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By P. R. Sahm, T. V. Pruss, D. A. Gandolfo

Cb 3 Sn powders were hot-pressed to estahlish densi-fication conditions and assess the possible use of such compacts in multiphase structures with ceramic or magnetic inclusions. Superconducting transition temperatures, Tc, were measured as a function of powder particle size, pressing temperature, and second-phase admixtures. The highest transition temperatures were found in coarse powder (5 to 500 u) compacts and were only weakly depended on pressing temperatures up to 1200°C. Fine powders (below 5 p), however, both single-phase CbsSn and Cb3 Sn-composites, showed a stronger dependence on hot-pressing temperatures. While Al2 O3 phase admixtures did not affect T, much more, a Pronounced T, degradation was observed upon the addition of ferrimagnetic Fe2 Mno. 5 Zno.5 O4 powders. Likewise, critical current densities, Jc, at 4.2° K were lowered appreciably in the ferrite doped samples, whereas the neutral A1203 inclusiow gave slightly improved Jc values. MULTIPHASE structures in electronically active materials have recently gained in interest as pointed out by Galasso in a review article.' In superconductors the most widely reported group are eutectic alloys which have been mostly investigated with respect to the proximity effect.2"4 In addition, "artificial eu-tectics", for example in the form of mercury-vycor glass sponge5 or fine niobium wires imbedded in a copper matrix,= have been prepared to attain higher critical fields and critical current densities. The idea was to enhance flux pinning phenomena by second-phase inclusions or ho1es. 7 Flux pinning should also be possible by the introduction of insulator inclusions into a superconducting matrix. Ceramic-metal combinations are most easily produced by hot pressing (= pressure sintering), as it permits an almost unlimited selection of material combinations. Cb 3 Sn has been prepared by vapor phase growths or in the form of thin films. Large compacts must be sintered,1° however, and normally present difficulties. At temperatures below 1350°C insufficient densities are obtained and at higher temperatures the loss of tin due to dissociation upsets the stoichiometry. Hot pressing is a natural approach to circumvent the problems, since one can obtain satisfactory densities despite low sintering temperatures. This work was mostly concerned with establishing conditions to hot press Cb3 Sn and Cb3 Sn multiphase structures (= composites), because no data are presently available, and to evaluate these with respect to their transition temperatures. However, a few measurements on critical current densities were also carried out, in particular to assess the value of ferrimagnetic inclusions. I) EXPERIMENTAL PROCEDURE The experimental procedure involved the preparation of feed material and powders, hot pressing, and evaluation of the resulting ingots. As no attempts were made to synthesize Cb3Sn from the elements during hot pressing, feed material had to be produced. For this purpose, a stoichiometric Cb-Sn powder mixture was compacted into a 3-cm-diam ingot (80,000 psi) and then inserted into a quartz tube and evacuated. Rf heating was employed. Above the tin melting point (230°C) liquid tin was forced out of the ingot, but was pulled back by capillary action after approximately 0.5 hr of continuous pumping at 700°C. Thus, it appears that evacuation at this temperature caused desorption of impurity gas creating wetting surfaces which, later on, favored alloying at relatively low temperatures. After a presintering period of 17 hr at 800°C, the quartz tube was tipped off and sealed into another such larger-diameter tube which, in turn, was connected to a pump system. This configuration permitted a temperature treatment at 1400°C, carried out for 65 hr, without collapsing of the glass walls or unfavorable chemical interaction of Cb3Sn with the quartz. The resulting material was

Jan 1, 1969

By R. M. Goldhoff, J. W. Spretnak

IN connection with establishing the mechanism by which boron enhances the hardenability of heat treatable steels, this research work has been undertaken. Spretnak and Speiser1,2 indicated the need for studying high temperature effects in boron steels and, chief among these, the possible nonhomogeneous distribution of boron in iron grains. The occurrence of this effect may be of significance in explaining the mechanism of enhancement of hardenability by boron as well as in explaining some of the observed characteristics of boron steel behavior. Primarily, then, this work was undertaken a) to establish whether or not boron is adsorbed in ? solid solutions, b) to determine the nature of any such adsorption effects, i.e., whether it is positive or negative as well as its temperature coefficient, and c) to establish the magnitude of any such effect. While past literature on this specific subject is rather sparse, a number of authors have postulated that the observed temporary loss of hardenability as well as the occurrence of the characteristic boron constituent in these steels is due to the nonuniform distribution of boron in austenite.3-0 Experimental Techniques Attempts to obtain direct evidence of grain boundary effects in boron steels have been unsuccessful, both by using the technique of Chalmers' in which small concentrations of solute made radioactive by irradiation are detected by autoradiographic means, and by means of studying cleavage fractures with the electron microscope.8 The present study attempts the design of experiments to measure the effect of boron on properties which might be subject to variation because of grain boundary effects. A study of the theoretical aspects of grain growth indicates that such studies may be pertinent. Another valid type of experiment involves the measurement in polycrystalline materials of properties whose values depend on the bulk of the grain, being negligibly influenced by grain boundaries. One such property is the lattice parameter measured by X-ray diffraction. The value of the lattice parameter reflects the average conditions which obtain over a relatively large number of atoms in a fixed crystalline lattice, and is therefore mainly dependent on bulk grain material. Measurement of lattice parameter variation over the austenite range of temperature in iron with and without boron should give evidence of concentration variations in the bulk grain material if adsorption effects are significant. Finally, use is made of the Grange and Garvey3 metallographic test for boron in which a characteristic boron constituent can be developed in austenite grain boundaries. The very occurrence of this phenomenon suggests grain boundary enrichment of boron and a study of the occurrence of this constituent and its varation with austenitizing temperature should help to detect grain boundary effects. Materials One lb ingots of pure iron, an Fe-B alloy, an Fe-C alloy, and an Fe-C-B alloy were prepared. The melting technique included an initial melting of electrolytic iron under vacuum followed by remelting under hydrogen and, finally, by melting under argon with the addition of alloying elements. Each ingot was surface machined between meltings. A quantitative spectrographic analysis was obtained on the pure ingot and, in addition, oxygen, nitrogen, and carbon were determined by the vacuum fusion method. The results of these analyses are given in Table I. Semiquantitative spectrographic analyses were performed on the alloy ingots, while quantitative determinations of the alloy additions were obtained. These analyses are shown in Table 11. The cast ingots were subjected to the following sequence of fabrication treatments: forging to 5/8 in. bars, swaging to 0.300 in. rounds, drawing to 0.025 and 0.010 in. wire. Portions of each ingot were retained in the swaged condition for experimental use. For certain portions of the work typical commercial steels were used. These materials were supplied by the Republic Steel Corp., Canton, Ohio, and correspond to AISI 8640 and AISI 86B40 compositions.

