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By J. A. Hren, G. Thomas

A high-temperature stage has been used to study precipitation and dissolution in thin foils of Al-20pct Ag alloy directly in the electron microscope. The results show that the aging characteristics are similar to those observed for bulk materials, and in addition, direct evidence is presented for clustering at the solid solution temperature. The limit of solubility of G. P. zones is-350°C. The heterogeneous precipitation, the growth and dissolution of ?&apos;have been studied in detail. Growth of ?&apos; parallel to the basal planes, occurs by continuous motion of inter -facial partial dislocations. Growth stops at intersecting particles due to formation of sessile a/6 <110> interfacial dislocations. Growth normal to the habit plane occurs by the spontaneous nucleation of partial dislocations on alternate (111) planes and the thickening rate is --10-3= times the lengthening rate. The precipitates dissolve in layers and the final product is a whole a/2 <110> dislocation . The nucleation -growth -dissolution processes are thus completely reversible. Kinetic data obtained from the dissolution rates of ?&apos;particles enable the diffusion coefficient to be determined and the activation energy is found to be 37.5(±4) kcal mol-1, which is that expected for dzffusion of silver in aluminum. The velocity of the interfacial dislocations is thus dependent solely on the rate of diffusion of silver atoms. RECENTLY it was demonstrated that a high-temperature stage could be effectively used in the electron microscope to follow directly the processes of precipitation and dissolution in thin foils of A1-4 pct Cu alloy.&apos; These experiments also provided kinetic data which enabled the diffusion coefficient to be estimated. This new development of electron metallography opens up many fruitful areas of research and it was decided to investigate the aging behavior in thin foils of A1-20 pct Ag alloy, particularly the mechanism of heterogeneous precipitation (i.e., precipitation on lattice defects). This system was chosen because the aging characteristics of bulk specimens are now well known,2"7 and because we wished to obtain more details of the role played by partial dislocations and stacking faults in the nucleation growth and dissolution of the hcp ?&apos; phase. This is of interest for the general case of fcc-- hcp transformations. Part of the A1-Ag phase diagram is shown in Fig. 1. The use of a high-temperature stage also enables a study to be made of the clustering process (formation of G. P. zones) and to determine the structure of the solid solution prior to the usual quenching and aging procedures. It is also possible to obtain kinetic data from measurements of the rates of dissolution of precipitate particles. Unlike the results of previous experiments on A1-4 pct CU 1 where much of the initial precipitation occurred on the foil surfaces, the results on the A1-20 pct A1 alloy were identical to those reported for bulk specimens6,7 and no surface precipitation was ever observed. Thus, it was possible to follow the aging sequence: G.P. zones — ?&apos; — ? directly in the thin foils. This paper is concerned with the formation and dissolution of zones and the ?&apos; phase, and no attempt has been made so far to follow the mode of discontinuous precipitation of ?. I) EXPERIMENTAL DETAILS The high-purity A1-20 pct Ag alloy was prepared by the Aluminum Co. of America in the form of 0.001-in.-thick sheets. These were cold rolled with intermediate anneals to a thickness of 0.0004 in.,

