Spiral Tunneling Cracks Induced by Environmental Stress Cracking in LaRC™-TPI Adhesives

Some currently-available formulations of LaRC?-TPI, a thermoplastic polyimide originally developed at NASA-Langley, were found to be highly susceptible to environmental stress cracking when exposed to solvents such as acetone, toluene, diglyme and methyl ethyl ketone. The combination of stress and solvent led to rapid cracking in films and adhesive layers of this material system. Residual cool-down stresses induced when the LaRC-TPI is used as an adhesive or coating led, in the presence of a solvent, to dense “mud crack” patterns which relieve a portion of the stored energy. Because these through-the-thickness cracks are not able to relieve the stored energy in the vicinity of the adherends, additional fractures in the form of curious spiral tunnel cracks initiated and grew inward within each adhesive fragment. Micrographs of the spiral fractures are given, along with a qualitative explanation for the failure process as observed in adhesives and coatings.     

Effects of static axial strain on the tensile properties and failure mechanisms of self-assembled collagen fibers

Collagen fibers form the structural units of connective tissue throughout the body, transmitting force, maintaining shape, and providing a scaffold for cells. Our laboratory has studied collagen self-assembly since the 1970s. In this study, collagen fibers were self-assembled from molecular collagen solutions and then stretched to enhance alignment. Fibers were tested in uniaxial tension to study the mechanical properties and failure mechanisms. Results reported suggest that axial orientation of collagen fibrils can be achieved by stretching uncrosslinked collagen fibers. Stretching by about 30% not only results in decreased diameter and increased tensile strength but also leads to unusual failure mechanisms that inhibit crack propagation across the fiber. It is proposed that stretching serves to generate oriented fibrillar substructure in self-assembled collagen fibers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1429–1440, 1997     

Soxhlet extraction of mucic acid from fungal biomass

Biologically produced mucic acid may form crystals before being separated from the biomass. Here we use Soxhlet extraction of fungal biomass to obtain mucic acid that was otherwise lost when separating biomass from the supernatant. Culture supernatant was used to extract the biomass, avoiding dilution of the mucic acid while retaining a cell-free suspension. Soxhlet extraction of biomass recovered 7% of total mucic acid produced at pH 4 and 24% at pH 6. The potential for mucic acid to cyclize to the 1,4-lactone was investigated by solid state NMR, confirming that very little lactone was present after the crystallization step.     

Recalibration of the Large Scale Gap‐Test to a Stress Scale

A series of gap‐test experiments were conducted in accordance with the EMTAP Test 22a guidelines to characterize the stress output from a donor charge of ROWANEX 3601. Forty eight successful gap‐tests were conducted at the University of Pardubice in addition to two supporting plate impact experiments performed at the Cavendish Laboratory, University of Cambridge. The experiments indicated that there are two principal release mechanisms, which produce the observed reduction in stress with increasing gap distance. The first is attenuation of the input wave, something which is expected during explosive loading due to the triangular nature of the loading pulse. The second is an interaction between the input wave and lateral release waves from the edges of the test sample at the measurement station. Attenuation of the input wave due to visco‐elastic loss in the PMMA “gap” used is likely to be less significant than these other two release mechanisms. The data generated by this investigation forms a robust dataset that gives an accurate calibration for ROWANEX 3601 for users of the EMTAP 22a test procedure. In addition the data represent an excellent “set problem” for those developing and wishing to validate, computational models of similar physical phenomena.     

Parametric study of a 2-d model of the nip region in a counter-rotating,non-intermeshing twin screw extruder

Within the polymer processing industry, the demand for more efficient mixing within the existing mixer geometries and keeping a tighter control over increasingly difficult applications calls for a quantitative understanding of the role of the mixer geometry on the mixing performance. An important extruder geometry to consider is the Counter-Rotating, Non-Intermeshing Twin Screw Extruder (CRTSE). Recent studies suggest that the greater than linear mixing performance in this geometry may be attributed to the flow in the nip region. Solution of the fluid dynamic equations for a 2-D model of the nip region was found in order to quantify mixing using a FEM software called FIDAP which was available to us on the CRAY X-MP supercomputer at San Diego Supercomputer Center. In order to study the effects of design parameters in the nip region, an arbitrary interface was placed in the entrance of the region. A program called “LINE” tracks the path and growth of the interface through the region. Measures of mixing are computed and compared. Effect of several design parameters on mixing performance are studied. Conclusions are presented as to the relative effect of various design parameters. Discussions regarding the measures of mixing and mixing efficiency are presented.     

