Transient liquid phase sintering of high-purity mullite for high-temperature structural ceramics

High-purity mullite ceramics, promising engineering ceramics for high-temperature applications, were fabricated using transient liquid phase sintering to improve their high-temperature mechanical properties. Small amounts of ultrafine alumina or silica powders were uniformly mixed with the mullite precursor depending on the silica-alumina ratio of the resulting ceramics to allow for the formation of a transient liquid phase during sintering, thus, enhancing densification at the early stage of sintering and mullite formation by the reaction between additional alumina and the residual glassy phase (mullitization) at the final stage of sintering. The addition of alumina powder to the silica-rich mullite precursor resulted in a reaction between the glassy silica and alumina phases during sintering, thereby forming a mullite phase without inhibiting densification. The addition of fine silica powder to the mullite single-phase precursor led to densification with an abnormal grain growth of mullite, whereas some of the added silica remained as a glassy phase after sintering. The resulting mullite ceramics prepared using different powder compositions showed different sintering behaviors, depending on the amount of alumina added. Upon selecting an optimum process and the amount of alumina to be added, the pure mullite ceramics obtained via transient liquid phase sintering exhibited high density (approximately 99%) and excellent high-temperature flexural strength (approximately 320 MPa) at 1500 °C in air. These results clearly demonstrate that pure mullite ceramics fabricated via transient liquid phase sintering with compositions close to those of stoichiometric mullite could be a promising process for the fabrication of high-temperature structural ceramics used in an ambient atmosphere. The transient liquid phase sintering process proposed in this study could be a powerful processing tool that allows for the preparation of superior high-temperature structural ceramics used in the ambient processing atmosphere.     

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.     

Antitumor effect of DT-5461, a lipid A derivative, against human tumor xenografts is mediated by intratumoral production of tumor necrosis factor and affected by host immunosuppressive factors in nude mice

PURPOSE OF THE STUDY: The purpose of this report was to study the repercussions of rotator cuff condition on unconstrained shoulder arthroplasty results. METHODS: Between 1986 and 1993, 40 unconstrained shoulder prostheses were performed (24 total and 16 hemiarthroplasties). At the time of the operation, rotator cuff condition was reported to be normal in 15 shoulders, atrophic in 10, scarred in 3, torn in 12. Clinical and radiographical results were analyzed and supplemented with a rotator cuff echography. Postoperative follow-up averaged 42.25 months (12 to 97 months). RESULTS: When the rotator cuff was intact at the time of operation, clinical results were the best at the time of review. Constant score, overall mobility, forward elevation, external rotation with the elbow along the side were better for intact than for atrophic, scarred or torn rotator cuffs (p < 0.01). Ruptures repaired by local tissue transfer or trapezo deltoidal flap substitution (3 cases) gave satisfactory results, whereas two dacron cuff prostheses failed. In the non repaired ruptures (7 cases), arthroplasty resulted in 3/4 fair or poor results. At the time of review, the total incidence of postoperative rotator cuff tears was high (12 cases), functional repercussions were variable. Among the 15 rotator cuff tears observed at the time of the review, the long head of the biceps was present and in place in 9 cases and ruptured in 6 cases. In these latter cases, Constant score (p < 0.01), the forward elevation (p < 0.01), external rotation with elbow along side (p < 0.05) and overall mobility (p < 0.05) were worse; moreover, humeral head superior migration was greater (p < 0.01). DISCUSSION: Our study confirms the superiority of clinical results when the cuff was intact at the time of the operation. The repair of rotator cuff tears seems to be justified. When the rupture has not been repaired, clinical results were fair or poor in 5 cases out of 7, the initial rupture spread to the other tendons in 3 cases out of 7. Secondary ruptures were frequent (12 cases). No predictive factor was identified, but an overlapping of the greater tuberosity appears to be detrimental. Among rotator cuff tears present at the time of review, long head of the biceps rupture jeopardized clinical results and was associated with a proximal migration of the humeral head which was significantly more severe than with an intact non displaced long head of the biceps. CONCLUSION: During unconstrained shoulder prosthesis implantation, it is therefore recommend to systematically repair any associated rotator cuff rupture, in order to avoid any greater tuberosity overlap relative to the prosthetic head and to preserve the long head of the biceps tendon which limits upward migration of the humeral head and improves prosthetic kinetics.     

Synthesis and antitumor activity of novel benzophenone derivatives

Novel benzophenone derivatives were synthesized and screened for cytotoxic and antitumor activity. Friedel-Crafts condensation was employed to construct the benzophenone skeleton. Among the compounds synthesized, morpholino and thiomorpholino benzophenones 3a-d exhibited potent cytotoxic activity against P388 murine leukemia and PC-6 human lung carcinoma cells in vitro, and compounds 3a, 3c, and 3j, when administered intraperitoneally, showed significant antitumor activity against the malignant ascites caused by intraperitoneal inoculation of P388 cells in mice.     