Jan 1, 1958

By R. H. Hiltz

Three titanium alloys, known to provide a mechanically unstable p structure after quenching, were selected as material for a study of the Origin and nature of stress-induced transformation. Data from hardness and tensile tests were used to study the initiation of marten site and the effect of the transfornation and transformation products on the mechanical properties of B titanium, particularly the stress-strain relationships. With the exception that the materials investigated showed a natural aging reaction in the P condition, their behavior is analogous to that of' stress-transforming stainless steels. The transformation starts after initial yielding and is essentially complete just prior to .maximum loading. Once initiated, the martensite itself is capable of propagating the transformation. The deforn-ing materials show low strength, high ductility, and a high strain-hardening exponent. In metallic systems which undergo a diffusionless transformation on cooling, it is possible to produce a similar transformatiorl by plastic deformation under special conditions. Dewez' in delineating Ms temperatures for the titanium-rich end of most titanium binary systems:, established the point of intersection of Ms with room temperature for those particular alloys. Alloy compositions which would quench to mechanically unstable p were established from these data. The first investigation into the possibility of stress-induced transformation occurring in titanium met with little success. It was concluded that such a transformation in titanium was possible only under very special conditions. Continued effort in this direction, however, showed certain Ti-Mo binaries to be highly susceptible to this phenomenon. This fact was utilized by Liu to study the habit planes of martensite and by Machlin and wenig5 to study the effects of stress and plastic deformation on the P to a prime transformation in titanium alloys. The first investigation of the mechanical properties of these alloys was conducted by Holden and his coworkers at Battelle Memorial Institute.' The potentiality of the alloys i3s sheet-forming material was recognized, and the data reappeared in a survey of this type of titanium material.? The initial optimism was tempered by the difficulties in obtaining homogeneous 2i-Mo alloys in commercial-size ingots. The increasing need for good sheet-forming material kept investigation in this direction active, resulting in the development of a commercial alloy of this type.' This study was undertaken to obtain a clearer picture of the mechanism of stress-induced transformation in titanium. MATERIALS AND TEST PROCEDURE Three alloys were selected for this investigation: one a Ti-Mo alloy; another a Ti-Cr-Mo alloy, known to deform martensitically; and the third, a Ti-V alloy with an Ms below room temperature and an Md above room temperature, but known to contain w phase in the quenched condition. The compositions of these alloys are given in Table I. These alloys were cast as 5-lb experimental ingots, employing skull melting. The ingots were hot-forged into 1-in.-round bars. Two 72-in.-thick slices were cut from each bar for hardness testing; the remainder was cut into 0.252-in. tensile blanks. The tensile blanks and one hardness disc from each bar were heated in salt to a temperature 100°F above the 0 transus, held 2/2 hr, and brine quenched. X-ray analysis showed the pieces to be 100 pct 8.* *Omega cannot be distinguished from p by the technique employed. Tensile blanks were machined to size after this treatment. TO prevent transformation due to machining stresses, the shoulders and gage length were ground. True stress-true strain curves were

Jan 1, 1960

By R. J. Schaefer, M. E. Glicksman

Direct, in situ observation of metallic alloys during solidification reveals that in some systems crystal multiplication occurs by means of a dendrite remelt-ing process, without the necessity of independent nu-cleation events. The solidification is observed on optically clean surfaces of supercooled molten alloys. In one system (Sn-3 wt pct Bi) , a fine-grained equi-axed structure is produced by the complete disintegration, via remelting, of transient initial dendrites. In contrast, several other metallic systems show little or no evidence of remelting activity. The behavior of these metallic systems is consistent with that expected on the basis of published observations of dendrite remelting in transparent organic alloy systems. It is concluded that dendrite remelting is an important crystal multiplication process in some metallic alloys, but is velatively unimportant in some other alloys. The detachment of dendrite branches from the primary stem by a remelting process has been observed by Jackson, Hunt, Uhlmann, and seward1 during the solidification of some transparent organic alloy systems. The branches released by this remelting process can drift free of the primary stem and serve as seeds for the formation of numerous independent crystals. This proliferation of new crystals does not require repeated independent nucleation events, but only modification of the initial solidification structure. The mechanism of dendrite remelting, as described by Jackson et a1.1 and by Tiller and O''Hara,2 is dependent on the transport of both heat and solute and is, therefore, expected to operate only in alloys, and not in pure substances. It was found in the transparent organic alloy systems that remelting occurred primarily in the constricted regions near the base of dendrite branches, where the branches had grown through the solute-rich liquid layer surrounding the primary dendrite stem. It was suggested that impure solid had formed in these constricted regions at a relatively low temperature and had later become unstable as further solidification of purer material raised the temperature. Jackson et al. proposed that the equiaxed zone of metal alloy castings originates from a similar remelting process, and they demonstrated the operation of this mechanism in "ingots" poured from saturated salt solutions. Although these substances were especially selected to show solidification behavior similar to that of metals,3 the remelting mechanism has, until now, been subject to the objection that its operation has not been directly observed in a metallic system. Considering the fact that thermal properties such as diffusivity may differ by as much as two or three orders of magnitude between metals and organic compounds, this objection was considered to be possibly serious. A method has now been developed by which it is possible to make direct optical observations of metals during solidification. This method has revealed transient solidification processes which would not be detected by metallographic examination of totally solidified specimens. In particular, a grain-refinement process in a metallic alloy has been observed to be a direct consequence of the total disintegration of an initial dendritic structure. The influence of an initial, transient solidification structure on the final solidification structure is demonstrated here for the first time in a metallic system. I) EXPERIMENTAL The technique of using a transparent flux to maintain an optically clean metal surface during solidification has been described by us elsewhere.* The

