Masao Fukusumi

Synthesis of positively charged calcium hydroxyapatite nano-crystals and their adsorption behavior of proteins.

Positively charged Hap nano-crystals were prepared by using beta-alanine and clarified the adsorption affinity of these surface amide functionalized Hap nano-crystals to proteins. Colloidal surface amide functionalized Hap nano-crystals were prepared by wet method in the presence of various amounts of beta-alanine by changing molar ratio of beta-alanine/Ca (beta/Ca ratio) in the solution. The rod-like nano-crystals were lengthened with addition of beta-alanine though their width did not vary; carboxyl groups of beta-alanine are strongly coordinated to Ca2+ ions exposed on ac and/or bc faces to inhibit particle growth to a- and/or b-axis directions and enhance the particle growth along to the c-axis. No difference can be recognized on the crystal structure among the synthesized Hap nano-crystals by XRD measurements. However, the large difference was recognized by TG-DTA and FTIR measurements. Those measurements revealed that beta-alanine is incorporated on the Hap nano-crystal surface up to the beta/Ca ratio of 1.0, though they are absent in the nano-crystals synthesized at beta/Ca ratio > or = 2.0. The zeta potential (zp) of beta-alanine-Hap nano-crystals prepared at beta/Ca = 0.4 and 1.0 of those incorporating beta-alanine exhibited positive charge at pH < or = 5.9. The saturated amounts of adsorbed BSA for the positively charged beta-alanine-Hap nano-crystals were increased 2.3-2.4-fold by their electrostatic attraction force between positively charged beta-alanine-Hap nano-crystals and negatively charged BSA molecules. We were able to control the adsorption affinity of Hap nano-crystal by changing their surface charge.

Effects of Modification of Calcium Hydroxyapatites by Trivalent Metal Ions on the Protein Adsorption Behavior

The effects of modification of calcium hydroxyapatites (Hap; Ca10(PO4)6(OH)2) by trivalent metal ions (Al(III), La(III), and Fe(III)) on protein adsorption behavior were examined using bovine serum albumin (BSA; isoelectric point (iep) = 4.7 and molecular mass (M(s)) = 67,200 Da). The Al(III)-, La(III)-, and Fe(III)-substituted Hap particles were prepared by the coprecipitation method with different atomic ratios, metal/(Ca + metal), abbreviated as X(metal). The particles precipitated at X(metal) = 0 (original-Hap) were rod-like and 10 x 36 nm2 in size. The short, rod-like original-Hap particles were elongated upon adding metal ions up to X(metal) = 0.10, and the extent of the particle growth was in the order of La(III) < Al(III) << Fe(III). The crystallinity of the materials was slightly lowered by increasing X(metal) for all systems. The adsorption isotherms of BSA onto the Al(III)-, La(III)-, and Fe(III)-substituted Hap particles showed the Langmuirian type. The saturated amounts of adsorbed BSA (n(s)(BSA)) values were strongly dependent on X(metal) in each system. The n(s)(BSA) values for the Fe(III)-substituted Hap system were increased with an increase in X(Fe) (X(metal) value of Hap particles substituted with Fe(III)); the n(s)(BSA) value obtained at X(Fe) = 0.10 was 2.7-fold more than that for the original-Hap particle, though those for the La(III) system were decreased to ca. 1/5. On the other hand, the n(s)(BSA) values for the Al(III) system were decreased with substitution of small amounts of Al(III), showing a minimum point at X(Al) = 0.01, but they were increased again at X(Al) over 0.03. Since the concentrations of hetero metal ions dissolved from the particles exhibited extremely low values, the possibility of binder effects of trivalent cations dissolved from the particle surface for adsorbing BSA to trivalent-ion-substituted Hap particles was excluded. The increase of n(s)(BSA) by an increase in X(Fe) was explained by elongation of mean particle length along with the production of surface hydroxo ions, such as Fe(OH)2+ or Fe(OH)2+, to induce the hydrogen bond between the Fe(III)-substituted Hap surface and BSA molecules, though the number of original C sites established by Ca(II) atoms was reduced. In the case of La(III)-substituted Hap particles, the number of original C sites established by Ca(II) atoms was reduced by La(III) substitution but the mean particle length remained almost constant. Furthermore, surface hydroxo La(III) groups were absent. Therefore, the reduction of n(s)(BSA) was explained by both the unaltered mean particle length and their low surface hydrophilicity. The change of n(s)(BSA) values by X(Al) resembled that of the mean particle length. These results implied that both the mean particle length and surface hydrophilicity of Al(III)-, La(III)-, and Fe(III)-substituted Hap particles are determining factors of the adsorption amounts of BSA.

