Enhancing low-temperature energy harvesting by lead-free ferroelectric Ba(Zr0.1Ti0.9)O3

The energy-harvesting ability of the lead-free ferroelectric Ba(Zr,Ti)O₃ was investigated and greatly enhanced using the Kim novel electrothermodynamic cycle for low-temperature application. Ba(Zr,Ti)O₃ was synthesized with a Zr:Ti ratio of 10:90 (BZT10) by hot-press sintering, which exhibited a mix relaxor-ferroelectric behavior. For power generation using the Kim cycle with low and high temperatures of T_L = 25°C, T_H = 120°C, the most optimized temperature pattern occurred for a heating time of 12.5 s and a cooling time of 22.5 s. Under these conditions, the electric field increased during the novel isodisplacement process, and the displacement variation in the isoelectric step reached the highest value and maximized the BZT10 cycle loop area. Applying these conditions while lowering T_L to 20°C, an energy density N_D = 504 mJ/cm³ was achieved. This value is the highest obtained energy density in a practical test for lead-free ferroelectric bulk material in the BaTiO₃ family.     

Effect of microstructures on dielectric breakdown strength of sintered reaction-bonded silicon nitride ceramics

Silicon nitride (Si₃N₄) was prepared from silicon by a sintered reaction-bonded silicon nitride method using yttria and magnesia as sintering additives. Post-sintering (PS) of nitrided compacts was carried out at 1850°C under a nitrogen pressure of 1 MPa. Effect of PS time on microstructure and dielectric breakdown strength (DBS) of the prepared Si₃N₄ ceramics was evaluated. The DBS was measured using specimens with four different thicknesses (0.30, 0.20, 0.10, and 0.05 mm) in order to examine the thickness dependence. The porosity of the sintered Si₃N₄ decreased by prolonging the PS time, and the full density could be achieved at the PS time of over 6 h. After full densification, rod-like β-Si₃N₄ grains grew up, and their maximum grain size increased from 45.1 to 154.7 μm by prolonging the PS time from 6 to 48 h. The DBS of the thick Si₃N₄ substrates (0.30 mm) showed little variation from 35.4 to 47.0 kV/mm, regardless of the PS time. On the other hand, that of the thin ones (0.05 mm) dramatically decreased from 99.5 to 9.8 kV/mm with increased the PS time from 6 to 48 h. Because the DBS sharply decreased at the thin substrate sintered for longer time in which some large-elongated grains might span the substrate thickness-wise throughout, it was inferred that the interface between β-Si₃N₄ grains and grain boundary phase/intergranular glassy films might be a path of the dielectric breakdown.     

Fractionation and enrichment of CLA isomers by selective esterification with Candida rugosa lipase

A commercial product of CLA contains almost equal amounts of cis-9,trans-11 (c9,t11)-CLA and trans-10,cis-12 (t10,c12)-CLA. We attempted to enrich the two isomers by a two-step selective esterification using Candida rugosa lipase that acted on c9,t11-CLA more strongly than on t10,c12-CLA. An FFA mixture containing CLA isomers was esterified with an equimolar amount of lauryl alcohol in a mixture of 20% water and the lipase. When the esterification of total FA reached 50%, two isomers were fractionated in a good yield: t10,c12-CLA was enriched in FFA, and c9,t11-CLA was recovered in lauryl esters. The FFA were esterified again to enrich t10,c12-CLA. At 27.3% esterification of total FA, the t10,c12-CLA content in FFA increased to 64.8 wt% with 89.3% recovery: The ratio of the content of t10,c12-CLA to that of two isomers was 95.9%. Lauryl esters obtained by the single esterification were employed for enrichment of c9,t11-CLA. After the esters were hydrolyzed, the resulting FFA were esterified again with lauryl alcohol. At 62.0% esterification of total FA, the c9,t11-CLA content in lauryl esters increased to 73.3 wt% with 79.4% recovery: The ratio of the content of c9,t11-CLA to that of two isomers was 95.6%. In a 600-g-scale purification, molecular distillation was effective in separating the reaction mixture into lauryl alcohol, FFA, and lauryl ester fractions.     

Preparation, Structure, and Properties of Thermally and Mechanically Improved Aluminum Titanate Ceramics Doped with Alkali Feldspar

Aluminum titanate (AT) ceramic materials doped with alkali feldspar ((Na_0.6K_0.4)AlSi₃O₈) have been prepared. These ceramics exhibited high sinterability, large resistance to thermal decomposition, and large flexure strength. The existence of liquid-phase feldspar at sintering temperatures promoted the formation of AT ceramics as the sintering agent. It was considered that silicon ions substituting for aluminum ions at the surface of AT crystal grains lowered the surface energy and hindered the diffusion of Ti⁴⁺ and Al³⁺, giving rise to the large resistance to thermal decomposition. As a result, doping with alkali feldspar was found to effectively improve the mechanical and thermal properties of AT ceramics.     

