Engineering topics

Day, D. E.

Publications and source records attributed to Day, D. E..

At least 19 records

NASA NTRS2006

XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass

The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

Fuss, T.↗

NASA NTRS2006

Isothermal Analysis of the Crystallization Kinetics in Lithium Disilicate Glass using Trans Temp Furnace

Crystallization kinetics for lithium disilicate, Li2O2SiO2, (LS2) glass has been studied extensively by nonisothermal methods, but only a few studies on the isothermal crystallization kinetics of LS2 are available. In the present research, isothermal crystallization experiments or the LS2 glass were conducted in a Trans Temp furnace between 600 and 635 C, and selected properties such as the activation energy for crystallization (E), crystal growth index or Avrami parameter (n), the concentration of quenched-in nuclei in the starting glass (Ni) and the crystal nucleation rate (I) were measured. The crystal nucleation rate (I) was measured at only one selected temperature of 452 C, at this time. This commercial furnace has a 13 cm long isothermal heating zone (+/- 1 C) that allows precise heat treatment of relatively large samples. By placing a thermocouple within approx. 2 mm of the sample, it was possible to detect the heat of crystallization in the form of an isothermal crystallization exotherm during isothermal heat treatment of the sample. The values of E (318 plus or minus 10 kJ/mol), n (3.6 plus or minus 0.l), and N(sub i) (1.6 x 10(exp l2) m(sup -3)) calculated by analyzing these isotherms using the standard Johnson-Mehl-Avrami (JMA) equation were reproducible and in agreement with the literature values. The value of I, 1.9 x 10(exp 10) m(sup -3) s(sup -1) at 452 C, is an order of magnitude higher than the reported value for LS2.

Fuss, T.↗

NASA NTRS2006

Containerless Processing of a Lithium Disilicate Glass

Glasses of Li2O.2SiO2 (LS2) and LS2 doped with 0.001 wt% platinum (LS2 + 0.001 wt% Pt) compositions were melted, cooled and re-heated at controlled rates while levitated (containerless) inside an Electrostatic Levitator (ESL) furnace at NASA Marshall Space Flight Center. The experiments were conducted in vacuum using spherical 2.5 - 3.0 mm diameter glass samples. The measured critical cooling rate for glass formation, Rc, for the LS2 and LS2 + 0.001 wt% Pt glasses processed at ESL were 14 plus or minus 2 C/min and 130 plus or minus 5 C/min, respectively. The values of Rc for the same LS2 and LS2 + 0.001 wt% Pt glasses processed in a container were 62 plus or minus 3 C/min and 162 plus or minus 5 C/min, respectively. The effective activation energy for crystallization, E, for the LS2 glass processed without a container at ESL was higher than that for an identical glass processed in a container. These results suggest that the glass formation tendency for a containerless LS2 melt is significantly increased compared to an identical melt in contact with a container. The absence of heterogeneous nucleation sites that are inherently present in all melts held in containers is believed to be the reason for the increased glass forming tendency of this containerless melt.

Ranasinghe, K. S.↗

NASA NTRS2006

In-Situ Crystallization of a Lithium Disilicate Glass--Effect of Pressure on Crystal Growth Rate

Crystallization of a Li2O.2SiO2 (LS2) glass subjected to a uniform hydrostatic pressure of 4.5 GPa and 6 GPa was investigated up to a temperature of 750 C. The density of the compressed glass is about 2% greater at 4.5 GPa than at 1 atm and, depending upon the processing temperature, up to 10% greater at 6 GPa. Crystal growth rates investigated as a function of temperature and pressure show that lithium disilicate crystal growth is an order of magnitude slower at 4.5 GPa than 1 atm resulting in a shift of +45 C (plus or minus 10 C) in the growth rate curve at high pressure compared to 1 atm condition. At 6 GPa lithium disilicate crystallization is suppressed entirely, while a new high pressure lithium metasilicate crystallizes at temperatures 95 C (plus or minus 10 C) higher than those reported for lithium disilicate crystallization at 1 atm. The decrease in crystal growth rate with increasing pressure for lithium disilicate glass up to 750 C is related to an increase in viscosity with pressure associated with fundamental changes in glass structure accommodating densification.

