Distribution of carbon contamination in MgAl2O4 spinel occurring during spark-plasma-sintering (SPS) processing: I – Effect of heating rate and post-annealing

Carbon contamination from the carbon paper/dies during spark-plasma-sintering (SPS) processing was examined in the MgAl₂O₄ spinel. The carbon contamination sensitively changes with the heating rate during the SPS processing. At the high heating rate of 100 °C/min, the carbon contamination having organized structures occurred over almost the entire area from the surface to deep inside the SPSed spinel disk. In contrast, at the slow heating rate of 10 °C/min, the carbon contamination having disordered structures occurred only around the surface area. The carbon phases transform into high pressure CO/CO₂ gases by post-annealing in air and lead to pore formation along the grain junctions. The pore formation significantly occurs at the high heating rate due to the large amount of the contaminant carbon phases. This suggests that if once the carbon contamination was formed in the materials, it is very difficult to remove the carbon phases from the materials.     

The effect of permanent dipole moments of adsorbates upon I-V characteristics of a bilayer tunneling junction between self-assembled monolayers on an Au(111) substrate and a gold tip

It is important to understand an electronic property of an interface between an organic material and a metal electrode. In the present work, we measured current-voltage (I-V) curves of self-assembled monolayers (SAMs) on Au(111) using a conducting atomic force microscope (AFM) with chemically modified Au-coated AFM tips. This contact resulted in a bilayer junction between the Au(111) substrate covered with one SAM and the Au-coated tip with the other SAM. An alkanethiol (octanethiol) and benzenemethanethiols with various terminal groups (-H, -CH(3), -Cl, -CF(3)) were used as the adsorbates. The shapes of the I-V curves depended on the terminal groups. This phenomenon was attributed to the change in the work function of gold due to different permanent dipole moments of the terminal groups.     

Genetically engineered brain drug delivery vectors: cloning, expression and in vivo application of an anti-transferrin receptor single chain antibodystreptavidin fusion gene and protein

A single chain Fv antibody–streptavidin fusion proteinwas expressed and purified from bacterial inclusion bodies followingcloning of the genes encoding the variable region of the heavychain and light chain of the murine OX26 monoclonal antibodyto the rat transferrin receptor. The latter undergoes receptormediated transcytosis through the brain capillary endothelialwall in vivo, which makes up the blood–brain barrier (BBB);therefore, the OX26 monoclonal antibody and its single chainFv analog may act as brain drug delivery vectors in vivo. Attachmentof biotinylated drugs to the antibody vector is facilitatedby production of the streptavidin fusion protein. The bi-functionalityof the OX26 single chain Fv antibody–streptavidin fusionprotein was retained, as the product both bound biotin and therat transferrin receptor in vitro and in vivo, based on pharmacokineticand brain uptake analyses in anesthetized rats. The attachmentof biotin–polyethyleneglycol–fluorescein to theOX26 single chain Fv antibody–streptavidin fusion proteinresulted in illumination of isolated rat brain capillaries inconfocal fluorescent microscopy. In conclusion, these studiesdemonstrate that genetically engineered single chain Fv antibody–streptavidinfusion proteins may be used for non-invasive neurotherapeuticdelivery to the brain using endogenous BBB transport systemssuch as the transferrin receptor.     

Effect of Ultrasonication on the Microstructure and Tensile Elongation of Zirconia-Dispersed Alumina Ceramics Prepared by Colloidal Processing

To obtain dense, fine-grained ceramics, fine particles and advanced powder processing, such as colloidal processing, are needed. Al₂O₃ and ZrO₂ particles are dispersed in colloidal suspensions by electrosteric repulsion because of polyelectrolyte absorbed on their surfaces. However, additional redispersion treatment such as ultrasonication is required to obtain dispersed suspensions because fine particles tend to agglomerate. The results demonstrate that ultrasonication is effective in improving particle dispersion in suspensions and producing a homogeneous fine microstructure of sintered materials. Superplastic tensile ductility is improved by ultrasonication in preparing suspensions because of the dense and homogeneous fine microstructure.     

Effect of stress wave shape on the crack propagation velocity in cyclic delayed failure

Crack propagation velocity in delayed failure under superposed repeating load, ($\text{d}\text{a/}\text{d}\text{t)}{}_{\mathrm{R}}$, was compared with that under static load, ($\text{d}\text{a/}\text{d}\text{t)}{}_{\mathrm{S}}$Two peaks appear on the relation between decreasing rate of crack propagation velocity, $\text{1-β = 1 ? (}\text{d}\text{a/}\text{d}\text{t))}{}_{\mathrm{R}}\text{/(}\text{d}\text{a/}\text{d}\text{t)}{}_{\mathrm{S}}$ and frequency, ?, both under sinusoidal and square load. By changing the ratio of holding time at maximum stress intensity factor to that at minimum stress intensity factor in square load, it was deduced that the existence of two peaks on the 1 ? β vs $\text{f}$ curve was caused by an asymmetric interaction between hydrogen atoms and cyclic moving of the position with triaxial tensile stress at crack tip. Moreover, the relation between 1 ? β and $\text{f}$ under the positive or negative saw tooth load could be well explained by the interaction model.     

