Creep and Creep Fracture in Hot-Pressed Alumina

The creep and creep fracture behavior of two hot-pressed aluminas are presented, for both flexural and tensile testing. Steady-state power-law creep is observed with a stress exponent of about 2 for each material. Three distinct fracture regimes are found. At high stress in flexure, fracture occurs by slow crack growth with a high stress dependence of the failure time. At intermediate stresses, in both flexure and tension, creep fracture occurs by multiple microcracking after modest strains. Failure times exhibit a modest stress dependence (stress exponent of 2.5 in tension and 3 in flexure), with a constant failure strain equal to 0.09. The failure times are considerably longer in flexure than in tension, because of the constraint imposed on crack growth by the bending geometry. We conclude that flexure cannot be used for creep lifetime assessment, even in simple, single-phase materials such as Al₂O₃. At low stresses, in tension, failure also exhibits a modest stress dependence but with a much higher failure strain. The material shows the onset of super-plastic behavior.     

Comparative study of homogeneous and heterogeneous styrene polymerizations with Ni(acac)2/MAO catalytic system

Styrene polymerization was carried out with Ni(acac)₂/MAO and Ni(acac)₂/SiO₂/MAO. The influence of reaction parameters (Al/Ni mole ratio, catalyst concentration, temperature and time polymerization) on styrene polymerization was evaluated. It was observed that both catalytic systems were affected by reaction parameters and that the heterogeneous catalyst presented higher activity than the homogeneous one. Polystyrenes with different molecular weight, stereoregularity and polydispersity were obtained. These results suggest that different active catalyst species could have been present. In addition, two types of methylaluminoxane (MAO) with different molecular weights were also evaluated as cocatalyst. As a result, the catalyst activity and stereospecificity were strongly affected by the MAO type.     

Variability for oil and fatty acid composition in castorbean varieties

Thirty-six castorbean varieties were surveyed for oil and fatty acid composition, in order to determine variability of these seed compounds. A large variability of seed oil percentage was observed, ranging from 39.6 to 59.5%. Concerning the fatty acids, little variability was observed for ricinoleic acid, which was the most abundant in the oil, ranging from 83.65 to 90.00%. The other fatty acids appeared in small concentrations and showed a small range: 0.87 to 2.35, 0.68 to 1.84, 2.96 to 5.64, 3.19 to 5.98, and 0.34 to 0.91%, for palmitic, stearic, oleic, linoleic, and linolenic acid, respectively. Non-significant correlations were observed between fatty acids and seed oil percentage. However, significant correlations were observed among fatty acid concentrations: positive and negative ones. These significant correlations could be associated with the biosynthetic pathways of the fatty acids, which are not fully elucidated. They suggest, however, that selection for a particular fatty acid will tend to increase those positively correlated, and decrease those negative ones. Selection and plant breeding techniques could then be applied to modify the oil content of the castorbean seeds, considering the variability observed. For the fatty acid composition, however, the variability was not large enough to make substantial changes in their concentrations by selection procedures. More varieties should be surveyed to find out if such variability is available.     

Model falsification using set‐valued observers for a class of discrete‐time dynamic systems: a coprime factorization approach

This article introduces a new method for model falsification using set‐valued observers, which can be applied to a class of discrete linear time‐invariant dynamic systems with time‐varying model uncertainties. In comparison with previous results, the main advantages of this approach are as follows: The computation of the convex hull of the set‐valued estimates of the state can be avoided under certain circumstances; to guarantee convergence of the set‐valued estimates of the state, the required number of previous steps is at most as large as the number of states of the nominal plant; and it provides a straightforward nonconservative method to falsify uncertain models of dynamic systems, including open‐loop unstable plants. The results obtained are illustrated in simulation, emphasizing the advantages and shortcomings of the suggested method. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis,characterization, and metal complexation of poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) as polychelatogens in aqueous solution

We carried out the free‐radical copolymerization of N‐phenylmaleimide with acrylic acid and acrylamide with an equimolar feed monomer ratio. We carried out the synthesis of the copolymers in dioxane at 70°C with benzoyl peroxide as the initiator and a total monomer concentration of 2.5M. The copolymer compositions were obtained by elemental analysis and ¹H‐NMR spectroscopy. The hydrophilic polymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymers were performed. Hydrophilic poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) were used for the separation of a series of metal ions in the aqueous phase with the liquid‐phase polymer‐based retention method in the heterogeneous phase. The method is based on the retention of inorganic ions by the polymer in conjunction with membrane filtration and subsequent separation of low‐molecular‐mass species from the formed polymer/metal‐ion complex. The polymer could bind several metal ions, such as Cr(III), Co (II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) inorganic ions, in aqueous solution at pH values of 3, 5, and 7. The interaction of the inorganic ions with the hydrophilic polymer was determined as a function of pH and a filtration factor. Hydrophilic polymeric reagents with strong metal‐complexing properties were synthesized and used to separate those complexed from noncomplexed ions in the heterogeneous phase. The polymers exhibited a high retention capability at pH values of 5 and 7. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Manipulating the microstructure and rheology in polymer‐organoclay composites