Jan 1, 1963

By M. Ahlers, Horace Pops

Slip features and formation of stress-induced mm-tensite have been studied in single crystals of fl phase Cu-Zn alloys in the composition range between 43 and 48 at. pct Zn. A phenomenological analysis is presented in which the glide planes and directions that me associated with the inhomogeneous shear in the martensite phase are predicted from the experimentally determined habit planes and macroscopic shear directions. It is shozun that the resolved shew component of the applied stress on the secondary shew system is a very important factor governing the formation of stress-induced martensite. A comparison is made between martensitic phases that form spontaneously upon cooling and those phases that arise from deformation. THE ß phase in Cu-Zn alloys is unstable and may transform spontaneously by a martensitic transformation1-3 during cooling. Thermoelastic and burst-type spontaneous martensitic phases have been observed3 in the composition range between 38 and 42 at. pct Zn. Martensite forms in alloys containing more than 42 at. pct Zn only by cold work below a temperature denoted as Md.4 Thus, alloys near the equiatomic composition can undergo a stress-induced transformation upon cold work at room temperature. Although data have been obtained concerning the effect of temperature5 and composition4 on the deformation of polycrystalline Cu-Zn alloys, it is rather surprising that few detailed studies6-8 on 6 brass have been conducted for single crystals where the stresses acting on crystallographic planes can be determined. A thorough understanding of transformation mechanisms requires knowledge of the role of stress and plastic strain. With this objective in mind we have made an investigation of the stress-induced rnartensite transformation in single crystals of 0 brass in the composition range between 43 and 48 at. pct Zn. Particular emphasis is given to the morphology and crystallographic features and a comparison is made between stress-induced and spontaneous martensite. I) EXPERIMENTAL PROCEDURE Master alloys having nominal zinc contents of 43, 45, and 48 at. pct were prepared from spectroscop-ically pure metals (>99.999 pct) in sealed quartz tubes under a partial pressure of helium. These alloys were cut into several pieces and converted into small rods by melting in quartz tubes. Subsequently, single crystals were grown from the rods by the Bridgman technique and homogenized for 3 hr at 820°C. Lattice parameter measurements were made from stress- relieved filings. Compositions, as determined from the reported variation of lattice parameter with atomic percent zinc,&apos; indicated a zinc loss of less than approximately 0.25 at. pct. The single crystals were electroturned using a phosphoric acid electrolyte into tensile specimens each with a center section of 1 mm diam and 1 cm gage length. Cylindrical specimens approximately 3 mm in diam and 10 mm long and spark-machined rectangular blocks approximately 3 by 3 by 10 mm were prepared for compression studies. These blocks were stress-relieved and electropolished to eliminate any stresses introduced by spark machining. Crystal orientations were determined to an accuracy of ±2 deg primarily from back-reflection Laue photographs, and sometimes by the rotating single-crystal method. Figs. 1 to 3 show the location of the tension and compression axes within unit stereographic triangles. All specimens were deformed plastically at room temperature using an Instron machine, the crosshead speed being 0.02 or 0.05 cm per min. A hard steel hemisphere was placed at the upper end of the compression samples to achieve uniaxial loading. Trace normals of slip markings and habit planes of strain-induced martensite were determined to an accuracy of ±4 deg from the rectangular blocks by a two-surface analysis and from cylindrical specimens by measuring the angle between the tensile (or compression) axis and the tangent to the surface trace for different rotations about the deformation axis. Slip

Jan 1, 1969

By C. G. Dunn, P. K. Koh

Microstructure, magnetic torque, and texture data before and after grain growth were obtained on two 3.25 pet Si-Fe specimens having initially the same cold-rolled textures and the same primary recrystallization textures. The latter textures consisted of four components, two only of which were strong; the strong components were near (120) [001] and (320) [001]. The textures of the two specimens obtained by grain growth were different. In one specimen the two weak components were converted into strong components by a secondary recrystallization process; in the other specimen the primary recrystallization texture was retained by a normal grain-growth process. The difference in behavior of the two specimens was interpreted in terms of a difference in the relative grain sizes between weak and strong components; i.e., in terms of a geometrical factor that would alter the early growth rates of grains belonging to the two weak components of the texture. Specifically the growth rate was considered as the product of two terms: a driving force and a boundary mobility. The texture changes observed are considered to favor the oriented-nucleation growth-selectivity theory more than the oriented-growth theory. WHEN primary recrystallization and grain-growth textures form as a result of annealing deformed metals or alloys, the fundamental processes involved are nucleation and growth. Knowledge, therefore, about nuclei and the factors influencing their growth is required not only for the understanding of texture development but also for its control. In the oriented-growth theory of texture formation1, 2, 3 the problem of nuclei is generally disposed of by the assumption that nuclei are available in all orientations; the theory then has to explain the final texture from the initial texture and the way boundary mobility depends on orientation. In the oriented nucleation theory of texture formation"&apos; nuclei are considered to be present only in certain orientations but the importance of growth selectivity is still recognized. For example, the mobility of boundaries of approximately the same orientation and of the coherent type in twins is believed to be low while that of high-angle boundaries, in general, is high. Because of this the theory may be described as an oriented-nucleation growth-selectivity theory. The main feature of the oriented-nucleation theory, however, is the importance given to nuclei; i.e., how they form in specific orientations and how they grow. In the present investigation two cold-rolled single crystals were used to study the effects of growth after primary recrystallization. The cold-rolled textures and the primary recrystallization textures were determined from portions of these specimens and reported earlier.",&apos; The two cold-rolled crystals were in the (111) [112] stable end orientation, the recrystallization textures were nearly identical and consisted of two strong components, designated M and M&apos;, which were near (120) [00l] and (320) [00l], respectively, and also some specific weak components near (111) [110] and (111) [110]. It is well recognized that a single strong component in the primary recrystallization texture may be needed for secondary recrystallization3, 5, 8 but unfortunately when this is the case the amount of material left in deviating orientation may be too small either for growth or for positive identification. The present samples proved to be almost ideal for the study of minor components and their influence on texture changes produced by growth after primary recrystallization. The results obtained are interpreted in terms of present knowledge of grain-growth processes. Experimental Procedure Two lots of silicon-iron alloy of essentially the same composition, namely, 3.25 pet Si, 0.004 C, 0.009 P, 0.010 S, 0.035 Mn, 0.070 Ni, 0.090 Cu, 0.009 Sn, with traces of A1 and Cr and the balance Fe, were converted into single crystals 0.025 in. thick and 1.25 in. wide. The orientations were predetermined by the method of reorienting a seed crystal as described elsewhere.3 pecimen 1 from one lot had the (335) [556] orientation while specimen 2 from the second lot had the (111) [112] orientation.* Both crystals were cold rolled to a reduction in thickness of 70 pet while widening approximately 20 pet. Samples of each were selected for determining 1) the cold-rolled texture, 2) the time required at

