On the effect of montmorillonite in the curing reaction of epoxy nanocomposites

The procedure for the fabrication of epoxy-based polymer layered silicate nanocomposites is important in respect of the nanostructure that is developed. To further our understanding of this, the influence of an organically modified clay (montmorillonite, MMT) on the curing kinetics of an epoxy resin has been studied by differential scanning calorimetry. Clay loadings of 10 and 20 mass% are used, and isothermal as well as dynamic cures have been investigated. For both cure schedules the effect of the MMT is to advance the reaction. Kinetic analysis yields values for the activation energy, but shows that the reaction cannot be described simply by the usual autocatalytic equation. The glass transition of the cured nanocomposites is lower than that for the cured neat resin, a result that is attributed to homopolymerisation taking place in addition to the epoxy–amine reaction.     

Cloning, sequencing, analysis, and heterologous expression of the fredericamycin biosynthetic gene cluster from Streptomyces griseus

Fredericamycin (FDM) A, a pentadecaketide featuring two sets of peri-hydroxy tricyclic aromatic moieties connected through a unique chiral spiro carbon center, exhibits potent cytotoxicity and has been studied as a new type of anticancer drug lead because of its novel molecular architecture. The fdm gene cluster was localized to 33-kb DNA segment of Streptomyces griseus ATCC 49344, and its involvement in FDM A biosynthesis was proven by gene inactivation, complementation, and heterologous expression experiments. The fdm cluster consists of 28 open reading frames (ORFs), encoding a type II polyketide synthase (PKS) and tailoring enzymes as well as several regulatory and resistance proteins. The FDM PKS features a KSalpha subunit with heretofore unseen tandem cysteines at its active site, a KSbeta subunit that is distinct phylogenetically from KSbeta of hexa-, octa-, or decaketide PKSs, and a dedicated phosphopantetheinyl transferase. Further study of the FDM PKS could provide new insight into how a type II PKS controls chain length in aromatic polyketide biosynthesis. The availability of the fdm genes, in vivo characterization of the fdm cluster in S. griseus, and heterologous expression of the fdm cluster in Streptomyces albus set the stage to investigate FDM A biosynthesis and engineer the FDM biosynthetic machinery for the production of novel FDM A analogues.     

Forces on a small grain in the nonlinear plasma wake of another

The transverse force on a spherical charged grain lying in the plasma wake of another grain is analyzed to assess the importance of ion-drag perturbation, in addition to the wake-potential-gradient. The ion-drag perturbation is intrinsically one order smaller than the wake-potential force in the ratio of grain size (r(p)) to Debye length (λ(De)). So ion-drag perturbation is important only in nonlinear wakes. Rigorous particle-in-cell calculations of the force are performed in the nonlinear regime with two interacting grains. It is found that even for quite large grains, r(p)/λ(De)=0.1, the force is dominated by the wake-potential gradient. The wake-potential structure can then help explain the preferred alignment of floating dust grains.     

Convergence of phase interfaces in the van der Waals-Cahn-Hilliard theory

We study the general asymptotic behavior of critical points, including those of non-minimal energy type, of the functional for the van der Waals-Cahn-Hilliard theory of phase transitions. We prove that the interface is close to a hypersurface with mean curvature zero when no Lagrange multiplier is present, and with locally constant mean curvature in general. The energy density of the limiting measure has integer multiplicity almost everywhere modulo division by a surface energy constant. Received March 16, 1999 / Accepted June 11, 1999     

Application of electromagnetic processing for development of high-performance sintered powder metal parts

Electromagnetic processing was used to study the effects of electro-magneto forming on the dimensional control and thermal stability of sintered powder metal (PM) parts. The investigation was carried out on sinter-hardened, low chromium-molybdenum bainitic steel. The results show an increase in the microhardness of about 14% for the electromagnetic processed parts compared to the as-sintered parts. This was attributed to the 2% increase in the density, 17% and 29% reduction in the volume fraction of porosity and width of the bainitic lath, respectively, due to the electromagnetic processing. Dimensional characterization was carried out using a vertically aligned push-rod dilatometer. After four thermal cycles of heating and cooling, at a controlled rate of 5 °C/min to 1000 °C, the electromagnetic processed parts exhibited reduced dimensional change of about 44% lower than for the as-sintered parts. This is significantly important for applications that demand high dimensional tolerance and performance, especially at elevated temperatures.     

Mode III effects on interface delamination

For crack growth along an interface between dissimilar materials the effect of combined modes I, II and III at the crack-tip is investigated. First, in order to highlight situations where crack growth is affected by a mode III contribution, examples of material configurations are discussed where mode III has an effect. Subsequently, the focus is on crack growth along an interface between an elastic-plastic solid and an elastic substrate. The analyses are carried out for conditions of small-scale yielding, with the fracture process at the interface represented by a cohesive zone model. Due to the mismatch of elastic properties across the interface the corresponding elastic solution has an oscillating stress singularity, and this solution is applied as boundary conditions on the outer edge of the region analyzed. For several combinations of modes I, II and III crack growth resistance curves are calculated numerically in order to determine the steady-state fracture toughness. For given values of K_I and K_II the minimum fracture toughness corresponds to K_III=0 in most of the range analyzed, but there is a range where the minimum occurs for a nonzero value of K_III.     

Neck propagation

Propagation of a neck along the length of a tensile specimen as occurs in certain polymeric materials and in a few metals is studied. Two material models are considered: a nonlinear elastic solid, and an inelastic flow theory solid with both rate-dependent and rate-independent behaviors. For the elastic solid the states ahead and behind the neck transition can be obtained fairly simply from just the jump conditions governing continuity of mass, momentum and energy. For the inelastic solid a full three-dimensional analysis must be performed to obtain the same information, and an analysis of axisymmetric neck propagation is carried out.     

Selective Alkylation of C‐Rich Bulge Motifs in Nucleic Acids by Quinone Methide Derivatives

A quinone methide precursor featuring a bis‐cyclen anchoring moiety has been synthesized and its capacity to alkylate oligonucleotide targets quantified in the presence and absence of divalent metal ions (Zn²⁺, Ni²⁺ and Cd²⁺). The oligonucleotides were designed for testing the sequence and secondary structure specificity of the reaction. Gel electrophoretic analysis revealed predominant alkylation of C‐rich bulges, regardless of the presence of divalent metal ions or even the bis‐cyclen anchor. This C‐selectivity appears to be an intrinsic property of the quinone methide electrophile as reflected by its reaction with an equimolar mixture of the 2′‐deoxynucleosides. Only dA‐N1 and dC‐N3 alkylation products were detected initially and only the dC adduct persisted for detection under conditions of the gel electrophoretic analysis.