The initial formation and growth of intermetallic phases in the Cu-Zn system
Diffusion kinetics of beta, gamma, and epsilon intermetallic phases in copper-zinc system
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Diffusion kinetics of beta, gamma, and epsilon intermetallic phases in copper-zinc system
A method for achieving both improved high strength and improved ductility ·in intermediate phases is provided. The method, briefly stated, comprises the steps of providing a melt whose composition substantially corresponds to that of a preselected intermetallic phase having a crystal structure of the L1 2 type, such as nickel. aluminide, modified with from about 0.01 to 2.5 atomic percent boron, and rapidly solidifying the melt at a cooling rate of at least about 10 3 ° C./second to form a solid body, the principal phase of which is of the L1 2 type crystal structure in either its ordered or disordered state.
El Goresy et al.'s observation of Nb, Zr, and Ta in refractory platinum metal nuggets (RPMN's) from Ca-Al-rich inclusions (CAI's) in the Allende meteorite led them to propose that these lithophile elements alloyed in the metallic state with noble metals in the early solar nebula. However, Grossman pointed out that the thermodynamic stability of Zr in the oxide phase is vastly greater than metallic Zr at estimated solar nebula conditions. Jones and Burnett suggested this discrepancy may be explained by the very non-ideal behavior of some lithophile transition elements in noble metal solutions and/or intermetallic compounds. Subsequently, Fegley and Kornacki used thermodynamic data taken from the literature to predict the stability of several of these intermetallic compounds at estimated solar nebula conditions. Palme and Schmitt and Treiman et al. conducted experiments to quantify the partitioning behavior of certain lithophile elements between silicate liquid and Pt-metal. Although their results were somewhat variable, they did suggest that Zr partition coefficients were too small to explain the observed 'percent' levels in some RPMN's. Palme and Schmitt also observed large partition coefficients for Nb and Ta. No intermetallic phases were identified. Following the work of Treiman et al., Jurewicz and Jones performed experiments to examine Zr, Nb, and Ti partitioning near solar nebula conditions. Their results showed that Zr, Nb, and Ti all have an affinity for the platinum metal, with Nb and Ti having a very strong preference for the metal. The intermetallic phases (Zr,Fe)Pt3, (Nb,Fe)Pt3, and (Ti,Fe)Pt3 were identified. Curiously, although both experiments and calculations indicate that Ti should partition strongly into Pt-metal (possibly as TiPt3), no Ti has ever been observed in any RPMN's. Fegley and Kornacki also noticed this discrepancy and hypothesized that the Ti was stabilized in perovskite which is a common phase in Allende CAI's.
The objectives of this paper are to learn: (1) what information a binary phase diagram can yield; (2) how to construct and heat treat a simple diffusion couple; (3) how to prepare a metallographic sample; (4) how to operate a metallograph; (5) how to correlate phases found in the diffusion couple with phases predicted by the phase diagram; (6) how diffusion couples held at various temperatures could be used to construct a phase diagram; (7) the relation between the thickness of an intermetallic phase layer and the diffusion time; and (8) the effect of one species of atoms diffusing faster than another species in a diffusion couple.
Hypoeutectic, eutectic, and hypereutectic nickel-molybdenum alloys were rapidly solidified by both bulk undercooling and melt spinning techniques. Alloys were undercooled in both electromagnetic levitation and differential thermal analysis equipment. The rate of recalescence depended upon the degree of initial undercooling and the nature (faceted or nonfaceted) of the primary nucleating phase. Alloy melts were observed to undercool more in the presence of primary Beta (NiMo intermetallic) phase than in gamma (fcc solid solution) phase. Melt spinning resulted in an extension of molybdenum solid solubility in gamma nickel, from 28 to 37.5 at % Mo. Although the microstructures observed by undercooling and melt spinning were similar the microsegregation pattern across the gamma dendries was different. The range of microstructures evolved was analyzed in terms of the nature of the primary phase to nucleate, its subsequent dendritic growth, coarsening and fragmentation, and final solidification of interfenderitic liquid.