Jan 1, 1968

By M. R. Tek, M. L. Katz

The flow of fluids in stratified porous systems, in which adjacent layers of the system are in communication over part or all of their common interface, in many instances involves crossflow between layers. A theoretical study has been made of the unsteady-state flow of slightly compressible fluids during depletion of bounded stratified porous systems. Consideration has been restricted to single-phase flow, with negligible capillary and gravity effects. Analytical expressions have been derived for pressure distribution and for (luxes at the producing face in two-layer systems with complete fluid communication between layers. These expressions occur in the form of double Fourier and Fourier-Bessel series. The method of extending the solution to any number of layers is demonstrated by deriving the equation for pressure distribution in a three-layer system. On the basis of the exact results for two-layer systems, certain generalizations regarding the behavior of stratified systems in general are presented. The performance of stratified systems, in terms of cumulative flux as a function of time, is shown to lie at all times between bounds established from single-layer theory. The upper bound is given by treating the system as a single layer with arithmetic average physical properties. The corresponding lower bound is the summation of the fluxes from each layer as treated individually. Variation in performance of stratified systems between the upper and lower bounds is determined by the extent to which crossflow occurs in the system. The principal parameters affecting the amount of crossflow are the vertical permeability of the system, the ratio of system thickness to "radius of drainage" and, for radial systems, the ratio of system thickness to interior radius. At very early times, the system performance is near the lower bound. As time and the radius of drainage increase, the per- formance tends toward the upper bound. INTRODUCTION One of the principal problems confronting the reservoir engineer today is the incorporation of the effect of reservoir heterogeneity into predictions of reservoir performance. The first part of this problem is the characterization of the actual reservoir heterogeneity in a mathematically useful manner.1, 2 It is then necessary to calculate the effect of this heterogeneity on the system performance. It is frequently possible to estimate this effect by comparison with the known behavior of an idealized system. One such idealized system is the stratified or "layer-cake" model. Many studies have been made of the behavior of stratified systems, from both a theoretical and experimental standpoint. The great majority of the theoretical studies have been concerned with systems of separated layers, with no fluid crossflow. Among the more noteworthy of such theoretical papers is that recently published by Lefkovits, et al,3 in which a comprehensive analysis was presented for the behavior of bounded stratified systems which are unconnected except at the wellbore. Three recent references have dealt with stratified systems including the effect of crossflow. Jacquard4 has presented mathematical derivations pertaining to depletion of two layer systems producing at constant rate. A doctoral dissertation by Katz5 contains analytical solutions and tables of results for pressure distribution and fluid flux during constant-terminal-pressure depletion of two-layer and three-layer systems with crossflow, together with tables of eigenvalues necessary in the computations. The dissertation also presents results from experimental studies of stratified systems using a heat-transfer analog model. This paper is largely based on the material in this dissertation. A third paper has been presented by Russell and Prats6 since completion of the work resented herein, containing mathematical derivations for and discussion of the behavior

By J. E. Spruiell, F. H. Patterson, B. F. Shuler

The microstructures and textures developed by the working of high-purzly thermochemically deposited tungstem sheet have been inuesligated. Greater than 60 pct reduction was required to deslroy the columnar grain structure which existed in the as-deposited sheet. With increasing reductions the texture gradu-ally charged from the initial as-deposited orientation with (100) parallel to the sheet normal to a (100}(011) ideal ovienlation with some spread about the rolling direction. This texture was retained after recrystalli-zation a1 2000°C. THE processes for depositing tungsten by hydrogen reduction of tungsten hexafluoride have been under development for the past several years.1,2 The nature of the deposition process is such that the as-deposited material contains a highly oriented columnar grain structure perpendicular to the deposition substrate. This well-defined columnar structure may be useful in certain applications293 but a wrought or equiaxed structure may be desired for some components such as tubing. Knowledge of the effects of working ther-mochemically deposited (TCD) tungsten is therefore necessary in order to establish the feasibility of obtaining worked and recrystallized microstructures and textures. The details of a recently developed technique for thermochemically depositing flat, uniformly thick tungsten sheet are presented with emphasis on the effects of deformation by rolling on the microstructure and texture. Although no work has been previously reported on the rolling and the annealing textures of TCD tungsten, there have been some determinations of textures for cold-rolled tungsten foil prepared from powder-metal -lurgy billets.4-8 The general description is that of a predominantly lurgy{100}(011) texture, with some spread about the rolling direction as an axis. pugh5 reports data both for cold-rolled and for annealed foil having about 96 pct initial cold work. He observed no change in texture, except for a decrease in the spread, for annealing treatments of 30 min at temperatures up to 1800°C. On annealing at 1900°C, both the low-temperature components plus new components which were described alternately as {001}(320) plus {001)(230) or as {100}(011) ± 12 deg about the sheet normal were observed. Above 1900°C, the new orientation existed alone, and it was stable up to 2500°C, the highest temperature that Pugh investigated. THERMOCHEMICAL DEPOSITION OF TUNGSTEN SHEET High-purity tungsten sheet was reproducibly deposited on the inner walls of a molybdenum mandrel by the thermochemical reaction WFs(g) + 3H2(g) - W(s) + 6HF(g). The mandrel was heated by a five-zone tube furnace which afforded a controllable fixed-temperature profile. Sheets measuring 1+ by 12 in. have been deposited with uniform thicknesses of up to 0.145 m. As shown schematically in Fig. 1, the purified reaction gases were metered into a mixing chamber at a Hz-to-WF6 ratio of 15 and preheated to 350°C. The flow rate of the WF6 was 300 cu cm per min at stp. These gases were directed through a conical injector into the deposition chamber. Inside this chamber hydrogen reduction of the WF6 to pure tungsten metal occurred on the hot walls of the molybdenum mandrel at a total pressure of 5 Torr. Typical temperatures for the five zones in the chamber were, respectively, 565", 540", 550°, 570°, and 590°C. The hydrogen fluorlde generated from the reaction, the excess hydrogen, and some un-reacted WF6 were pumped on through the scavenger

Jan 1, 1968

By R. H. Doremus, E. F. Koch

The first carbide phase that precipitates at 120°C from a iron containing about 0.02 wt pct, C was studied with the electron microscope. In both strained and unstrained material the carbide particles appeared to form on the dislocations in the iron, in agreement with the results of the kinetic study in part II. The structure of the carbide was tentatively identified as an expanded a-iron lattice (body-centered tetragonal) with about 0.7 wt pct C. This phase appeared to be metastable and apparently transformed into cementite or epsilon carbide when the iron was over-aged. WhEN a iron containing less than about 0.025 wt pct C is quenched from 700°C to room temperature the carbon is retained in solid solution and precipitates out slowly with time. The morphology and structure of the precipitating phase are still in doubt, two different carbide phases, epsilon carbide and cementite, have been identified, but there is considerable disagreement about the time and temperature at which they appear.1-4 Epsilon carbide seems to form at lower temperatures than cementite, although one group of investigators4 found only the latter phase over a wide range of aging temperatures. Usually these two phases have been identified after aging times much longer than needed to drain the carbon from supersaturated solution, at least for aging temperatures below 200oC. The precipitated carbides have been observed with the electron microscope,'-5 but again most results have come from samples aged much longer than necessary to reduce the carbon concentration in solution to a low value. In this study the carbide phases were observed in earlier stages of precipitation with the electron microscope, in order to learn more about the shape, size, and distribution of the carbide particles. Samples strained small amounts before aging, as well as unstrained samples, were studied, and the structure of the carbide phase was tentatively identified. EXPERIMENTAL "Ferrovac E" vacuum-melted iron, from which the wires for kinetic studies were also made (Refs. 6 and 7 and the following paper) was used for this work. An analysis of this material is given in Table I; it agrees well with the manufacturer's values. The number of inclusions in the iron was very small, as can be seen in the optical micrograph in the following paper. Pieces of iron about 1 mm thick and 5 to 10 mm in diam were used for all the studies except for those in which the sample was strained before aging; then the specimen was a rod 3 to 6 mm in diam and 20 cm long. The samples were held at about 700°C in wet hydrogen for at least an hour to remove residual carbon and nitrogen, after which they were heated to 950" (in the y region) and cooled to room temperature in the furnace. This treatment gave an average grain diam of more than 1 mm, so that the effect of grain boundaries on the precipitation process was negligible. The samples were carburized at 710°C for about 2 hr in hydrogen that had passed over toluene held at -30°C; then they were rapidly quenched into water. From chemical analysis this treatment gave a carbon concentration of from 0.012 to 0.016 wt pct, which is less than the solubility of carbon at this temperature. After quenching, the samples were aged at 120 "C in an oil bath for vari-

