Plastic flow localization due to non-uniform void distribution

Infinite band calculations indicate that the process of flow localization in voided solids is highly sensitive to non-uniformity in void distribution. In this paper, a model is proposed for an elastic-plastic solid with an excess of voids in a disk-shaped cluster embedded in a uniform background distribution. The model is used to study the effect of a void cluster on plastic flow localization. Substantial reductions in ductility due to nonuniformity only occur for quite large clusters when the triaxiality of the overall stresses is low, as in uniaxial tension. At higher stress triaxialities, a small cluster can be severely deleterious.     

Crack deflection at an interface between dissimilar elastic materials: Role of residual stresses

A crack intersecting an interface between two dissimilar materials may advance by either penetrating through the interface or deflecting into the interface. The competition between deflection and penetration can be assessed by comparison of two ratios: (i) the ratio of the energy release rates for interface cracking and crack penetration; and (ii) the ratio of interface to material fracture energies. Residual stresses caused by thermal expansion misfit can influence the energy release rates of both the deflected and penetrating crack. This paper analyses the role of residual stresses. The results reveal that expansion misfit can be profoundly important in systems with planar interfaces (such as layered materials, thin film structures, etc.), but generally can be expected to be of little significance in fiber composites. This paper corrects an earlier result for the ratio of the energy release rate for the doubly deflected crack to that for the penetrating crack in the absence of residual stress.     

An analytical model of rumpling in thermal barrier coatings

Multilayer thermal barrier coatings (TBCs) deposited on superalloy turbine blades provide protection from combustion temperatures in excess of 1500 °C. One of the dominant failure modes comprises cracking from undulation growth, or rumpling, of the highly compressed oxide layer that grows between the ceramic top coat and the intermetallic bond coat. In this paper, a mechanistic model providing an analytical approximation of undulation growth is presented for realistic cyclic thermal histories. Thickening, lateral growth straining and high temperature yielding of the oxide layer are taken into account. Undulation growth in TBC systems is highly nonlinear and characterized by more than 20 material and geometric parameters, highlighting the importance of a robust yet computationally efficient model. At temperatures above 600 °C, the bond coat creeps. Thermal expansion mismatch occurs between the superalloy substrate and the oxide layer and, in some systems, the bond coat. In addition, some bond coats, such as PtNiAl, exhibit a martensitic phase transformation accompanied by nearly a 1% linear expansion, giving rise to a large effective mismatch. These two mismatches promote undulation growth. Nonlinear interaction between the stress in the bond coat induced by the constraining effect of the thick substrate and normal tractions applied at the surface of the bond coat by the compressed, undulating oxide layer produces an increment of undulation growth during each thermal cycle, before the stress decays by creep. A series of problems for systems without the ceramic top coat are used to elucidate the mechanics of undulation growth and to replicate trends observed in a series of experiments and in prior finite-element simulations. The model is employed to study for the first time the effect on undulation growth of a shift in the temperature range over which the transformation occurs, as well as the relative importance of the transformation compared to thermal expansion mismatch. The role of the top coat and other viable ways of reducing undulation growth are considered.     

The production of high polymer to surfactant microlatexes

Starved‐feed microemulsion polymerization of styrene was investigated. The influence of the type (SDS or Dowfax 2A1) and concentration of anionic surfactant on the final particle size of latex made by the polymerization of microemulsions of styrene was studied. In addition, the influence of 1‐pentanol and acrylic acid as cosurfactants was examined. Latexes with 20% solids content and polymer to surfactant ratio of 22 were produced, with a particle diameter of 42 nm and very low polydispersity indexes. Smaller particles are produced using SDS than Dowfax 2A1 for the same weight fraction of surfactant; however, similar particle sizes were obtained with the same molar concentrations of SDS and Dowfax 2A1. Further shot additions of monomer increased solids level as high as 40% and polymer to surfactant ratios greater than 40, with particles remaining monodisperse with average diameter smaller than 60 nm. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 48–54, 2010     

Controlled Activity Polymers with Pendently Bound Herbicides

Abstract

Controlled activity or controlled release polymeric systems are becoming increasingly important in a variety of pharmaceutical, medical, and agricultural applications. The macromolecular nature of these delivery systems allows for control of rate of delivery, mobility, and period of effectivness for the biologically active component.     

