Engineering topics

Spaepen, F.

Publications and source records attributed to Spaepen, F..

9 records

NASA NTRS1985

Bulk Formation of Metallic Glasses and Amorphous Silicon from the Melt

By using metallic glass compositions with a high relative glass transition temperature, such as Pd40Ni40P20, homogeneous nucleation also becomes negligible. Large (5g) masses of this alloys were obtained using a molten B2O3 flux. Presently, bulk glass formation in iron based glasses is being investigated. It is expected that if an undercooling of about 250K can be achieved in a Ge or Si melt, formation of the amorphous semiconductor phase (rather than the crystal) may be kinetically favored. The volumetric behavior of undercooled liquid Ga droplet dispersion is investigated by dilatometry. A theoretical model (both analytical and numerical) was developed for transient nucleation in glass forming melts. The model, originally designed for isothermal conditions, was extended to continuous quenching. It is being applied to glass formation in various metallic and oxide systems. A further refinement will be the inclusion of diffusion controlled interfacial rearrangements governing the growth of the crystal embryos.

Spaepen, F.↗

NASA NTRS1984

Crystal nucleation and glass formation in metallic alloy melts

Homogeneous nucleation, containerless solidification, and bulk formation of metallic glasses are discussed. Homogeneous nucleation is not a limiting factor for metallic glass formation at slow cooling rates if the reduced glass transition temperature is high enough. Such glasses can be made in bulk if heterogeneous nucleants are removed. Containerless processing eleminates potential sources of nucleants, but as drop tube experiments on the Pd-Si alloys show, the free surface may still be a very effective heterogeneous nucleant. Combination of etching and heating in vacuum or fluxing can be effective for cleaning fairly large ingots of nucleants. Reduced gravity processing has a potentially useful role in the fluxing technique, for example to keep large metallic ingots surrounded by a low density, low fluidity flux if this proved difficult under ground conditions. For systems where heterogeneous nucleants in the bulk of the ingot need gravity to segregate to the flux-metal interface, reduced gravity processing may not be appropriate for bulk glass formation.

Spaepen, F.↗

NASA NTRS1984

Bulk formation of metallic glasses and amorphous silicon from the melt

Procedures and compositions for producing metallic glasses in bulk at slow cooling rates were investigated. An attempt was made to form the amorphous phase of the tetrahedrally coordinated elements (Si or Ge) by undercooling the melt. The crystal nucleation behavior of pure liquids and glass formers were examined.

Spaepen, F.↗

NASA NTRS1983

Homogeneous crystal nucleation in binary metallic melts

A method for calculating the homogeneous crystal nucleation frequency in binary metallic melts is developed. The free energy of crystallization is derived from regular solution models for the liquid and solid and is used, together with model-based estimates of the interfacial tension, to calculate the nucleation frequency from the classical theory. The method can account for the composition dependence of the maximum undercooling observed in a number of experiments on small droplet dispersions. It can also be used to calculate the driving force for crystal growth and to obtain more precise estimates of the homogeneous crystal nucleation frequency in glass-forming alloys. This method, although approximate, is simple to apply, and requires only knowledge of the phase diagram and a few readily available thermodynamic quantities as input data.

Thompson, C. V.↗

NASA NTRS1983

Crystal nucleation in amorphous (Au/100-y/Cu/y/)77Si9Ge14 alloys

Because, unlike most metallic glasses, melt-spun alloys of the series (Au/100-y/Cu/y/)77Si9Ge14 exhibit well separated glass transition and kinetic crystallization temperatures, crystallization can be studied in the fully relaxed amorphous phase. An isothermal calorimetric analysis of the devitrification kinetics of the amorphous alloy indicates sporadic nucleation and a constant growth rate. It is found for the cases of alloys with y values lower than 25 that the classical theory of homogeneous nucleation is consistent with observations, including transient effects. An analysis of the crystallization kinetics shows that slow crystal growth rates play an important role in glass formation in these alloys. Although the reduced glass transition temperature increases with Cu content, glass formation is more difficult at high Cu contents, perhaps because of a difference in nucleus composition.

Thompson, C. V.↗

NASA NTRS1982

Crystal nucleation in glass-forming alloy and pure metal melts under containerless and vibrationless conditions

The undercooling behavior of large spheroids of Pd40Ni40P40 was investigated. By surface etching, supporting the specimens on a fused silica substrate, and successive heating and cooling, crystallization can be eliminated, presumable due to the removal of surface heterogeneities. By this method samples up to 3.2g with a 0.53 mm minor diameter, were made entirely glassy, except for some superficial crystals comprising less than 0.5% of the volume. These experiments show that a cooling rate of approximately 1 K/sec is adequate to avoid copious homogeneous nucleation in the alloy, and that by eliminating or reducing the effectiveness of heterogeneous nucleation sites, it is possible to form bulk samples of this metallic glass with virtually unlimited dimensions.

Spaepen, F.↗

NASA NTRS1982

The effect of solute on the homogeneous crystal nucleation frequency in metallic melts

A complete calculation that extends the classical theory for crystal nucleation in pure melts to binary alloys has been made. Using a regular solution model, approximate expressions have been developed for the free energy change upon crystallization as a function of solute concentration. They are used, together with model-based estimates of the interfacial tension, to calculate the nucleation frequency. The predictions of the theory for the maximum attainable undercooling are compared with existing experimental results for non-glass forming alloys. The theory is also applied to several easy glass-forming alloys (Pd-Si, Au-Si, Fe-B) for qualitative comparison with the present experimental experience on the ease of glass formation, and for assessment of the potential for formation of the glass in bulk.

Thompson, C. V.↗

NASA NTRS1980

The mechanism of growth of quartz crystals into fused silica

It is proposed that the growth of quartz crystals into fused silica is effected by a mechanism involving the breaking of an Si-O bond and its association with an OH group, followed by cooperative motion of the nonbridging oxygen and the hydroxyl group which results in the crystallization of a row of several molecules along a crystalline-amorphous interfacial ledge. This mechanism explains, at least qualitatively, all the results of the earlier experimental study of the dependence of quartz crystal growth upon applied pressure: large negative activation volume; single activation enthalpy below Si-O bond energy; growth velocity constant in time, proportional to the hydroxyl and chlorine content, decreasing with increasing degree of reduction, and enhanced by nonhydrostatic stresses; lower pre-exponential for the synthetic than for the natural silica.

Fratello, V. J.↗

NASA NTRS1979

Negative pressures and melting point depression in oxide-coated liquid metal droplets

Negative pressures and melting point depression in oxide-coated liquid metal droplets are studied. The calculation presented show the existence of large negative pressures when the oxide coating is thick enough. The change in the melting point caused by these negative pressures should be considered in studies of homogeneous crystal nucleation. Furthermore, since the negative pressure raises the entropy of the melt, it increases the entropy loss at the crystal-melt interface; the resulting increase of the surface tension could have a large effect on the homogeneous nucleation frequency.

Spaepen, F.↗