Jan 1, 1961

By P. K. Koh

Isothermal salt bath annealing of 0.014-in. thick 3 pct Si-Fe sheet was conducted at temperatures ranging from 927" to 1260°C in order to investigate the grain-growth behavior. Within the temperature range studied normal grain growth did not take place; instead nucleated grain growth prevailed. The nucleation frequency was found to increase with the annealing temperature, with corresponding decrease in grain diameter of ultimate secondaries after long-time annealing. Large secondaries grown by low-temperature isothermal annealing are essentially of (110)[001] orientation, and the (110)[001] texture is strong. The relatively small secondaries grown by high-temperature isothermal annealing also have orientations near (110)[001] as an average but widely scattered; thus the amount of (110)[001] texture is found to decxease with isothermal annealing temperature. Grain growth and texture development at various annealing temperatures can be described by families of sigmoidal curves with the time axis. ThE cube-on-edge (110)[001] texture and predominating large secondaries in fully annealed 3 pct Si-Fe are customarily produced by a 1100°C annealing of a primary recrystallized sheet. On annealing the primary recrystallized sheet above the temperature at which secondary recrystalliza-tion starts May and turnbull' have demonstrated that secondary grains decrease in size as the temperature is increased. The phenomenon was attributed to a decrease in the (G/N) ratio where G is the growth rate of secondary grains and N is their nucleation frequency. In addition, the growth of grains in orientations rather far from (110) [0011 occurred. The present investigation is devoted to detailed rate studies of the same phenomenon. Mi-crostructure, magnetic anisotropy, and texture data were obtained on strips of 3 pct Si-Fe isothermally annealed for various lengths of time in a BaC12 salt bath at temperatures ranging from 927' to 1260°C. The texture results are reported elsewhere.2 EXPERIMENTAL PROCEDURE Commercial 0.014-in. cold-rolled silicon-iron strip (3.16 pct Si), prepared by two stages of cold rolling with an intermediate short anneal, was given a decarburizing 3-min anneal at 800°C. Metallo- graphic studies indicated complete recrystallization. In order to provide a protective atmosphere and to obtain a rapid rise to an elevated temperature, a BaC12 and NaCl fused salt bath was used to heat samples isothermally at temperatures from 927" to 1260°C for various lengths of time. Torque magnetometer measurements were made on 1-in.-diam disc specimens before and after annealing, since magnetic torque curves supply information on textures and texture changes. Surface layers of the strip samples were polished and etched to reveal the grain structure. The diameters of grains were measured from micrographs at X100. The average value of diameters of matrix grains was established. Individual grains in the micrograph were cut out separately along grain boundaries. These grains were classified either as matrix grains or growth grains. The percent weight of growth grains in the cut-out patterns was reported as percent growth. Manv of the individual grains in the annealed samples were large enough to be X-rayed with a 5-mil beam for Lauegrams. Complete (110) pole figures were obtained for the primary recrystallized structure and short-time annealed structure with CoKa radiation at 30 kv in the back-reflection range, such as (220) for (110) poles, as described recently by Newkirk and ~ruce.~ Both the X-ray optics and the technique for pole figure differed slightly from those adapted previously.4

Jan 1, 1960

By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Cryolite, sodium aluminum fluoride, Na3AlF6, is a rare mineral which has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. History Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in sixteenth century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open-hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and II. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940s were outstanding technological advances that facilitated increased production. Recently, pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. Uses of Fluorspar Fluorspar is used to make hydrogen fluoride, also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride (HF) is produced by reacting acid grade (97% CaF2) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation, the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, which is an ingredient in high-octane fuel for aircraft and automobiles, in steel pickling, enamel stripping, glass etching and polishing, and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 50 to 60 lb of fluorine content in synthetic cryolite and alumnium fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly.

Jan 1, 1983

By L. O. Brockway, W. C. Bigelow, J. A. Amy

Specimens of Inconel-X alloy solution-treated at 2050°F and aged for periods of 1, 10, 100, and 1000 hr at 1200°, 1400°, and 1600°F have been examined by electron microscopy and by electron and X-ray diffraction. Four minor phases were identified: titanium nitride, niobium nitride, an M23C6 complex carbide, and the intermetallic ? phase. The two nitrides were found in all of the aged specimens and in the solution-treated alloy, the y' phase formed at all aging temperatures, while the M23C6 carbide formed only on aging at 1200° and 1400°F. Variations in the hardness, rupture strength, creep strength, and yield strength of the alloy have been shown to be related to variation in the size and distribution of the particles of the y' phase within the matrix grains of the alloy, with maximum values of these properties occurring when there is a maximum amount of the phase present and a fine state of dispersion of the particles prevails. THE nickel-chromium alloys containing titanium and aluminum are widely used in applications requiring high strength at elevated temperatures. Studies on relatively simple ternary and quaternary alloys'-4 have indicated that the favorable high-temperature properties of these alloys are related to the precipitation of an intermetallic ?'-phase having a structure based On that of the Ni3A1 phase of the nickel-aluminum system. The present investigation was undertaken to identify the minor phases and to study the microstructural changes occurring in one of the more complex commercial alloys as a result of aging in the service temperature range, with particular emphasis on investigating the role of the ?' -phase. The microstructural changes were studied by electron microscopy and the minor phases were identified by X-ray and electron diffraction. MATERIALS AND METHODS Inconel-X alloy was selected for this investigation because the previous studies of Frey, Freeman, and white6 provided extensive information on the variations in metallurgical properties of this alloy resulting from high-temperature aging treatments. Specimens aged 1, 10, 100, and 1000 hr at 1200°, 1400°, and 1600°F were made available for the present use. These were taken from 1-in. round-bar stock of a commercial heat having the following weight composition: 0.04 C, 0.56 Mn, 6.59 Fe, 0.007 S, 0.38 Si, 0.03 Cu, 73.22 Ni, 14.97 Cr, 0.78 Al, 2.38 Ti, and 1-02 Nb. They were solutjon-treated at 2050 for 4 hr and then water-quenched prior to aging. Powder X-ray diffraction patterns were obtained from insoluble minor phases which were separated from the alloys by digestion in the reagent of Mahla and Nielsen.6 Back-reflection patterns were obtained from electrolytically polished surfaces of the bulk search to detect the ?'-phase' Cu-K a radiation was used in both cases. In the electron-diffraction studies, the general method developed by Heidenreich, Sturkey, and