Effects of Heat Treatment of Calcium Hydroxyapatite Particles on the Protein Adsorption Behavior

The effects of heat treatment of calcium hydroxyapatite (Hap) on the protein adsorption behavior were examined using typical proteins of bovine serum albumin (BSA: isoelectric point (iep) = 4.7, molecular mass (Ms) = 67,200 Da, acidic protein), myoglobin (MGB: iep = 7.0, Ms = 17,800 Da, neutral protein), and lysozyme (LSZ: iep = 11.1, Ms = 14,600 Da, basic protein). The TEM, XRD, and gas adsorption measurements ascertained that all of the Hap particles examined were highly crystallized and nonporous. The Hap single phase was continued up to the heat treatment temperature of 600 degrees C. However, after treatment above 800 degrees C in air, the beta-Ca3(PO4)2 (beta-TCP) phase slightly appeared. TG and ICP-AES measurements suggested that all of the Hap particles are Ca2+-deficient. Also, it was indicated from FTIR and XPS measurements that a partially dehydrated oxyhydroxyapatite (pd-OHap) was formed after treatment at high temperature. The saturated amounts of adsorbed BSA (nsBSA) did not vary on the Hap particles after heat treatment at 200 and 400 degrees C. However, nsBSA values were increased by raising the heat treatment temperature above 600 degrees C. The adsorption coverage of BSA was increased up to ca. 1.4. This adsorption coverage of BSA (thetaBSA) over unity suggests that the BSA molecules densely adsorbed and a part of BSA molecules adsorbed as end-on type on the Hap particle surface or BSA molecules became contracted. Similar adsorption behavior was observed on the LSZ system, but the adsorption coverage of LSZ (thetaLSZ) values are much less than thetaBSA. On the other hand, no effect of the heat treatment of Hap particles was observed on the adsorption of MGB. The increases of nsBSA and nsLSZ were explained by the increase of calcium and phosphate ions in the solutions dissolved from beta-TCP formed after heat treatment of Hap, especially treated at high temperature. The dissolved Ca2+ and PO(4)3 - ions may act as binders between proteins and Hap surfaces; the adsorption of Ca2+ ions on the Hap surface offers an adsorption site for BSA owing to its positive charge. In the case of adsorption of positively charged LSZ molecules, PO43- ions act as a binder in an opposite way. Since the MGB molecules are neutral, no binding effect of either ion was observed.

Tension-Compression Asymmetry Under Superplastic Flow in Magnesium Alloys

Superplastic magnesium alloys prepared by ingot metallurgy and powder metallurgy were processed and characterized. By performing uniaxial tension and compression tests of the extruded alloys along the longitudinal direction, it was found that both alloys were highly symmetric at low-strain rates within the superplastic regime. However, near the maximum strain rate within the superplastic regime, the symmetric flow disappeared. Specifically, the flow stress in early deformation under tension was slightly lower than that under compression, and the strain hardening under tension was higher than that under compression. The asymmetry was explained using the hypothesis that grain-boundary sliding under tension is easier than under compression. As indirect evidence for easier grain-boundary sliding under tension, it was shown that the coarsened intergranular precipitates tended to agglomerate on grain boundaries experiencing a tensile stress.

Control of the Morphology and Porosity of Hematite Particles through the Use of Tannic Acids

The shape and porosity of hematite particles formed from the forced hydrolysis of acidic FeCl3 solutions could be controlled by the use of two types of tannic acid (hydrolysable and non-hydrolysable) within the concentration range 0–2 × 10−2 wt%. The system with hydrolysable tannic acid (AL) initially provided quite small spherical particles at concentrations up to 10−2 wt% and finally irregular small hematite particles at 2 × 10−2 wt%. In the system with condensed non-hydrolysable tannic acid (KT), on the other hand, the hematite particles became ellipsoidal in shape at concentrations above10−2 wt%. The formation of ellipsoidal particles was explained by the adsorption of KT molecules onto the growing polynuclear primary particles. TEM and XRD measurements revealed that all the hematite particles produced from FeCl3/HCl solutions with tannic acids are polycrystalline. The rate of phase transformation from β-FeOOH to hematite was accelerated as the concentration of AL increased, whereas no significant change was observed for the KT system. Analysis by t-plots revealed that the porosity of the hematite particles changed from mesoporous to microporous when the concentration of AL increased. In contrast, the presence of very low amounts of KT molecules (10−5 and 10−4 wt%) produced non-porous hematite particles via strong aggregation of polynuclear (PN) particles by hydrogen bonding between hydroxy and carboxy groups. Not only the morphology but also the pore size of hematite particles was controlled from non-porous to mesoporous by using different kinds of tannic acids.