ABSORPTION OF CO2 INTO AQUEOUS SOLUTIONS OF STERICALLY HINDERED METHYL AMINOETHANOL USING A HYDROPHOBIC MICROPOROUS HOLLOW FIBER CONTAINED CONTACTOR

The absorption of dilute CO₂ into aqueous solutions of sterically hindered 2-methyl aminoethanol (MAE) and the desorption of CO₂ from CO₂-loaded MAE solutions into N₂ stream were investigated separately for the various combinations of operational variables, using a hydrophobic microporous hollow fiber (polytetrafluoroethylene, PTFE) contained gas-liquid contactor with aqueous solutions of MAE as liquid media in the shell side at 30°C. The absorption of CO₂ in this contactor is governed by resistance in the liquid and hollow fiber phases. The resistance to diffusion in the hollow fiber phase amounts to 76-80% of the total resistance. Nevertheless, the absorption rates of CO₂ into aqueous MAE solutions in this contactor are higher than those into aqueous solutions of sterically hindered 2-amino-2-methyl-1-propanol (AMP) in the stirred tank with a plane unbroken gas-liquid interface. The process of desorption of CO₂ from CO₂-loaded MAE solutions can be regarded as being controlled by diffusion and chemical reaction in both the stagnant film of the liquid phase and the liquid-filled pore of the hollow fiber phase under the slow or intermediate reaction regime. Both absorption and desorption rates under the simultaneous absorption-desorption operation in a single unit tend to approach the respective constant values as process time elapses. The total absorption rate here seems to be almost balanced with the total desorpion rate at the constant mass transfer rate periods.     

Transport of oxygen and carbon dioxide through polycarbonate membrane

Sorption equilibria and permeation rates for oxygen and carbon dioxide in polycarbonate membrane were measured at different temperature between 30 and 60°C and at pressures up to 2.5 MPa. The pressure dependence of mean permeability coefficient to oxygen obeyed the conventional dual-mode mobility model, whereas that to carbon dioxide followed a modified dual-mode mobility model with concentration-dependent diffusivities, as that of polystyrene to the same gas did.     

SYNTHESIS OF ACICULAR GOETHITE PARTICLES BY OXIDATION OF AQUEOUS FERROUS HYDROXIDE SUSPENSION IN A BUBBLE COLUMN WITH DRAFT TUBE

Acicular goethite particles were synthesized by oxidation of an alkaline suspension of ferrous hydroxide using a bubble column with draft tubes of different diameters at a constant temperature of 40°C. The oxidation rate increased with decreasing draft tube diameter. The mean size based on the major axis of acicular particle decreased with increasing oxidation rate and decreasing draft tube diameter. The major axis was found to grow preferentially compared with the minor axis. The mean size of major axis was correlated well to the modified reaction rate defined as a product of the reaction rate per unit volume of the reactor multiplied by the ratio of the column diameter to the draft tube diameter, irrespective of the draft tube diameter.     

Pyrolysis of kraft lignin in molten ZNCL2-KCL media with tetralin vapor addition

Kraft lignin was pyrolyzed in molten salt media of ZnCl₂-KCl mixture with tetralin vapor added in 0.4 and 4 mol% diluted with N₂ in the temperature range of 400 to 700°C. The gas chromatographic analyses of pyrolysis products revealed that the yield of H₂ was not increased by tetralin vapor addition. This fact implies that the hydrogen radical produced from tetralin is consumed in the formation of phenolic compounds and light liquids but not in the formation of H₂. p-Cresol was the most abundant phenolic compound. The yield of total phenolic compounds with 4 mol% tetralin vapor added was increased by ca. 80% as compared to that in neat pyrolysis of Kraft lignin.     

Preparation of barium titanate ultrafine particles from amorphous titania by a hydrothermal method and specific dielectric constants of sintered discs of the prepared particles

Barium titanate ultrafine particles were synthesized from amorphous titania by a hydrothermal method. The mean size of the barium titanate particles prepared at a hydrothermal treatment time of 4 h, was nearly equal to 0.04 5 m in the range of barium-to-titanium molar ratio (BT) 2, and approximately agreed well with the crystallite size. At a BT molar ratio of 1.0, the mean particle size increased to 0.2 m, while the crystallite size remained constant at 0.045 m. When the particle size ranged from 0.12–0.20 m, prepared for the BT molar ratio of 1.0–1.4, the specific dielectric constant for a sintered disc composed of these particles attained a value of 5000 or more. As the BT molar ratio increased to exceed 1.5, when the mean particle size decreased from 0.13 m to 0.045 m, the specific dielectric constant for the sintered disc was decreased greatly. The specific dielectric constant for the sintered disc can be correlated well with the size of the composing particles.