Synthesis and characterization of a positive‐working,aqueous‐base‐developable photosensitive polyimide precursor

A positive‐working, aqueous‐base‐developable photosensitive polyimide precursor based on poly(amic ester)‐bearing phenolic hydroxyl groups and a diazonaphthoquinone photosensitive compound was developed. The poly(amic ester) was prepared from a direct polymerization of 2,2′‐bis‐(3‐amino‐4‐hydroxyphenyl)hexafluoropropane and bis(n‐butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. Subsequently, the thermal imidization of the poly(amic ester) precursor at 300°C produced the corresponding polyimide. The inherent viscosity of the precursor polymer was 0.23 dL/g. The cyclized polyimide showed a glass‐transition temperature at 356°C and a 5% weight loss at 474°C in nitrogen. The structures of the precursor polymer and the fully cyclized polymer were characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. The photosensitive polyimide precursor containing 25 wt % diazonaphthoquinone photoactive compound showed a sensitivity of 150 mJ/cm² and a contrast of 1.65 in a 3 μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 10 μm was obtained from this composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 352–358, 2002     

Particle motion in the fountain flow region during filling of a tube with a viscoelastic fluid

We present the results of an investigation of particle motion behind the advancing free surface during the filling of an initially empty tube with a viscoelastic fluid. Particle motion in the vicinity of an advancing free surface (the fountain flow region) is of significance in a number of processes used to form composite materials, notably injection and compression molding. This motion determines, to a large extent, the distribution of the reinforcing phase in the molded part. We show experimentally that an isolated spherical particle moves behind the interface in characteristic orbits, remaining in close proximity to the advancing free surface. This is in stark contrast to what happens in a Newtonian fluid. In that case, the particle is deposited on the tube walls by the fountain flow and never again reaches the faster moving free surface. The particle motion behind the interface is modeled with a combination of equations that describe the advection of the particle due to convective/fountain flow and its lateral migration due to viscoelasticity. This model neglects the finite size of the particle and is thus unable to capture the full details of the observed motion. However, the qualitative agreement between the experimental results and the modeling predictions suggests that the observed particle motion is the result of the combined effect of viscoelasticity and fountain flow.     

Structure-function studies of an IGF-I analogue that can be chemically cleaved to a two-chain mini-IGF-I

The structure and biological activities of two disulphide isomersof a C-region deletion mutant of insulin-like growth factor-I(IGF-I) which has an Asn–Gly link engineered at the junctionof the A- and B-regions were studied before and after chemicalcleavage. Circular dichroism (CD) spectra and binding affinityto IGF binding protein 3 (IGFBP3) indicated that the treatmentwith hydroxylamine did not disrupt the overall tertiary foldof the hormones. Cleavage restored some binding affinity forthe IGF-I receptor in both isomers and weakly restored the abilityto stimulate incorporation of tritiated thymidine into DNA inNIH 3T3 fibroblasts transfected with the human IGF-I receptor.Cleavage also restored metabolic capacity, as measured by theability of the isomers to promote lipogenesis in isolated ratadipocytes through the insulin receptor. These results are consistentwith the theory that binding of IGF-I to the IGF-I receptorrequires a conformational change similar to that involved ininsulin binding the insulin receptor. The weak affinity forthe IGF-I receptor after cleavage is consistent with the beliefthat residues in the C-region interact with the IGF-I receptor.This structural difference between insulin and IGF-I gives eacha higher binding affinity for its own receptor.     

Devitrification Kinetics and Mechanism of K2O–CaO–SrO–BaO–B2O3–SiO2 Glass-Ceramic

The devitrification kinetics and mechanism of a low-dielectric, low-temperature, cofirable K₂O–CaO–SrO–BaO–B₂O₃–SiO₂ glass-ceramic have been investigated. Crystalline phases including cristobalite (SiO₂) and pseudowollastonite ((Ca,Ba,Sr) SiO₃) are formed during firing. Activation energy analysis shows that the nucleation of the crystalline phases is controlled by phase separation of the glass. The crystallization kinetics of both cristobalite and pseudowollastonite obey Avrami-like behavior, and the results show an apparent activation energy close to that of the diffusion of alkaline and alkali ions in the glass, suggesting that diffusion is rate limiting. The above conclusion is further supported by analysis of measured growth rates.     