Fuss, T.↗

NASA NTRS2004

Crystallization of a Li2O2SiO2 Glass under High Hydrostatic Pressures

The crystallization behavior of a Li2O.2SiO2 (LS2) glass subjected to a uniform hydrostatic pressure of 4.5 or 6 GPa was investigated between 550 and 800 C using XRD, IR, Raman, TEM, NMR, and DTA. The density of the glass subjected to 6 GPa was between 2.52 plus or minus 0.01 and 2.57 plus or minus 0.01 grams per cubic centimeters, depending upon the processing temperatures, and was higher than that of the stoichiometric LS2 crystals, 2.46 plus or minus 0.01 grams per cubic centimeter. Thus, crystallization in 6 GPa glass occurred in a condition of negative volume dilatation, deltaV = V(sub glass) - V(sub crystal), while that for the 4.5 GPa glass occurred in the condition deltaV greater than 0. For deltaV greater than 0, which also includes the control glass at ambient (one atmosphere) pressure, the glasses always crystallize Li2Si2O5 (orthorhombic, Ccc2) crystals, but for deltaV less than 0 (6 GPa), the glasses crystallize Li2SiO3 crystals with a slightly deformed structure. The crystal growth rate vs. temperature curve moved to higher temperature with increasing pressure, and was independent of the sign of deltaV. These results for the effect of hydrostatic pressure on the crystallization of LS2 glass were discussed from thermodynamic considerations.

Fuss, T.↗

NASA NTRS2004

Verification of an Analytical Method for Measuring Crystal Nucleation Rates in Glasses from DTA Data

A recently proposed analytical (DTA) method for estimating the nucleation rates in glasses has been evaluated by comparing experimental data with numerically computed nucleation rates for a model lithium disilicate glass. The time and temperature dependent nucleation rates were predicted using the model and compared with those values from an analysis of numerically calculated DTA curves. The validity of the numerical approach was demonstrated earlier by a comparison with experimental data. The excellent agreement between the nucleation rates from the model calculations and fiom the computer generated DTA data demonstrates the validity of the proposed analytical DTA method.

Ranasinghe, K. S.↗

NASA NTRS1996

Non-Isothermal Calorimetric Studies of the Crystallization of Lithium Disilicate Glass

The influence of preannealing treatments on the polymorphic crystallization of lithium disilicate glasses is examined. As expected, glasses heated at different rates through the temperature range where there is significant nucleation develop widely different numbers of nuclei. This can dramatically influence the stability and transformation characteristics of the annealed glass. Non-isothermal differential scanning calorimetry (DSC) and differential thermal analysis (DTA) measurements are demonstrated to be useful to probe the nucleation behavior. The first systematic investigations of particle size effects on the non-isothermal transformation behavior are presented and discussed. Based on DTA and microscopy experiments, we show that small particles of lithium disilicate glasses crystallize primarily by surface crystallization. The relative importance of surface versus volume crystallization is examined by varying particle size, by introducing nucleating agents and by exposing glasses to atmospheres of different water content. These data are analyzed quantitatively using a numerical model developed in a second paper following in this volume.

Ray, C. S.↗

NASA NTRS1988

Containerless processing of glass forming melts in space

The near weightlessness of a material in the reduced gravity environment of space offers the opportunity of melting and cooling glass forming compositions without a container. This reduces the heterogeneous nucleation/crystallization which usually occurs at the walls of the container, thereby, extending the range of glass forming compositions. Based primarily on this idea, containerless glass forming experiments, which used a single axis acoustic levitator/furnace (SAAL), were conducted on SPAR rocket flights, 6 and 8, and on Space Shuttle mission, STS-7 and STS-61A. The experiments on the Space Shuttle were designed to include other studies related to melt homogenization and mixing, development of techniques for preparing uncontaminated preflight samples, and simple shaping experiments.