Promotive effect of isopentane on cyclohexane isomerization catalyzed by sulfated zirconia

Cyclohexane isomerization to methylcyclopentane over sulfated zirconia is markedly enhanced in the presence of isopentane which acts as a hydride transfer agent to facilitate the slow step of hydride transfer from cyclohexane to isopropyl cation. This was revealed by deuterium tracer studies. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effects of heating rate on microstructure and transparency of spark-plasma-sintered alumina

Commercial alumina powder was densified by spark plasma sintering (SPS) at 1150 °C. During SPS processing, the effects of the heating rate were examined on microstructure and transparency. With decreasing heating rate, the grain size and the residual porosity decreased, while the transparency increased. At a heating rate of 2 °C/min, the grain size was 0.29 μm, and the in-line transmission was 46% for a wavelength of 640 nm. The mechanisms for the fine microstructure and low porosity at slow heating, which are conflicting with some existing results, were explained by considering the role of defect concentration and grain-boundary diffusion during densification.     

Coating of TiB2 dispersed Ti50Ni50 superelastic alloy layer onto Ti-6Al-4V alloy by spark and resistance sintering

The spark and resistance sintering (SRS) of a mixture of Ti, Ni, and TiB₂ powders was carried out to form a TiB₂ dispersed TiNi alloy layer onto a Ti-6Al-4V alloy substrate. The strength and delamination resistance of the surface layer were evaluated by three-point bending tests. The results showed that the bending strength of the specimen with the TiNi alloy surface layer without TiB₂ particles sintered at 1273 K was low because the crack initiation occurred at an early stage of loading in a thick interface layer containing brittle Ti-Ti₂Ni eutectic. By decreasing the sintering temperature to 1200 K, the bending strength increased and the crack initiation occurred from the surface because the interface layer was thin and did not contain the brittle Ti-Ti₂Ni eutectic. For the specimens with TiB₂ dispersed TiNi surface layer that was sintered at 1273 K, the bending strength was larger than that of the specimens with TiNi surface layer because the interface layer does not contain the Ti-Ti₂Ni eutectic and compressive residual stress generated in the surface layer during cooling process after SRS suppresses the crack initiation on the surface. The coating of TiB₂ dispersed TiNi alloy onto titanium alloys by SRS provides strong interface to prevent delamination of the surface layer, strong surface due to residual compressive stress, and wear-resistant surface due to the existence of hard TiB₂ particles and superelastic deformation of TiNi matrix.     

The effect of repeating load on the crack growth initiation and crack propagation in delayed failure

The delayed failure test under repeating load was carried out with pre-cracked specimen. The incubation time and the crack propagation rate were correlated with the stress intensity factor K.

The incubation time is decreased by the superposition of repeating load, as the range of stress intensity factor ΔK or the repeating frequency f increase. The reason can be explained by the promotion of corrosion reaction due to, e.g. the destruction of oxide film on the crack tip, which facilitates the invasion of hydrogen atoms into the material.

The crack propagation rate da/dt is decreased by the superposition of repeating load, and there exist two valleys of crack propagation rate minima on the da/dt vs f and da/dt vs ΔK curves. One valley corresponds to the interaction between the cyclic movement of the region with tri-axial tensile stress and the hydrogen atoms diffused from crack tip, which disturbs the concentration of hydrogen atoms. Another seems te correspond to the generation of retained compressive stress which reduces the effective stress intensity at crack tip and supresses the invasion and diffusion of hydrogen atoms.     

Doping amount and temperature dependence of superplastic flow in tetragonal ZrO2 polycrystal doped with TiO2 and/or GeO2

The doping amount and temperature dependence of superplastic flow in a TiO₂- and/or GeO₂-doped tetragonal ZrO₂ polycrystal (TZP) were investigated in the doping range of 0.2–8 mol.% and in the temperature range of 1200–1550 °C. While the tensile ductility in the TZP is significantly improved by the co-doping of TiO₂ and GeO₂, there is an optimum combination of doping amount and temperature for enhancing the tensile ductility. The present study also shows that the flow stress decreases with an increase in the doping amount, but this decrease levels off with a 2–3 mol.% addition of GeO₂ or (TiO₂–GeO₂). The data for the flow behavior and thermal groove experiment indicated that TiO₂ and/or GeO₂ doping enhances the grain boundary diffusion of zirconium cations and reduces the grain boundary energy, respectively. These effects of grain boundary segregation can be regarded as the cause of the improved high-temperature ductility of (TiO₂–GeO₂)-doped TZP.