Hypoeutectic, eutectic, and hypereutectic nickel-molybdenum alloys were rapidly solidified by both bulk undercooling and melt spinning techniques. Alloys were undercooled in both electromagnetic levitation and differential thermal analysis equipment. The rate of recalescence depended upon the degree of initial undercooling and the nature (faceted or nonfaceted) of the primary nucleating phase. Alloy melts were observed to undercool more in the presence of primary Beta (NiMo intermetallic) phase than in gamma (fcc solid solution) phase. Melt spinning resulted in an extension of molybdenum solid solubility in gamma nickel, from 28 to 37.5 at. pct Mo. Although the microstructures observed by undercooling and melt spinning were similar, the microsegregation pattern across the gamma dendries was different. The range of microstructures evolved was analyzed in terms of the nature of the primary phase to nucleate, its subsequent dendritic growth, coarsening and fragmentation, and final solidification of interfenderitic liquid.
Pt additions substituted for Ni in NiTi alloys are known to increase the transformation temperature of the alloy but only at fairly high Pt levels. However, until now only ternary compositions with a very specific stoichiometry, Ni50-xPtxTi50, have been investigated and then only to very limited extent. In order to learn about this potential high-temperature shape memory alloy system, a series of over twenty alloys along and on either side of a line of constant stoichiometry between NiTi and TiPt were arc melted, homogenized, and characterized in terms of their microstructure, transformation temperatures, and hardness. The resulting microstructures were examined by scanning electron microscopy and the phase compositions quantified by energy dispersive spectroscopy."Stoichiometric" compositions along a line of constant stoichiometry between NiTi to TiPt were essentially single phase but by any deviations from a stoichiometry of (Ni,Pt)50Ti50 resulted in the presence of at least two different intermetallic phases, depending on the overall composition of the alloy. Essentially all alloys, whether single or two-phase, still under went a martensitic transformation. It was found that the transformation temperatures were depressed with initial Pt additions but at levels greater than 10 at.% the transformation temperature increased linearly with Pt content. Also, the transformation temperatures were relatively insensitive to alloy stoichiometry within the range of alloys examined. Finally, the dependence of hardness on Pt content for a series of Ni50-xPtxTi50 alloys showed solution softening at low Pt levels, while hardening was observed in ternary alloys containing more than about 10 at.% Pt. On either side of these "stoichiometric" compositions, hardness was also found to increase significantly.
The feasibility of using metal alloys as thermal energy storage media was determined. The following major elements were studied: (1) identification of congruently transforming alloys and thermochemical property measurements; (2) development of a precise and convenient method for measuring volume change during phase transformation and thermal expansion coefficients; (3) development of a numerical modeling routine for calculating heat flow in cylindrical heat exchangers containing phase change materials; and (4) identification of materials that could be used to contain the metal alloys. Several eutectic alloys and ternary intermetallic phases were determined. A method employing X-ray absorption techniques was developed to determine the coefficients of thermal expansion of both the solid and liquid phases and the volume change during phase transformation from data obtained during one continuous experimental test. The method and apparatus are discussed and the experimental results are presented. The development of the numerical modeling method is presented and results are discussed for both salt and metal alloy phase change media.
The microstructures of niobium aluminides produced by chill block melt spinning were compared to those of niobium aluminides produced by conventional casting. The rapidly solidified alloys were rapidly solidified by melt spinning in an argon atmosphere, and the melt-spun ribbons were examined by optical, X-ray, and TEM techniques. Microstructures were found to range from single-phase for Nb-75 at. pct Al (NbAl3) to two phase for Nb-46 at. pct Al (NbAl3 + Nb2Al). It was found that the melt spinning of Nb-aluminides produced finer grained microstructures than those produced in induction-melted ingots or in powders produced by the rotating electrode process. Ternary additions such as Cr, Ti, and Si tended to form intermetallic phases along the grain boundaries.
Dissimilar metals are reliably joined by diffusion bonding when the surfaces are electroplated with silver. The process involves cleaning and etching, anodization, silver striking, and silver plating with a conventional plating bath. It minimizes the formation of detrimental intermetallic phases and provides greater tolerance of processing parameters.
This report is concerned with the experimental determination of pseudo binary eutectic compositions and the directional solidification of the Ni-Cr-Hf,Zr, and Ni-Cr-Zr eutectic alloys. To determine unknown eutectics, chemical analyses were made of material bled from near eutectic ingots during incipient melting. Nominal compositions in weight per cent of Ni-18.6Cr-24.0Hf, Ni-19.6Cr-12.8Zr-2.8Hf, and Ni-19.2Cr-14.8Zr formed aligned pseudo-binary eutectic structures. The melting points were about 1270 C. The reinforcing intermetallic phases were identified as noncubic (Ni,Cr)7Hf2 and (Ni,Cr)7(Hf,Zr)2, and face centered cubic (Ni,Cr)5Zr. The volume fraction of the reinforcing phases were about 0.5.