Day, D. E.↗

NASA NTRS1987

Glass properties in the yttria-alumina-silica system

The glass formation region in the yttria-alumina-silica system was investigated. Properties of glasses containing 25 to 55 wt pct yttria were measured and the effect of the composition was determined. The density, refractive index, thermal-expansion coefficient, and microhardness increased with increasing yttria content. The dissolution rate in 1N HCl increased with increasing yttria content and temperature. These glasses were also found to have high electrical resistivity.

Hyatt, M. J.↗

NASA NTRS1987

Glass formation in microgravity

An account is given of containerless glass-forming experiments conducted aboard the Space Shuttle in 1985, using a single-axis acoustic levitator furnace apparatus. An attempt was made to obtain quantitative evidence for the suppression of heterogeneous nucleation/crystallization in containerless melts under microgravity conditions, as well as to study melt homogenization in the absence of gravity-driven convection and assess the feasibility of laser fusion target glass microsphere preparation with a microgravity apparatus of the present type. A ternary calcia-gallia-silica glass thus obtained indicated a 2-3-fold increase in glass-formation tendency for this material composition in microgravity, by comparison with 1g.

Ray, C. S.↗

NASA NTRS1986

Containerless processing of glass forming melts: D-1, MEA/A-2 experiment 81F01 conducted on STS-61A flight, October 1985

Results of experiment 81F01, which was conducted in the Material Experiment Assembly MEA/A-2 on the D-1 Spacelab Mission (STS-61A), are presented. The general plan of the experiment was to heat, melt, and quench six spherical samples of different glass forming compositions while they were levitated in a single axis acoustic levitator furnace (SAAL). In addition, two non-melting sintered alumina samples were used to check the operational characteristics of the SAAL under reduced gravity conditions. Three of the eight samples were levitated between 1250 and 1500 C before the lack of coolant created an over-temperature condition that caused the SAAL to shut down prematurely. Two of the three samples processed were calcia-gallia-silica and soda-lime-silica glass forming compositions. Evidence of a two to three times increase in the tendency for glass formation was obtained for the calcia-gallia-silica. The final glass appeared reasonably homogeneous even though it was made from hot pressed powders containing deliberate heterogeneities. A photographic record was obtained of the microgravity sample processing sequences.

Day, D. E.↗

NASA NTRS1986

Dependence of the critical cooling rate for lithium-silicate glass on nucleating agents

The critical cooling rate, Rc, for glass formation of a glass containing 40 mol pct Li2O and 60 mol pct SiO2, doped with small amounts of Pt, Au, P2O5, and TiO2 nucleating agents, has been measured. Rc increases with increasing Pt and Au additions, but Pt has a larger effect than Au. Additions of P2O5 tend to decrease Rc, whereas TiO2 has practically no effect on Rc. The devitrified glass nucleated with Pt contains only crystalline Li2O-SiO2, but all the other devitrified glasses, including the undoped glass, contain both Li2O-SiO2 and Li2O-2SiO2. Analysis shows that Rc increases as the concentration of the Li2O-SiO2 phase in the devitrified glass increases.

Huang, W.↗

NASA NTRS1985

Effect of R(3+) ions on the structure and properties of lanthanum borate glasses

The present investigation of glass formation in the (mole percent) systems 25La2O3 (x)R2O3 (75-x)B2O3, where R = Al, Ga, and (25-x)La2O3 (x)Ln2O3 75B2O3, where Ln = Gd, Er, Y, notes that up to 25 mol pct Al2O3 or Ga2O3 can be substituted for B2O3, while no more than about 5 mol pct Ln2O3, substituted for La2O3, caused macro-phase separation. The substitution of either R2O3 or Ln2O3 in the lanthanum borate system changes the separation distance between adjacent B3O6 chains. The effect of this structural change on the molar volume, transformation temperature, thermal expansion coefficient, and transformation-range viscosity is discussed.