A field-dependent CIDNP study of the photochemical reduction of benzoquinones in 2-propanol

The CIDNP behaviour in the photochemical reduction of a series of 1,4-benzoquinones in 2-propanol was studied systematically in detail at low fields. The radical pair model formulated by Lawler and co-workers was extended to interpret the present results. It is of interest to note that the polarization crossover occurs at relatively high fields compared to other known systems and it is insensitive to the number of protons in the various quinones.     

Copper‐mediated controlled radical polymerization in continuous flow processes: Synergy between polymer reaction engineering and innovative chemistry

Copper(0)‐mediated controlled radical polymerization (CRP), or single‐electron transfer‐living radical polymerization (SET‐LRP) is a robust and dynamic technique that has attracted considerable academic and industrial interest as a synthetic tool for novel value‐added materials. Although SET‐LRP possesses many advantages over other forms of CRP, this novel chemistry still requires concurrent engineering solutions for successful commercial application. In this highlight, the evolution of atom‐transfer radical polymerization chemistry and development in continuous processes is presented, leading to recent research on the use of SET‐LRP in continuous flow tubular reactors. The proofs of concept are reviewed, and remaining challenges and unexplored potential on the use of continuous flow processes with SET‐LRP as a powerful platform for the synthesis of novel polymeric materials are discussed. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3081–3096     

Enthalpy relaxation in polymethyl(α-n-alkyl)acrylates: Effect of length of alkyl chain

In this work, we have investigated by DSC the structural relaxation of amorphous polymethyl(α-n-alkyl)acrylates in which it is possible to change the length of the alkyl chain. We have evaluated the Narayanaswamy parameter, x, which controls the relative contribution of temperature and of structure to the relaxation time, the apparent activation energy, Δh*, and the nonexponentiality parameter, β, of the stretched exponential response function. The results suggest that x increases while Δh* decreases and β remains constant as the length of the side chain increases. This allows us to comment on the effect of chemical modification on the relaxation kinetics. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 583–593, 1998     

Magnetic normalization of particle size effects in a heavy metal pollution study of intertidal sediments from the Yangzte Estuary

Magnetic, granulometric and geochemical analyses were conducted on an intertidal sediment core from the Yangtze Estuary to evaluate the possibility of normalizing samples for particle size effects in a heavy metal pollution study by means of magnetic proxies. It has been found that the magnetic parameter XARM, indicating fine grained ferrimagnetic minerals, correlates well with the clay content and organic matter concentration of the sediments. XARM also shows significant relationship with heavy metals. Therefore XARM is proposed as a proxy for clay content in the sediments, and can be used to compensate for the particle size effect in sedimentary heavy metal records, where magnetic minerals are not subject to significant post-depositional alteration.     

Insights about the biosynthesis of the avermectin deoxysugar L-oleandrose through heterologous expression of Streptomyces avermitilis deoxysugar genes in Streptomyces lividans.

BACKGROUND: The avermectins, produced by Streptomyces avermitilis, are potent anthelminthic agents with a polyketide-derived macrolide skeleton linked to a disaccharide composed of two alpha-linked L-oleandrose units. Eight contiguous genes, avrBCDEFGHI (also called aveBI-BVIII), are located within the avermectin-producing gene cluster and have previously been mapped to the biosynthesis and attachment of thymidinediphospho-oleandrose to the avermectin aglycone. This gene cassette provides a convenient way to study the biosynthesis of 2,6-dideoxysugars, namely that of L-oleandrose, and to explore ways to alter the biosynthesis and structures of the avermectins by combinatorial biosynthesis. RESULTS: A Streptomyces lividans strain harboring a single plasmid with the avrBCDEFGHI genes in which avrBEDC and avrIHGF were expressed under control of the actI and actIII promoters, respectively, correctly glycosylated exogenous avermectin A1a aglycone with identical oleandrose units to yield avermectin A1a. Modified versions of this minimal gene set produced novel mono- and disaccharide avermectins. The results provide further insight into the biosynthesis of L-oleandrose. CONCLUSIONS: The plasmid-based reconstruction of the avr deoxysugar genes for expression in a heterologous system combined with biotransformation has led to new information about the mechanism of 2,6-deoxysugar biosynthesis. The structures of the di-demethyldeoxysugar avermectins accumulated indicate that in the oleandrose pathway the stereochemistry at C-3 is ultimately determined by the 3-O-methyltransferase and not by the 3-ketoreductase or a possible 3,5-epimerase. The AvrF protein is therefore a 5-epimerase and not a 3,5-epimerase. The ability of the AvrB (mono-)glycosyltransferase to accommodate different deoxysugar intermediates is evident from the structures of the novel avermectins produced.