Microscopic aspects of interfacial reactions are discussed, such as interdiffusion, formation of intermetallic phases, generation and annihilation of lattice defects, effect of temperature, grain size, etc., which normally occur in diffusion bonding processes. Relationships between properties and microstructure in thin film couples are examined utilizing a unique combination of contact resistance measurements and characterization by transmission electron microscopy.
The feasibility of using metal alloys as thermal energy storage media was investigated. The elements selected as candidate media were limited to aluminum, copper, magnesium, silicon, zinc, calcium, and phosphorus on the basis of low cost and latent heat of transformation. Several new eutectic alloys and ternary intermetallic phases were determined. A new method employing X-ray absorption techniques was developed to determine the coefficients of thermal expansion of both the solid and liquid phases and the volume change during phase transformation. The method and apparatus are discussed and the experimental results are presented for aluminum and two aluminum-eutectic alloys. Candidate materials were evaluated to determine suitable materials for containment of the metal alloys. Graphite was used to contain the alloys during the volume change measurements. Silicon carbide was identified as a promising containment material and surface-coated iron alloys were also evaluated. System considerations that are pertinent if alloy eutectics are used as thermal energy storage media are discussed. Potential applications to solar receivers and industrial furnaces are illustrated schematically.
An oxidation resistant coating is produced on carbon-base materials, and the same processing step effects an infiltration of the substrate with silicon containing material. The process comprises making a slurry of nickel and silicon powders in a nitrocellulose lacquer, spraying onto the graphite or carbon-carbon substrate, and sintering in vacuum to form a fused coating that wets and covers the surface as well as penetrates into the pores of the substrate. Optimum wetting and infiltration occurs in the range of Ni-60 w/o Si to Ni-90 w/o Si with deposited thicknesses of 25-100 mg/sq. cm. Sintering temperatures of about 1200 C to about 1400 C are used, depending on the melting point of the specific coating composition. The sintered coating results in Ni-Si intermetallic phases and SiC, both of which are highly oxidation resistant.
Eutectic compositions and congruently melting intermetallic compounds in binary and multicomponent systems among common elements such as Al, Ca, Cu, Mg, P, Si, and Zn may be useful for high temperature heat storage. In this work, heats of fusion of new multicomponent eutectics and intermetallic phases are reported, some of which are competitive with molten salts in heat storage density at high temperatures. The method used to determine unknown eutectic compositions combined results of differential thermal analysis, metallography, and microprobe analysis. The method allows determination of eutectic compositions in no more than three steps. The heats of fusion of the alloys were measured using commercial calorimeters, a differential thermal analyzer, and a differential scanning calorimeter.
The B2 nickel aluminide, NiAl, is of potential use for high temperature structural applications because of its high melting point, low density, and oxidation resistance. An overview of recent attempts to improve the low temperature ductility as well as the high temperature strength of this alloy is presented. Room temperature tensile ductility of 2.5 percent can be obtained in a stoichiometric binary alloy by careful control of the composition and processing conditions. Alloying additions to improve high temperature creep resistance are most effective when fine distributions of ternary intermetallic phases can be obtained. A promising direction for exploiting the advantages of this alloy may be as a matrix for composite materials.
In order to impart ductility into NiAl-Ni2AlTi alloys, small grain size single (Ni-45Al-5Ti) and two (Ni-40Al-10Ti) phase intermetallics are fabricated by a process which yields fine microstructures in NiAl. The results of a study of elevated temperature compressive properties of two small grain size NiAl-Ni2AlTi alloys are then described. In addition, the behavior of the Ti-modified nickel aluminides with 20 vol pct TiB2 particles of approximately 1 micron in diameter is also investigated, since these compositions have the potential for being the matrix material in high temperature particulate-strengthened composites.
The creep resistance and elevated temperature deformation mechanisms in CoAl, FeAl, and NiAl are reviewed. The stress and temperature dependencies of the steady state creep rate, the primary creep behavior, the dislocation substructure, and the response during transient tests are used as the main indicators of the deformation processes. In single phase intermetallics, the influence of grain size, stoichiometry, and solid solution hardening have been examined. In addition, the effect of adding dispersoids, precipitates, and other types of reinforcements to improve creep strength are compared.