A series of nanocomposites prepared by melt‐blending of cloisite‐based organoclays with poly(ethylene‐vinylacetate) (EVA) and neutralized poly (ethylene‐methacrylic acid) (EMA) copolymers were investigated via DSC, small‐angle X‐ray scattering (SAXS), and rheological techniques. SAXS results indicated partial clay exfoliation in all samples. In both EMA and EVA systems, the nominal melting temperature T_m and bulk crystallinity are not significantly affected by the presence of organoclays, suggesting that clay particles are predominantly confined in the amorphous phase. In rheological measurements (above T_m), the EVA‐clay system demonstrated a solid‐like rheological behavior under the small‐strain oscillatory shear, yet it was able to yield and flow under a steady shear, which is the characteristic of physical crosslinking. In contrast, the EMA‐clay system exhibited a melt‐like rheological behavior, where the influence of organoclay on the thermorheological behavior of the EMA composite was quite minimal. We propose that the carbonyl groups of vinylacetate in EVA interact with the clay surface, resulting in a strong physically crosslinking like interaction in the melt. On the other hand, the interaction between EMA and clay is weak because of repulsion between carboxyl anions and negatively charged clay surface.     

Metabolic behavior in rats of a nonprotein microemulsion resembling low-density lipoprotein

A protein-free microemulsion (LDE) with a lipid composition resembling that of low-density lipoprotein (LDL) was used in metabolic studies in rats to compare LDE with the native lipoprotein. LDE labeled with radioactive lipids was injected into the bloodstream of male Wistar rats, and plasma kinetics of the labeled lipids were followed on plasma samples collected at regular intervals for 12 h after injection. The 24-h LDE uptake by different tissues was also measured in tissue samples excised after the animals had been sacrificed. We found that LDE plasma kinetics were similar to those described for native LDL [fractional clearance rate (FCR) of cholesteryl ester, 0.42±0.11 h⁻¹]. The major site for LDE uptake was the liver, and the tissue distribution of the LDE injected radioactivity was as one would expect for LDL. To test whether LDE was taken up by the specific LDL receptors, the LDE emulsion was injected into rats treated with 17α-ethinylestradiol, which is known to increase the activity of these receptors; as expected, removal of LDE from the bloodstream increased (FCR=0.90±0.35 h⁻¹). On the other hand, saturation of the receptors that remove remnants by prior infusion of massive amounts of lymph chylomicrons did not change LDE plasma kinetics. These results indicate that LDE is cleared from plasma by B,E receptors and not by the E receptors that remove remnants. Incorporation of free cholesterol into LDE increased LDE plasma clearance. Incubation studies also showed that LDE incorporates a variety of apolipoproteins, including apo E, a ligand for recognition of lipoproteins by specific receptors. Our data suggest that LDE can be a useful tool to test LDL metabolism and B,E receptor function.     

Metastable Phase Selection and Partitioning for Zr(1−x)AlxO(2−x/2) Materials Synthesized with Liquid Precursors

Aqueous solutions of zirconium acetate and aluminum nitrate were spray pyrolyzed at 250°C and upquenched to different temperatures to yield metastable solid solutions of composition Zr_{(1− x )}Al_xO_{(2− x /2)}. An amorphous oxide forms first during pyrolysis which subsequently crystallizes as a single phase for x ≤ 0.57 (≤40 mol% Al₂O₃). The crystallization temperature increased with Al₂O₃ content. Electron diffraction, supported by Raman spectroscopy, indicates that the initial phase is tetragonal. At higher temperatures, the initial solid solation partitions to other metastable phases, viz., t -ZrO₂+γ-Al₂O₃, prior to achieving their equilibrium phase assemblage, m -ZrO₂+α-Al₂O₃. Partitioning yields a nanocomposite microstructure with grain sizes of 20–100 nm, compared to the 3 to 5 nm in the initial, single phase. Compositions containing 45 to 50 mol% Al₂O₃ concurrently crystallize and partition. The structure selected during crystallization and the partitioning phenomena are discussed in terms of diffusional constraints during crystallization, which are conceptually similar to those operating during rapid solidification.     

Crack–Tip Toughness of a Soft Lead Zirconate Titanate

Crack–opening displacement (COD) measurements were performed on a commercial lead zirconate titanate (PZT). The intrinsic fracture toughness (or crack–tip toughness) of this material was determined using a new evaluation procedure, which takes into account the near–tip CODs and complete crack profile CODs. The crack–tip toughness K _I0 was determined from an extrapolation of COD data obtained at various loading stages, thus avoiding the complications caused by subcritical crack growth in PZT. Results for plane strain and plane stress condition are presented.