Jan 1, 1959

By R. Stickler, A. Vinckier

An optical and electron microscope study was made on a commercial 302 stainless steel heat treated for massive carbide precipitation. Convincirg evidence was obtained that the grain boundary precipitate does not grow away from the grain boundary into the matrix, but grows as a network of large thin dendrites in between the grains. IN austenitic stainless steels the carbon in supersaturated solution precipitates when the steel is heated in the temperature range 450" to 1000°C. During such heat treatments the chromium-rich carbide occurs primarily at the grain boundaries and has adverse effects on the corrosion resistance and low-temperature ductility of the material. It has been shown that the morphology of the precipitated particles differs widely depending on the time and temperature of the heat treatment, the nature of the boundary, the misfit between the grains, and so forth.1"5 It was assumed by Mahla et al.,&apos; Streicher,&apos; and Mc Nutt&apos; that the carbide particles which nucleate in the grain boundary grow in various geometric or dendritic forms away from the boundary into the matrix. However, Kinzel,&apos; Hatwell et a, and Plateau et aL4 found that the particles nucleate in the grain boundary and grow as a network of thin dendrites in the grain boundary interface. We have made a comprehensive studyg of the precipitation occurring in a commercial 302 austenitic stainless steel heat treated for times ranging from 0.15 to 1500 hr at various temperatures from 480" to 1065"~. This study was made to elucidate the influence of heat treatments on both the mechanical and the corrosion properties of this steel. Part of this investigation which is pertinent to the morphology of the grain boundary carbides referred to above is separately reported here. We found that the particles which nucleated in the boundaries grew in the interface of these boundaries, thus supporting the viewpoints of Kinzel,&apos; Hatwell et al.,3 and Plateau et al.4 Furthermore, when carbide particles nucleated in the matrix very close to the boundaries, they possessed a morphology distinctively different from the particles growing in the grain boundaries. MATERIAL A study of metallographic samples and of fracture surfaces of a 302 stainless steel is reported in this paper. The composition and heat treatments are listed in Table I. Polished and etched samples were examined und813r the optical microscope, and carbon extraction replicas of etched micrographic samples and various fracture surfaces3&apos;8&apos;9 were examined under the electron microscope. RESULTS AND DISCUSSION A representative optical micrograph of the 302 steel, condition A, is shown in Fig. l(a). Particles can be seen on the grain boundaries but no traces can be found of particles which grow from the grain boundaries into the matrix. A carbon extraction replica of this sample shows numerous large thin dendrites, Fig. l(b). The lateral dimension of such carbide particles vary up to 100 p, and their thickness estimated from the amoun! of electron penetration i:; between 500 and 1000A. Such large dendrites are extracted from almost all grain boundaries and, if they had grown into the grains, they would definitely be revealed by etching traces in the matrix, Fig. l(a). The reason why these large dendrites on the extraction replica appear to be grown into the grain is due to the mechanism of the extraction replica process. Thus, these dendrites are supported by the carbon replica film only at the edges originally along the grain boundary trace A-A, Fig. l(b), in the polished metal section and have subsequently fallen over onto the carbon replica film during handling. Although such dendrites generally fall only to one particular side of the grain boundary trace, one finds occasionally that parts of a dendrite have fallen to both sides, as shown in Fig. l(b). Further evidence for the growth of carbide in the grain boundary can be obtained from the appearance of fracture surfaces. A small impact specimen of the 302 steel, condition A, was broken at liquid nitrogen temperature. The fracture path follows the

Jan 1, 1962

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20&apos;- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes&apos;5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1&apos;8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.&apos; Esin and his coworkers5&apos;10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,&apos;~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,&apos;~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "&apos;~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