Extraction and characterization of soluble protein fractions from Phaseolus lunatus L seeds

Legume proteins as a potential source of valuable nutrients, are the object of several studies in order to obtain the best use. A basic knowledge becomes more important for those proteins from species not wholly utilized, before using them as food ingredients. The objective of this work was to determine several structural and nutritional characteristics of the protein fractions from Phaseolus lunatus, separated in different solvents. The relative amount of extraction for the albumins (ALB), globulins (GLB), prolamines (PRL), and glutelins (GLT) was 62.3, 34.8, 1.4 and 1.5%, respectively. The SDS-PAGE electrophoretic profile of both ALB and GLB, showed seven common bands in intervals from 10 to 95 kDa, and 14 to 99 kDa, respectively; the amino acids profile showed that PRL was the rich fraction in sulfurated amino acids (11.5 g/100 g protein); the content of lysine in the fraction of ALB was smaller than expected but the requirement of the FAO in the fractions of GLB and GLT was covered. In general, the fraction of GLB had the best balance of amino acids and digestibility (80%); however, it had a relationship of calculated protein efficiency ratio (C-PER) of 0.11, smaller than the ratio in ALB (0.97). The calorimetric analysis showed denatured temperatures around 90 degrees C for the ALB, GLB, and GLU fractions. The PRL fraction probably did not present a thermal transition because the proteins were denaturalized by the extraction conditions.     

Disruption of ergosterol biosynthesis,growth, and the morphological transition in <Emphasis Type="Italic">Candida albicans</Emphasis> by sterol methyltransferase inhibitors containing sulfur at C-25 in the sterol side chain

The sterol substrate analog 25-thialanosterol and its corresponding sulfonium salt were evaluated for their ability to serve as antifungal agents and to inhibit sterol methyltransferase (SMT) activity in Candida albicans. Both compounds inhibited cell proliferation, were fungistatic, interrupted the yeastlike-form to germ-tube-form transition, and resulted in the accumulation of zymosterol and related Δ²⁴-sterols concurrent with a decrease in ergosterol, as was expected for the specific inhibition of SMT activity. Feedback on sterol synthesis was evidenced by elevated levels of cellular sterols in treated vs. control cultures. However, neither farnesol nor squalene accumulated in significant amounts in treated cultures, suggesting that carbon flux is channeled from the isoprenoid pathway to the sterol pathway with minor interruption or redirection until blockage at the C-methylation step. Activity assays using solubilized C. albicans SMT confirmed the inhibitors impair SMT action. Kinetic analysis indicated that 25-thialanosterol inhibited SMT with the properties of a time-dependent mechanismbased inactivator K _i of 5 =gmM and apparent k _inact of 0.013 min⁻¹, whereas the corresponding sulfonium salt was a reversible-type transition state analog exhibiting a K _i of 20 nM. The results are interpreted to imply changes in ergosterol homeostasis as influenced by SMT activity can control growth and the morphological transition in C. albicans, possibly affecting disease development.     

Thermochemical model on the carbothermal reduction of oxides during spark plasma sintering of zirconium diboride

Carbon was used to reduce oxides in spark plasma sintered ZrB₂ ultra-high temperature ceramics. A thermodynamic model was used to evaluate the reducing reactions to remove B₂O₃ and ZrO₂ from the powder. Powder oxygen content was measured and carbon additions of 0.5 and 0.75 wt% were used. A C–ZrO₂ pseudo binary diagram, ZrO₂–B₂O₃–C pseudo ternaries, and Zr–C–O potential phase diagrams were generated to show how the reactions can be related to an open system experiment in the tube furnace. Scanning transmission electron microscopy identified impurity phases composed of amorphous Zr–B–O with lamellar BN and a Zr–C–O ternary model was calculated under SPS sintering conditions at 1900°C and 6 Pa to understand how oxides can be retained in the microstructure.     

α-Alumina and spinel react into single-phase high-alumina spinel in <3 seconds during flash sintering

In situ X-ray diffraction measurements at the Advanced Photon Source show that α-Al₂O₃ and MgAl₂O₄ react nearly instantaneously and completely, and nearly completely to form single-phase high-alumina spinel during voltage-to-current type of flash sintering experiments. The initial sample was constituted from powders of α-Al₂O₃, MgAl₂O₄ spinel, and cubic 8 mol% Y₂O₃-stabilized ZrO₂ (8YSZ) mixed in equal volume fractions, the spinel to alumina molar ratio being 1:1.5. Specimen temperature was measured by thermal expansion of the platinum standard. These measurements correlated well with a black-body radiation model, using appropriate values for the emissivity of the constituents. Temperatures of 1600-1736°C were reached during the flash, which promoted the formation of alumina-rich spinel. In a second set of experiments, the flash was induced in a current-rate method where the current flowing through the specimen is controlled and increased at a constant rate. In these experiments, we observed the formation of two different compositions of spinel, MgO•3Al₂O₃ and MgO•1.5Al₂O₃, which evolved into a single composition of MgO•2.5Al₂O₃ as the current continued to increase. In summary, flash sintering is an expedient way to create single-phase, alumina-rich spinel.