Jan 1, 1959

By J. E. Burke

RECENT investigations have elucidated many of the phenomena of the grain growth process, but have also revealed some conflicting and unexplained results. Beck and his co-workers1,2,3 have shown that grain growth continues with continued heating at one temperature until the average grain size approaches the thickness of the specimen, Plotting the logarithm of the average grain diameter, D, against the logarithm of the annealing time, t, they find the straight line relationship given by the equation: [D=Ktn [11] with possible small deviations at short annealing times. K and n are constants at constant temperature. On the other hand, Walker4 finds that, in alpha brass, the rate of growth falls off more rapidly than indicated by Eq I after long annealing, so that an equilibrium grain size is approached. Burke5 showed, using Walker's data, that time and temperature for grain growth are apparently related through an activation energy, H, according to the relationship: [t, Hr i '_ III t„ = R \T, - ~) [2]] where t1 and t2 are the annealing times necessary for the average grain size to increase from Do to D at temperatures T1 and T2 and R is the gas laws constant. In the case quoted, H had the value 60,000 cal per mol. The apparent validity of this relationship, at least up to 700°C, and the approximate value of H were later confirmed by Beck.' The results obtained by Beck, Kremer, Demer and Holzworth2 for aluminum and aluminum-magnesium alloys could not be satisfied by such a relationship, since the slope of the isothermal curves increased with increasing temperature. These data indicate and Beck, Holzworth and Hu6 later demonstrated experimentally that the only apparent factor controlling the rate of grain growth at constant temperature is the grain size. While many of the phenomena have been elucidated, a reasonably quantitative explanation of the process is lacking. There exists uncertainty even as to the primary driving force for grain growth, although there is a considerable body of indirect evidence that the interfacial energy of the grain boundary is responsible.7,8,10 Making implicit use of this assumption, several authors14,15 have pointed out that grain boundaries should migrate toward their center of curvature. Harker and Parker' have advanced this concept furthest, and show that one can expect grain boundary migration to occur only when the grain faces are curved, or when they meet at non-equilibrium angles. When the face is curved toward a grain A, for example, the atoms in the surface of grain B, on the other side of the boundary, are on the average more surrounded by the atoms of their lattice than the atoms on the surface of grain A. Because of thermal motion, the atoms at the interface will sometimes be attached to grain A and

Jan 1, 1948

By A.J. PHILLIPS, Wm. B. Price

ADMIRALTY nickel is a new corrosion-resisting and heat-resisting white metal alloy composed of 70 per cent. copper, 29 per cent. nickel and 1 per cent. tin. It has been given the trade name "Adnic." In 1924, Win. B. Price1 described this alloy and its successful use as a diaphragm metal. The physical properties of Adnic at ordinary and elevated temperatures were given in Mining & Metallury.2 A patent3 was granted on Adnic, April 28, 1925. Work was first started on this alloy during December, 1921. An investigation of the patent situation in this country and abroad, and also a search of the literature, did not reveal any work on the ternary diagram, copper-nickel-tin; and the only wrought copper-nickel-tin alloy found was that known as "Newloy," composed of copper, 64 per cent.; nickel, 35 per cent.; tin, 1 per cent. This was being manufactured and sold by Wm.. Gallimore & Sons, Ltd., Sheffield, England, for unplated spoon and fork stock, and first came to our attention in January, 1922. The preliminary work in connection with the development of Adnic was started by casting four, binary copper-nickel alloys of the compositions shown in Table 1. Various amounts of tin were added to each of these mixtures, to produce the series of ternary copper-nickel-tin alloys also given in Table 1. A 200-gm. sample of each of these was cast by melting in a clay graphite crucible and allowing the melt to slowly cool with the furnace. A longitudinal section from each of these castings was polished and etched for-examination. The castings were not homogeneous solid solutions, but showed the usual cored structure associated with cast alloys. However, from an examination of these sections we roughly determined

Jan 1, 1928

By Lyall Zickrick, R. S. Dean, F. C. Nix

The first attempt to establish an equilibrium diagram of the lead-antimony series was made by Roland-Gosselinl in 1896. This investigation classified the system as a purely eutectiferous one, with the eutectic at 12.5 per cent. antimony and 228" C. In the next year, Stead2 placed the eutectic temperature at 247' C. The error in temperature made by Roland-Gosselin, however, has been perpetuated in the literature with a remarkable degree of persistency; this value was accepted by Campbell (1902), and Ewen (1910),3 and will be found in the last edition of Desch's3 Metallography (1922). Gonterman's investigation, made in 1907, was the most complete one available at the time .the present investigation was started. He concluded4 that the system was a simple eutectiferous one and placed the eutectic at 13 per cent. antimony and 247° C. Other investigations by Tammann (1907),5 Garbow (1909),6 Rudolfi (1910),7 Loebe (1911),8 and Leroux (1913)9 added little, if anything, to Gonterman's diagram. A number of investigations have been made of physical properties of the alloys. The electrical conductivity of the series was studied by Matthiessen (1860)10 and by A. W. Smith (1921);11 the thermoforce by Rudolfi (1910),12 and Pelabon (1923) ;13 the specific heat by Durrer

Jan 1, 1926

By C. A. Zapffe

BOTH the foundryman and the theoretical metallurgist are now generally agreed that the anomalous "rising" or "bleeding" of certain ferrous castings of killed metal is primarily attributable to hydrogen. How and why the phenomenon occurs, however, have not been made clear. The following discussion is intended to harmonize foundry experience with metallurgical theory so that the foundryman may possibly improve his ability to prognosticate whether a certain casting may bleed or not. BLEEDING, RISING, AND PIPING The "rising" to be discussed here is not to be confused with the action in rimming ingots as a result of the carbon-oxygen reaction, although a conclusion will be drawn that may apply to the art of controlling the rimming action. Only killed metal is considered, which includes both steels and irons. In Fig. I, three killed, chill-cast ingots are shown: a porous ingot whose evolution of gas during late stages of solidification has ejected metal through the top; an ingot in which moderate gas evolution during solidification has lifted the mushy central metal, i.e., it has "risen"; and, third, a sound ingot with good piping characteristics. The first type is referred to as "bleeding," and generally infers that a solid skin had first formed through which the liquid metal later erupted. There is no fundamental distinction between bleeding and rising in reference to killed metal.* POROSITY Hydrogen appears as a cause of bleeding because the gas evolution simultaneously leaves a porosity of a type traceable to hydrogen. Twenty years ago, Melmoth1 noted that killed steel that rose unexpectedly in the mold, if returned while liquid to the furnace and heated further under a reducing lime slag, would again rise in the mold; but that if the ingot were allowed to solidify and was then remelted no rising occurred. A critical quantity of the responsible gas is therefore removed by the rising action. Melmoth associated rising with high silicon (0.7 to 0.9 per cent) and concluded that silicon increased gas absorption. Because silicon is a strong deoxidizer, oxygen must, therefore, be eliminated from consideration of the three common gases in steel-oxygen, nitrogen, and hydrogen. Butterworth2 later decided that pinhole porosity was caused by gases dissolved in the metal and that hydrogen was obtained from steam in the mold. Allen's classical work on copper castings,3 soon followed by