Microstructural Evolution of Body-Centred Cubic Fe-Al Alloy by Friction Stir Processing with SiC Particles Addition

The surface of body-centred cubic Fe-7Al (mass%) alloy plate was successfully modified by friction stir processing with SiC particles addition. The stir zone with SiC addition had an average grain size of 5.9 μm, smaller than that of 10.1 μm in the stir zone without SiC addition. SiC particles introduced by friction stir processing were converted to fine Fe3AlCx particles by reaction with the ferrite matrix. The hardness near the surface of the stir zone was significantly increased to 351 HV by introduction of particles, compared to the hardness of 200 HV in the stir zone without particles addition. The dispersed particles also contributed to suppression of grain growth of the matrix at elevated temperature.

Nanostructurization of Magnesium Alloy via Friction Stir Lap Processing

Friction stir processing (FSP) in a lap configuration of a metal sheet and an alloy plate has been examined to produce surface alloy layer with nanostructures. The 1-pass friction stir lap processing (FSLP) over 0.5 mm-thick Cu sheet on an AZ91 substrate produced multilayer structure with nanograins and/or nanoprecipitates in each layer, but the structure distributed only partially in the stir zone (SZ). Through the 3-pass FSLP along the same line, the multilayer structure has disappeared and the fine structure with precipitates in size ranging from several 100 nanometer to 3 micrometer has yielded among the entire SZ. 2-dimensional microhardness mapping have shown that the standard deviation of microhardness values in the SZ has decreased by half from 1-pass to 3 pass FSLP. Homogeneous microstructure involving nanostructures has been successfully produced via multi-pass FSLP.

Corrosion resistance of ultrasonic soldered aluminium joint using Zn-based solder alloy

In order to obtain high strength aluminium butt joints with high corrosion resistance, ultrasonic soldering of 1070 and 5056 rods was conducted using quasi-melting Zn–18Sn (mass%) alloy and Zn–38A1 alloy. Ultrasonic vibrations were applied at soldering temperature ranging 533–723 K through aluminium rods without using of a solder bath. To evaluate the corrosion resistance of solder joints, tensile tests were conducted after immersion in a 5% NaCl aqueous solution. Though joint strength decreased with an increase in immersion time in the NaCl aqueous solution because of corrosion in the joints, corrosion resistance of 5056 joints with Zn–38A1 alloy was higher than that of joints with Zn–18Sn alloy irrespective of aluminium base material. The strength of joints with Zn–18Sn alloy rapidly decreased by immersion in the NaCl aqueous solution. In these joints, corrosion occurred locally in the soldered interface. Corrosion potential of these joints was unusually lower than that of the solder alloy. In contrast, corrosion occurred slowly in the solder layer in 5056 joints with Zn–38A1 alloy. Corrosion potential of the joints was equivalent to that of the solder alloy.

Microstructural Evaluation of Friction Stir Processed D2 Tool Steel

Modification of AISI D2 tool steel was conducted by friction stir processing (FSP). Effects of tool rotational speed on microstructural evolution and mechanical properties were investigated. Though coarse primary carbides in the size of 10-50 m were observed before FSP, fine carbides smaller than 20 m and martensitic matrix with fine grains were obtained after FSP. High hardness of over 900 HV, higher than the hardness in conventional D2 tool steel, was achieved under the condition of moderate rotational speed.

Strength and corrosion resistance of a solder joint in ultrasonic soldering of aluminium using quasi-melting solder

In order to obtain high-strength aluminium butt joints with corrosion resistance, ultrasonic soldering of A1070 rods was conducted using quasi-melting Sn–xZn (x = 23, 40, 82 mass%) hypereutectic alloy. Ultrasonic vibrations were applied at soldering temperatures ranging 220–300°C through A1070 rods without a solder bath. The tensile strength of the solder joints with Sn–23Zn or 40Zn alloy were higher than that of the joint soldered with Sn–9Zn eutectic alloy. The joints soldered with Sn–23Zn or 40Zn alloy showed the same strength as A1070 rods which employed the same heat treatment as the ultrasonic soldering process. The thickness of the hypereutectic solder layer in the joints was thicker than that of the Sn–9Zn solder layer because unmelted α-Zn solid solution should have prevented the solder from being pressed out of the joint gap by the applied pressure during soldering. Tensile tests of the joints after immersion in NaCl aqueous solution revealed that the corrosion resistance of the joints soldered with hypereutectic alloy was higher than that of the joint soldered with Sn–9Zn alloy. It is considered that the improvement was achieved by the thick hypereutectic solder layer which should have reduced the notch effect in the joints.