer regime, the two-dimensional, cubic van der Waals equation of state is applied to determine the dependence of the surface diffusion coefficient on the film thickness, as experimental surface diffusion coefficients increase with increasing film thickness. For the multilayer regime, a conventional fluid mechanics analysis with position dependent viscosity and a van der Waals disjoining pressure gradient is applied to investigate the surface diffusion characteristics. The present theoretical analysis qualitatively agrees with the experimental results.     

The onset of Taylor-Görtler vortices in impulsively decelerating swirl flow

The onset of hydrodynamical instability induced by impulsive spin-down to rest in a cylinder containing a Newtonian fluid is analyzed by using propagation theory. It is well-known that the primary transient swirl flow is laminar, but with initial high velocities secondary motion sets in at a certain time. The dimensionless critical time Τ_c to mark the onset of instability is presented here as a function of the Reynolds number Re. Available experimental data indicate that for large Re deviation of the velocity profiles from their momentum diffusion occurs starting from a certain time Τ≈4Τ_c. This means that secondary motion is detected at this characteristic time. It seems evident that during Τ_c⪯Τ⪯4Τ_c, secondary motion is relatively very weak and the primary diffusive momentum transfer is dominant.     

Phase inversion and its effect on the properties of polyester polyurethane cationomers

Polyester polyurethane cationomers are prepared using polyester polyol of molecular weight 2000 as soft segments, N-methyl diethanolamine as chain extender, glycolic acid as quaternization agent, methyl ethyl ketone as solvent, and 4,4'-diphenylenemethylene diisocyanate (MDI) as diisocyanate. Properties of the films cast from solutions and emulsions are studied by infrared spectroscopy, dynamic mechanical analysis, thermogravimetric analysis, differential scanning calorimetry, and tensile-elongation testing. Ionization can cause phase separation and produces increased cohesion in the hard domains. The dispersion process can be divided into three stages involving a separation of hard segment aggregates due to adsorption of water on their surface, water entering into hard segment microionic lattics, and finally a rearrangement of agglomerates to form microspheres. The dispersion can disrupt the order in the hard domains and an increased phase separation.     

Modeling nonisothermal impregnation of fibrous media with reactive polymer resin

The manufacture of polymer composites through resin transfer molding (RTM) or structural reaction injection molding (SRIM) involves the impregnation of a fibrous reinforcement in a mold cavity with a reactive polymer resin. The design of RTM and SRIM operations requires an understanding of the various parameters, such as materials properties, mold geometry, and mold filling conditions, that affect the resin impregnation process. Modeling provides a potential tool for analyzing the relationships among the important parameters. The present work provides the physical model and finite element formulations for simulating the mold filling stage. Resin flow through the fibers is modeled using two-dimensional Darcian flow. Simultaneous resin reaction and heat transfer among resin, mold walls, and fibers are considered in the model. The proposed technique emphasizes the use of the least squares finite element method to solve the convection dominated mass and energy equations for the resin. Excellent numerical stability of the proposed technique provides a powerful numerical method for the modeling of polymer processing systems characterized by convection dominated transport equations. Results from example numerical studies for SRIM of polyurethane/glass fiber composites were presented to illustrate the application of the proposed model and numerical scheme.     

Calcium binding mode of {gamma}-carboxyglutamic acids in conantokins

Conantokin-T (con-T) and conantokin-G (con-G) are two highlyhomologous peptide toxins found in Conus venom. The former isa 21-residue peptide with four -carboxyglutamic acid (Gla) residues(at positions 3, 4, 10 and 14), while the latter is a 17-residuepeptide with five -carboxyglutamic acid residues (at positions3, 4, 7, 10 and 14). Despite the apparent similarity in numberand relative positions of the -carboxyglutamic acid residues,¹¹³Cd-NMR studies indicated a distinct metal binding behaviorfor con-G and con-T. There appears to be four binding sitesin con-G in contrast to one metal binding site in con-T. Toelucidate the mode of calcium binding by the -carboxyglutamicacid residues in these conantokins, we designed various analogouspeptides with their -carboxyglutamic acid replaced by otheramino acid residues. ¹¹³Cd-NMR experiments on conantokin analoguesreveal that the major difference in the number of metal bindingsites between con-G and con-T is due to the residue at position7. We also performed molecular simulations to calculate therelative binding free energies of several potential bindingsites. Based on our theoretical and experimental results, wepropose a `four-site' binding model for conantokin-G and a `single-site'binding model for conantokin-T.