Jan 1, 1942

By C. A. Zapffe

BOTH the foundryman and the theoretical metallurgist are now generally agreed that the anomalous "rising" or "bleeding" of certain ferrous castings of killed metal is primarily attributable to hydrogen. How and why the phenomenon occurs, however, have not been made clear. The following discussion is intended to harmonize foundry experience with metallurgical theory so that the foundryman may possibly improve his ability to prognosticate whether a certain casting may bleed or not. BLEEDING, RISING, AND PIPING The "rising" to be discussed here is not to be confused with the action in rimming ingots as a result of the carbon-oxygen reaction, although a conclusion will be drawn that may apply to the art of controlling the rimming action. Only killed metal is considered, which includes both steels and irons. In Fig. I, three killed, chill-cast ingots are shown: a porous ingot whose evolution of gas during late stages of solidification has ejected metal through the top; an ingot in which moderate gas evolution during solidification has lifted the mushy central metal, i.e., it has "risen"; and, third, a sound ingot with good piping characteristics. The first type is referred to as "bleeding," and generally infers that a solid skin had first formed through which the liquid metal later erupted. There is no fundamental distinction between bleeding and rising in reference to killed metal.* POROSITY Hydrogen appears as a cause of bleeding because the gas evolution simultaneously leaves a porosity of a type traceable to hydrogen. Twenty years ago, Melmoth1 noted that killed steel that rose unexpectedly in the mold, if returned while liquid to the furnace and heated further under a reducing lime slag, would again rise in the mold; but that if the ingot were allowed to solidify and was then remelted no rising occurred. A critical quantity of the responsible gas is therefore removed by the rising action. Melmoth associated rising with high silicon (0.7 to 0.9 per cent) and concluded that silicon increased gas absorption. Because silicon is a strong deoxidizer, oxygen must, therefore, be eliminated from consideration of the three common gases in steel-oxygen, nitrogen, and hydrogen. Butterworth2 later decided that pinhole porosity was caused by gases dissolved in the metal and that hydrogen was obtained from steam in the mold. Allen's classical work on copper castings,3 soon followed by

Jan 1, 1942

By H. H. Podgurski, F. N. Davis

In silver alloys containing less than 0.2 wt pet Cu. the reaction 9 + 1/2 0, = CuO(s) was found to proceed to equilibrium between 700o and 808oC. From measurements of the equilibrium dissociation pressures of the CuO at several temperatures, the differential heat of solution and the activity coeflicients for copper in silver were calculated. These values were found to be in reasonable agreement with those calculated from data appearing in the literature. A metastable "copper oxide" with an atom ratio of oxygen to copper as high as 1.7 was formed by internal oxidation at 300°C of these same dilute Ag-Cu alloys. No anomalous behavior was noted in the temperature dependence of oxygen solubility in silver. The solubility minima between 300" and 800°C reported several years ago can be accounted for, at least in part, by reactions with trace impurities, such as copper. Cold-worked siloer exhibits an enhanced permeability to oxygen. THIS investigation was undertaken because of our interest in interactions between solute and lattice defects in metals. The reason for the choice of the O-Ag system for study is the anomaly in the solubility of oxygen in silver reported by Steacie and Johnson1 in 1926, specifically that isobars between 100 and 800 Torr show solubility minima at 400°C. It was also claimed that the copper impurity in the silver was not responsible for the minima. Recently, Eichenauer and Müller2 proposed that surface adsorption might have been responsible for this solubility anomaly, but no adsorption isotherms are available to check the pressure and temperature dependence observed at the low temperatures. Surface-tension measurements on silver made by Buttner, Funk, and udin3 suggest that a considerable fraction of a monolayer of oxygen exists on silver at 922°C and at an oxygen pressure of 150 Torr. To account for the pressure sensitivity reported by Steacie and Johnson1 at 300°C, the oxygen bound to the surface at 922°C cannot be considered relevant; the existence of a surface layer at 300°C characterized by a lower energy of binding would be required to explain the effect. All of our attempts to detect an interaction of this type with surface sites have failed. In this investigation we have not been able to associate the dissolution of oxygen in silver with a dislocation interaction. Evidently, severely cold-worked silver does not contain a sufficient number of trapping -sites for oxygen. Indeed, our work shows that oxidation of trace impurities in the silver was probably responsible for Steacie and Johnson's results. In addition, we have been able to establish the nature of the reaction with copper impurity in silver by thermodynamic considerations. EXPERIMENTAL PROCEDURE Measurements of both the internal oxidation rates and the solubility were made volumetric ally in a system equipped with a gas burette, a mercury manometer, a McLeod Gage, and a mass spectrometer. The silver and the silver-alloy samples were protected from contamination by mercury vapor from our pressure gages by suitably placed refrigerated (-78°C) traps. Silica reaction vessels were employed for experiments performed above 500°C. Spectroscopically pure gases were used in this investigation. The highest-purity silver used in the solubility measurements was 99.999 pet. By chemical analysis 2 ppm of Cu were found in this silver. The two Ag-Cu alloys used in this research were made up to 0.14 and 0.15 wt pet Cu starting with 99.999 pet Ag. An unexpected source of error was discovered in the course of the work. At temperatures near 800°C silver distilled from the hot silica reaction tubes into cooler regions of our system. Although the weight loss of silver from the sample was not important in itself, oxygen was being consumed by the silver distilled into the cooler part of the system to form a stable oxide phase from which the oxygen was not recovered. In a separate experiment conducted to determine the necessary correction, losses between 0.2 and 0.3 cu cm (stp) of 0, in 24 hr were measured at 810°C. On the assumption that the flux of silver from the vessel to form Ag2O de-