The effect of various fire‐exposed surface dimensions on the spalling of concrete specimens

Concrete spalling due to fire exposure is often defined as the sudden detachment of fragments from a concrete surface. It can be quantified by various parameters of which weight loss and spalling depth are the most common ones. The risk of spalling is influenced by many factors such as concrete composition, heating rate and applied testing methods. A reduced scale testing method should be developed to analyse the spalling behaviour and to understand its effectiveness in more detail. As a subsection of this development, this study aimed to analyse the effect of different‐sized, circular heated areas in semi full‐scale fire tests. Therefore, vermiculite slabs with varying cut‐outs in their centre were placed between a specimen made of a spalling‐sensitive concrete and the combustion chamber. The combustion chamber was heated following a standard fire curve. Our experimental results show that the thermal expansion inside of equal‐sized specimens is strongly dependent on the size of the heated area. In addition, this area also affects thermal stresses. They decrease as a result of lower temperature gradients for tests with smaller unheated boundary areas. Apart from this, the analysis of fragments shows no correlation between their relative volume distribution and the heated area. Copyright © 2014 John Wiley & Sons, Ltd.     

Biological Evaluation and X‐ray Co‐crystal Structures of Cyclohexylpyrrolidine Ligands for Trypanothione Reductase,an Enzyme from the Redox Metabolism of Trypanosoma

The tropical diseases human African trypanosomiasis, Chagas disease, and the various forms of leishmaniasis are caused by parasites of the family of trypanosomatids. These protozoa possess a unique redox metabolism based on trypanothione and trypanothione reductase (TR), making TR a promising drug target. We report the optimization of properties and potency of cyclohexylpyrrolidine inhibitors of TR by structure‐based design. The best inhibitors were freely soluble and showed competitive inhibition constants (K_i) against Trypanosoma (T.) brucei TR and T. cruzi TR and in vitro activities (half‐maximal inhibitory concentration, IC₅₀) against these parasites in the low micromolar range, with high selectivity against human glutathione reductase. X‐ray co‐crystal structures confirmed the binding of the ligands to the hydrophobic wall of the “mepacrine binding site” with the new, solubility‐providing vectors oriented toward the surface of the large active site.     

Experimental study of the burner for FAA fire test: NexGen burner

The NexGen (Sonic) burner is the new burner developed by the Federal Aviation Administration, FAA, to replace old oil burners used for the required fire certification tests on power plant‐related materials, as it provides the capability to control both air and fuel flow rates. During a fire test, the burner is supposed to simulate a certain fire condition, so the flame properties should be robust and repeatable. The NexGen burner can achieve this due to the precise fuel and air controls. However, the current calibration criterion (ISO2685:1998 and AC20‐135) may not be good enough to ensure consistent flame properties. In the presented work, the sensitivity of the burner performance to air and fuel flow rate, as measured by the temperature and heat flux for calibration purposes, was studied. Additionally, the influence of the turbulator and the thermocouple size used for flame calibration was also studied. The impact of varying fuel/air ratio and thermocouple sizes was studied by conducting fire tests on aluminum samples, to show the inadequacies in the current calibration standards.     

Three-dimensional microstructural changes in the Ni–YSZ solid oxide fuel cell anode during operation

Microstructural evolution in solid oxide fuel cell (SOFC) cermet anodes has been investigated using X-ray nanotomography along with differential absorption imaging. SOFC anode supports composed of Ni and yttria-stabilized zirconia (YSZ) were subjected to extended operation and selected regions were imaged using a transmission X-ray microscope. X-ray nanotomography provides unique insight into microstructure changes of all three phases (Ni, YSZ, pore) in three spatial dimensions, and its relation to performance degradation. Statistically significant 3D microstructural changes were observed in the anode Ni phase over a range of operational times, including phase size growth and changes in connectivity, interfacial contact area and contiguous triple-phase boundary length. These observations support microstructural evolution correlated to SOFC performance. We find that Ni coarsening is driven by particle curvature as indicated by the dihedral angles between the Ni, YSZ and pore phases, and hypothesize that growth occurs primarily by means of diffusion and particle agglomeration constrained by a pinning mechanism related to the YSZ phase. The decrease in Ni phase size after extended periods of time may be the result of a second process connected to a mobility-induced decrease in the YSZ phase size or non-uniform curvature resulting in a net decrease in Ni phase size.     

Oxidation with air of cyclohexanone to carboxylic diacids on carbon catalysts

Carbons derived from phenolic resins were used as catalysts for the aqueous phase oxidation of cyclohexanone at 140°C under air pressure. The reaction yielded mainly adipic, glutaric and succinic acids. The samples were modified by heat treatments in CO₂, air or N₂ at different temperatures and characterized to determine their surface area and porosity and to evaluate the functional groups on the surface. Treatments under CO₂ or air increased the oxidation activity. The selectivity to adipic acid was maximum (33%) after activation in air which greatly increased the surface concentration of oxygen-containing functional groups. However, it was not possible to attribute the selectivity to specific acidic, neutral or basic groups present at the surface of carbons. This revised version was published online in June 2006 with corrections to the Cover Date.