Pulsed Electric Current Sintering of Silicon Nitride

Pulsed electric current sintering (PECS) has been used to densify α-Si₃N₄ powder doped with oxide additives of Y₂O₃ and Al₂O₃. A full density (>99%) was achieved with virtually no transformation to β-phase, resulting in a microstructure with fine equiaxed grains. With further holding at the sintering temperature, the α-to-β phase transformation took place, concurrent with an exaggerated grain growth of a limited number of elongated β-grains in a fine-grained matrix, leading to a distinct bimodal grain size distribution. The average grain size was found to obey a cubic growth law, indicating that the growth is diffusion-controlled. In contrast, the densification by hot pressing was accompanied by a significant degree of the phase transformation, and the subsequent grain growth gave a broad normal size distribution. The apparent activation energy for the phase transformation was as high as 1000 kJ/mol for PECS, almost twice the value for hot pressing (∼500 kJ/mol), thereby causing the retention of α-phase during the densification by PECS.     

Effect of polymer density on polyethylene hollow fiber membrane formation via thermally induced phase separation

Microporous high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) hollow fiber membranes were prepared from polyethylene–diisodecyl phthalate solution via thermally induced phase separation. Effect of the polyethylene density on the membrane structure and performance was investigated. The HDPE membrane showed about five times higher water permeability than the LDPE membrane because it had the larger pore and the higher porosity at the outer membrane surface. The formation of the larger pore was owing to both the initial larger structure formed by spinodal decomposition and the suppression of the diluent evaporation from the outer membrane surface due to the higher solution viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 471–474, 2004     

EFFECTS OF OPERATIONAL CONDITIONS ON DRYING CHARACTERISTICS IN CLOSED SUPERHEATED STEAM DRYING

The effects of operational conditions on the drying performance in closed superheated steam drying were examined theoretically and experimentally. The vapor generated from the sample was circulated in the drying chamber. In the theoretical analysis, the replacement of air with vapor in drying chamber and the convective vapor transfer in sample were considered. At the start of drying, the drying chamber was filled with air. As the drying proceeded, the air was replaced with the vapor generated from sample. The calculated results explained the characteristics of experimental data. The pore diameter of sample had little effect on the drying characteristics. During the internal evaporation period, the evaporation occurred in the narrow zone, which moved from the surface to the bottom of sample. The convective vapor transfer in sample had a significant influence on the drying performance. The excess increments in temperature and velocity of drying gas hardly contributed to shortening the drying time.     

EFFECT OF FLUIDIZING PARTICLE ON DRYING CHARACTERISTICS OF POROUS MATERIAL IN FLUIDIZED BED

The drying characteristics of porous material in fluidized bed were examined theoretically and experimentally. The brick ball was used as the sample and immersed in the fluidized bed. The glass beads were used as the fluidizing particles and the particle diameters were changed. When the pore diameter of sample was relatively large, the fluidizing particles were adhered on the sample surface. In the theoretical analysis, the heat and mass transfers in adhered particle layer were considered. The fluidizing particles were adhered on the sample surface during the earlier period of drying. The sample temperature largely decreased when the mass of adhered particle decreased. The calculated results are in good agreement with experimental data. The diameter of fluidizing particle had a small effect on the drying time. The excess increments in drying gas temperature hardly contributed to shortening the drying time.     

Thermal Decomposition of Titanium Alkoxide and Silicate Ester in Organic Solvent: A New Method for Synthesizing Large-Surface-Area, Silica-Modified Titanium(IV) Oxide of High Thermal Stability

Silica-modified titanium oxide (S-TiO₂) powders that have an anatase structure were synthesized via the thermal decomposition of mixtures of titanium(IV) isopropoxide (TIP) and tetramethyl orthosilicate (TMOS) in toluene at 300°C. These S-TiO₂ materials had high rutile-transformation temperatures and maintained large surface areas at elevated temperatures (550°–1000°C). For example, the product that was prepared from a 9:1 TIP:TMOS mixture transformed to rutile at ∼1100°C and possessed a surface area of 160 m²/g, even after calcination at 800°C for 1 h.     

Effect of Coarse-Powder Portion on Abnormal Grain Growth during Hot Pressing of Commercial-Purity Alumina Powder

By classification, two powder portions, one consisting of coarse particles and the other consisting of fine particles, were separated from a MgO-doped (1000 ppm) commercial-purity Al₂O₃ powder. Examinations of microstructure evolution during hot pressing showed that extensive abnormal grain growth occurred for the coarse portion. For the fine portion, although there was an indication that grain-size distribution deviated from normal distribution on prolonged hot pressing, such extensive abnormal grain growth did not occur. Extensive abnormal grain growth also occurred when the coarse portion was mixed into a high-purity powder that exhibited no abnormal grain growth alone. Chemical analyses revealed that the coarse portion contained the higher concentration of impurities but lower concentration of magnesium than the fine portion. It was discussed that particle aggregates in the coarse portion might have been responsible for the higher concentration of impurities but lower concentration of magnesium and, thus, for the extensive abnormal grain growth.