Jan 1, 1964

By Bryan J. Travis, Thomas L. Cook

INTRODUCTION Our growing concern for adequate and secure sources of energy and minerals has stimulated vigorous exploration for new sources, research toward a better understanding of geological processes, and development of new extraction technologies. The need for control, or at least prediction, of subsurface fluid flow is important for many of these technologies for example: primary, secondary and tertiary recovery of oil; ground water and waste management; in-situ fossil energy extraction (oil shale, coal, tar sands); and solution mining of uranium, copper and other minerals. These technologies, especially the last two, are characterized by highly complex systems. A partial list of the physical processes occurring would include flow in porous/fractured media, multi-phase and multi-component flow with heat transport, chemically active fluids and soils, tracers, diffusion and dispersion, fracturing and dissolution. A great deal of understanding of how these processes behave and interact can be obtained from models. MODELS Theoretical models are valuable because they: 1) provide a frame of reference for interpreting results of laboratory and field experiments; 2) once validated by experiments, allow a variety of geometries, injection/production strategies, etc., to be examined (at relatively low cost) for efficiency and stability; 3) can provide guidance to the design of experiments and field operations. Most models are based on the fundamental principles of mass, momentum and energy balance. But from this starting point, many paths can be taken. For example, there is the theory of Payatakes (1973) which concentrates on the microscale dynamics. In this approach, the rock or soil matrix is represented by a complex of characteristic channels (such as periodically constricted smooth tubes). Detail of flow within the characteristic channel is calculated very accurately. A difficulty with this model is that description of a representative channel can require several parameters which may not be easily measured. Also, it is not clear how the channels can be combined practically to model a large scale flow. Another type of model is the "global" one described by Bear (1972). Here, the continuum equations for conservation of mass, momentum and energy are averaged over a distribution of pore channels, resulting in a set of conservation equations in which the small scale structure of the medium is replaced by quantities such as porosity, permeability, dispersion coefficients and tortuosity. This approach allows computation of large scale flows. However, additional constitutive equations are needed which relate averaged quantities such as permeability to observables such as local saturation, particle size distributions, and others. An important difference between models is the way they handle the momentum equation. Payatakes' model solves the full equation. In others, it is replaced by a simpler relation such as Darcy's law (valid for slow flow rates) or by Forchheimer's equation which extends Darcy's law to higher flow rates. These simple relations can nevertheless match a great deal of experimental data (Dullien 1975). The permeability term which appears in Darcy's law and in Forchheimer's expression has been related to other quantities such as porosity and particle surface area. The Kozeny-Carmen equation is a well-known example, valid for some ranges of porosity and particle sizes and for some materials. Several other semi-theoretical, semi-empirical formulations have been devised, none of which are entirely satisfactory. One goal of researchers has been the ability to predict permeability of a porous material from basic measurable quantities such as grain size distributions without recourse to adjustable parameters. This effort has proceeded from consideration of distributions of idealized, non-intersecting channels, to intersecting channels, to consideration of both distributed pore radii and pore neck radii. This last approach has been used successfully to predict permeabilities (ranging over several orders of magnitude) in sandstones (Dullien 1975). Additionally, studies on explicit networks of channels (e.g., Fatt 1956) and percolation theory (e.g., Larson et. al. 1981) have been used to examine interconnectivity effects in porous media with the hope of eventually being able to predict permeability accurately. To be of more than theoretical interest, a model must be compared s controlled laboratory conditions where boundary and initial conditions and relevant material properties can be accurately determined. Also, extraneous forces can be eliminated so that the interactions between processes of interest can be clearly seen and flow models can be vigorously tested. In contrast to the well-defined environment and

Jan 1, 1982

By J. T. Norton, A. L. Mowry

The monocarbides of the A subgroup elements in the fourth and fifth group of the periodic table in addition to being hard and refractory are of special interest in that they are isomorphous in crystalline structure. They are cubic with a sodium chloride type structure in which the metal atoms are essentially close packed in a face-centered cubic arrangement with the carbon atoms placed in the interstices between. Interstitial structures of this close packed type were first investigated systematically by Egg1 and he gave the rule for their formation, stating that the radius ratio of the nonmetal to the metal atom should not exceed the value of 0.59. The carbides of interest are those of titanium and zirconium of the fourth group and vanadium, columbium and tantalum of the fifth group. Table 1 shows the radius ratio using the Goldschmidt radii for 12 coordination for the metal atoms and the diamond radius for the carbon atom. It will be noted that while there is considerable variation in the size of the metal atom, in all cases the ratio is smaller than the limit of 0.59 placed by Hägg. It has been known for some time that these cubic carbides are soluble in one another, at least to some extent or, in other words, the metal atoms can be replaced, one by another without destroying the stability of the structure. Since the stability of these close packed interstitial substances appears to depend more upon geometry than upon the exact chemical nature of the atoms involved, it is of interest to examine the possibilities of replacement in these carbides in some detail. Hume-Rothery2 has pointed out the importance of the difference in size of solute and solvent atom as a factor in limiting the solubility in simple binary solid solutions. Largely on an empirical basis, he states that if the difference in size between solvent and solute atom is more than 14-15 pct of the solvent atom, the range of solubility is very restricted. The atom size was based on the distance of closest approach in the elements involved. While there is some question as to how one should calculate the size of the metal atom in the carbide structures, reference to Table 1 will show that zirconium is the largest and vanadium the smallest of the group and that the difference is about 15 pct. The Ti-Zr difference is about 9 pct and the others are smaller. Thus one would predict that if the size factor controls the solubility, all of the pairs except VC-ZrC would have wide or complete solubility whereas this latter pair is on the border line and might have restricted solubility. The purpose of the present investi- gation was to examine the solubility of the several pairs of carbides by heating them together until equilibrium was established and then examining the product by X rays. Previous Work Agte3 and his associates prepared various transition metal carbides and determined the melting points of binary mixtures. He concluded from the shapes of the melting point curves that there was extensive solubility in the case of the cubic carbides. Umanskii and his colleagues made an investigation of a number of pairs of the cubic carbides, using X rays and plotted lattice parameter vs. composition curves for the systems TaC-Tic, CbC-Tic, TaC-ZrC and CbC-ZrC. All pairs showed a continuous series of solid solutions. The first two pairs gave a linear relation while the latter two showed a negative deviation from Vegard's law. Kiefer and Nowotny, in a paper which became available after the present work was well advanced, investigated the binary pairs of the five cubic carbides by means of X rays. Relatively few points were obtained and results indicated that in some cases, at least, equilibrium was not reached at the temperatures used. The results indicated that solubility in the VC-ZrC system was not complete. All of the results of previous investigations indicated the desirability of a more detailed study. Materials The raw materials used were mono-carbides of titanium, zirconium, vanadium, columbium and tantalum and were the purest which could readily be obtained commercially. Spectrographic qualitative analysis showed that the CbC and TaC contained less than 1 pct