Chakraborty, I. N.↗

NASA NTRS1985

Glass formation and properties in the system calcia-gallia-germania

The critical cooling rate for glass formation, R sub c was measured for four compositions in the system calcia-gallia-germania. The activation energy, E, and frequency factor, nu, for the crystallization process were determined by reheating the glasses at varied constant heating rates and measuring the temperature of crystallization. Both E and nu increased, with increasing germania content of the glass, whereas R sub c decreased. The density, refractive index, and Abbe number were also measured; all decreased with increasing GeO2 content. These results are compared with those for calcia-gallia-silica glasses of comparable compositions.

Angel, P. W.↗

NASA NTRS1985

Structure-property relations in lanthanide borate glasses

Glass formation in the system Ln2O3-B2O3 (Ln = Nd, Sm) was studied. Glasses could be formed in the range from 0 to 28 mol pct rare-earth oxide (Ln2O3), but liquid immiscibility in these systems limits the range of homogeneous glasses to 0 to 1.5 and 25 to 28 mol pct Ln2O3. The infrared spectra indicate that the rare-earth-rich glasses are structurally similar to rare-earth metaborates (LnB3O6) which contain (B3O6)-infinity chains. The variation in density, transformation temperature, thermal expansion coefficient, and transformation-range viscosity of these glasses with the size of the rare-earth ion is discussed. Glasses near the metaborate composition have a transformation temperature of about 700 C, which is high for binary borate glasses. Glasses could not be formed in the systems Eu2O3-, Gd2O3-, Ho2O3-, and Er2O3-B2O3, even by quenching at 1300 C/s. The sudden lack of glass formation in the system Ln2O3-B2O3 with Ln(3+) ions smaller than Sm(3+) is explained on the basis of the size effect of the Ln(3+) ion on the stability of (B3O6)-infinity chains in these metaborates.

Chakraborty, I. N.↗

NASA NTRS1984

Crystallization of calcia-gallia-silica glasses

A thermal image furance is presently used to study the critical cooling rate for glass formation, and the kinetics of crystallization, of the compositions 18.4CaO-(81.6-X)Ga2O3-XSiO2, where X = 3, 6, 9, and 13.8. Crystallization was studied nonisothermally, and the data were analyzed in light of the Avrami (1939) equation. Critical cooling rate and crystallization activation energy are both found to decrease with increasing silica content, and the results obtained by the present technique are noted to agree with those obtained on the basis of differential thermal analysis measurements.

Ray, C. S.↗

NASA NTRS1984

Glass formation and properties in the gallia-calcia system

The critical cooling rate for glass formation was measured for five compositions in the Ga2O3-CaO system and varied from a low of (315 + or - 85) C/s for a eutectic melt containing 37.5 mol pct Ga2O3 to a high of (840 + or - 60) C/s for a melt containing 52 mol pct Ga2O3. The density and refractive index both increased with increasing Ga2O3 content, but the crystallization temperature and microhardness varied only slightly. The IR spectra of these glasses suggest that both GaO4 tetrahedra and GaO6 octahedra are present.

Whichard, G.↗

NASA NTRS1983

MEA/A-1 experiment 81F01 conducted on STS-7 flight, June 1983. Containerless processing of glass forming melts

The space processing of containerless, glassforming melts on board the space shuttle flight STS-7 is investigated. Objectives include; (1) obtain quantitative evidence for the supression of heterogeneous nucleation/crystallization, (2) study melt homogenization without gravity driven convection, (3) procedural development for bubble free, high purity homogeneous melts inmicro-g, (4) comparative analysis of melts on Earth and in micro g, and (5) assess the apparatus for processing multicomponent, glass forming melts in a low gravity environment.

Day, D. E.↗