Jan 1, 1950

By G. Wakefield, A. H. Daane, D. H. Dennison, F. H. Spedding

Preparation of pure scandium metal was accomplished by calcium reduction of the fluoride by two methods; a low-temperatzdre alloy process and direct reduction with subsequent distillation of the product. The following properties were determined: melting point: 1181OK; boiling point (calculated): 3000°K; lattice constants at 298°K (hexagonal lattice): a = 3.308 * 0.001 A, c = 5.267 * 0.003A; calculated density at 298°K, g per cm3: 2,990 + 0.007; electrical resistivity, ohm-cm: 299°K, 66.6 ± 0.2 x 10 -6; 373oK, 77.4 * 0.2 x 10 -6; thermal coefficient at 299°K, ohm-cm per deg: 5.4 X x; heat of sublimation at 298°K, kcal pel- mole: 80.79. The vapor pressure was determined as a function of temperature between 1505o and 1748°K, with the data fitted to a straight line shielding the equation: Log Pmm = -1.718 X 104/ToK + 8.298. SCANDIUM, element number 21, was first discovered by Nilson in 1879 and was recognized as the Ekaboron as predicted by Mendeleff. As it is in group III of the periodic table, the general properties are a little like aluminum and also resemble quite closely the properties of yttrium and the rare-earth metals, in both the metallic and ionic form. Although the earth's crust contains approximately 5 ppm of scandium (the element is as abundant as arsenic and twice as abundant as boron) it generally occurs so widely distributed that it has earned the reputation of being very rare. The one exception to this is the mineral thortveitite, which has been found in Madagascar (20 pct Sc2O3) and in Norway (35 pct Sc2O3). Scandium also occurs in small but distinct amounts in uranium and rare-earth ores; the recent larger scale processing of these materials has made some scandium available from these sources. As with other naturally-occurring monoisotopic elements (except Be), scandium contains an odd number of protons and an even number of neutrons. Scandium metal was first prepared by Fischer and coworkers1 in 1937 by electrolysis of scandium chloride in a molten eutectic mixture of lithium and potassium chlorides, using molten zinc as a cathode and collector of the scandium metal produced. The zinc was removed from the Zn-2 pct Sc alloy by vacuum distillation, leaving a product reported to be 94 to 98 pct Sc, with the main impurities being iron and silicon. They reported a melting point of 1400° C for this material. Scandium has also been prepared by the reduction of scandium chloride with potassium metal in a glass apparatus by Bommer and Hohmann in 1941,' resulting in a mixture of metal and potassium chloride; these workers did not isolate the metal proper, but the X-ray diffraction of the slag-metal mixture showed it to be hexagonal with a = 3.30A, c = 5.45A. petru3, 4 and coworkers have recently reported the preparation of the metal in a compact form by the reduction of either ScF3 or ScC13 with calcium metal and subsequent distillation of the product. This process probably yielded a metal of high purity, but they list no chemical analysis nor do they list any of the properties of their product. Previous related work in this Laboratory has been concerned with the production of yttrium and the rare-earth metals and the determination of their physical properties. Because of its similarity to these metals, scandium is being included in this study. PREPARATION OF SCANDIUM METAL The preparation of yttrium and the rare-earth metals may be accomplished by reduction of their fluorides with calcium metal in tantalum crucibles.5 This process leads to the introduction of tantalum (up to 0.5 pct) as an impurity in the higher melting rare earths, but since the tantalum occurs as dendrites, uncombined with the rare-earth metals, its presence is not objectionable in some cases. The preparation of scandium metal in this manner, however, was found to yield a product containing 2 to 5 pct Ta. To obtain a purer product, the following two methods were developed for the reduction of scandium fluoride with calcium metal: i) a low-temperature process utilizing zinc to form a low

Jan 1, 1961

By G. W. P. Rengstorff, H. B. Goodwin

A method is described for purifying iron in batches of 150 Ib or more. Oxygen, carbon, nitrogen, and sulphur are removed from flakes of electrolytic iron by treatment in wet and then dry hydrogen. A special consumable-electrode arc furnace is used to remove hydrogen and to melt the flakes into ingots. A LTHOUGH iron and steel have been made and used for hundreds of years, there are still wide gaps in the knowledge of these metals. One reason for this is that the true properties of the base metal, iron, are not well known, simply because really pure iron has never been readily available for research purposes. Commercial iron, and even the "pure" irons which are readily available, are really complex alloys of iron with oxygen, nitrogen, hydrogen, carbon, sulphur, silicon, and other elements. With such materials, it has not been possible to prepare steels and other iron-base alloys in which all elements are present in exactly controlled amounts. It is an almost impossible task to determine the separate effects of each element or the intereffects of several elements unless alloys can be prepared containing only the desired elements. The ability to make controlled alloys of low impurity content is of far more than academic interest. It will assist in the study of such practical problems as the brittle failure of ship hulls or high pressure gas pipelines, determination of the factors which affect the deep-drawing properties of steels, the improvement of magnetic and electrical properties, the phenomenon of aging, and many others. In 1949, the American Iron and Steel Institute asked Battelle Memorial Institute to prepare high purity iron on a larger scale than had been attempted up to that time. The work was directed toward the preparation of iron as low as possible in carbon, oxygen, nitrogen, hydrogen, and sulphur because these are the contaminating elements of major interest in many research investigations on iron-base alloys. The initial goal was to prepare iron with not more than a few thousandths of one percent of each of these impurities. The purpose was to set up a "bank" of high purity iron on which researchers could draw when a supply was needed and which could be replenished from time to time as the stock became depleted. Of several possible purification methods, heating in hydrogen was selected as the most promising for the removal of both carbon and oxygen from solid iron. Metallic impurities are not removed by hydrogen. Electrolytic iron was chosen as a starting material because it is the most readily available form of iron low in metallic impurities. Decarburization and desulphurization were obtained by annealing in wet hydrogen at relatively low temperatures. The optimum temperature, as found by previous investigators,' is about 1400°F. This treatment also removes nitrogen. Deoxidation is favored by dry hydrogen and higher temperature. There is evidence from previous work that an anneal at 2200°F in dry hydrogen will deoxidize the iron, reduce the nitrogen content, and reduce the sulphur content. These facts suggested the use of a two-stage process: treatment in wet hydrogen followed by treatment in dry hydrogen. To carry out the purification process in a reasonable time, it was necessary that the iron be in thin pieces. Flakes of electrolytic iron were used. Because most research requires that the iron be in massive form, it was nccessary to melt the purified iron to consolidate it into large pieces. For this work, it was decided to prepare ingots weighing at least 15 lb by using a cold hearth arc-melting process in which the iron was melted in an inert atmosphere of argon or helium. This method of melting was selected because the water-cooled copper crucible is not wet by the iron and does not contaminate it as a refractory crucible would. Because the crucible is also the ingot mold, contamination from mold materials was also eliminated. Contamination from electrodes was avoided by making them from purified electrolytic iron. The melting procedure finally developed was an adaptation of the Kellogg electric ingot process.' Two batches of purified iron weighing about 100 Ib each in ingot form were prepared with analyses as shown in Table I. The remainder of this paper describes the procedures in more detail. In general, the process con-

Jan 1, 1956