By J. L. Huitt, B. B. McGlothlin

The introduction of new fracture propping agents that are brittle but much stronger than sand created the problem of what loading strength is required for a propping agent to be effective in a given formation. It is shown that the load at which the propping agent crushes should exceed the load at which total embedment in the fracture faces is possible. Simple laboratory tests to determine loading strength of the propping agent and embedment in the fracture faces, and use of these data in selecting a propping agent for a given formation, are discussed. INTRODUCTION One of the most important factors in the design of hydraulic fracturing treatments is the selection of a propping agent that can effectively provide the fracture flow capacity needed for stimulation of a well. Sand, once generally accepted as being synonymous with propping agent in hydraulic fracturing, is now recognized as having limited effectiveness in many formations because of its low resistance to crushing. Sand particles are brittle and have relatively low strength. Because of this property, sand particles are crushed in rocks that offer high resistance to the penetration of fracture faces by the proppant particles when the fracture attempts to close under the action of the overburden load. For rocks that offer a high resistance to penetration, deform able particles are more effective propping agents than sand. However, for this same type of rock, a propping agent that does not deform, yet does not crush, is often more effective. Thus, a rigid propping agent with sufficient strength to prevent crushing is desirable. A method for determining the strength required for a rigid propping agent to function effectively in given formations is discussed. BEHAVIOR OF RIGID PROPPANTS AND FRACTURE FACES RELATED STUDIES An early qualitative description of the reaction of propping sand in fractures was given by Hassebroek et al.&apos; In discussing fracturing in deep wells, the authors mentioned that even though propping sand entered the fractures, a high flow capacity did not result due to crushing or embedding of the propping sand. Dehlinger et al.2 in discussing the reaction of propping sand surmised that, because of the hardness of sand particles, deformation occurred in the fracture faces contacting the propping sand. In later studies,3,4 methods of determining the embedment of propping sand in fracture faces of soft rock and the critical load at which propping sand is crushed by the fracture faces in hard rock were discussed. In working with de-formable proppants, Kern et al. considered proppant particles to be deformed into cylindrical disks by action of the overburden and then pressed slightly into the fracture faces by further action of the overburden. Rixie et al.&apos;0 reported on embedment pressure and presented a method of selecting a propping agent for use in given formations. The propping agents included sand, walnut shells and aluminum pellets. All these studies have contributed materially to a better understanding of propping agent behavior; however, the strength of brittle proppants (sand, glass and ceramics) required to result in embedment rather than crushing has not been discussed. This topic will be covered in the ensuing discussion. PROPPANT PARTICLE CRUSHING—-EMBEDMENT For this discussion, a rigid propping agent is considered to be one that is brittle and fails under tensile stress when loaded to a critical value. In an earlier study4 it was shown that the Hertzian4 loading theory could be applied to a spherical brittle propping agent if the propping agent and fracture faces behaved elastically. At the failure of the proppant, the ratio of the load to the square of the diameter of the particle should be constant for a given material combination, or: Lc/dp2=C ............(1) A partial derivation of this equation from proppant and formation properties is included in the Appendix. Should a rigid particle not be crushed as a load is applied, it embeds in the fracture faces. A study3 of particle embedment in fracture surfaces has been published. The embedment can be described by an equation based on Meyer&apos;s metal penetration hardness relationships: d1/dp=B 1/2[L/dp2]m/2..........(2) In Eq. 2, B and m are constants that are characteristic of the rock; the significance of the other terms is shown in Fig. 1. A STANDARD DEFINITION FOR PROPPANT LOADING STRENGTH Eq. 1 is useful in appraising propping agent strength," but it is strictly applicable only when the area of contact between a particle and a fracture face (or loading plate)

Jan 1, 1967

By Vittal S. Bhandary, B. D. Cullity

Swaged iron wire has a cylindrical {001} <110> texture. The texture is also cylindrical after re-crystallization in the absence of a magnetic field, but <111> and <112> components are added to this texture when recrystallization occurs in a field. The mecizanical properties in tension and in torsion are not greatly altered by these changes in texture. AS shown in a previous paper,1 cold-worked wires of the two fcc metals copper and aluminum can be made relatively strong in torsion and weak in tension, or vice versa, by proper control of preferred orientation (texture). The deformation texture can be controlled by selection of the starting texture (texture before deformation), because certain initial orientations are stable during deformation. The present paper reports on similar work performed on bcc iron. In this case it was clear at the outset that there was no hope of controlling the deformation texture, which is one in which <110> directions are aligned parallel to the wire axis. (1t has usually been regarded as a fiber texture, but Leber2 has recently shown that it is a cylindrical texture of the type {001} <110>. In either case, <110> directions are parallel to the wire axis.) There is general agreement on this texture among a large number of investigators, which in itself suggests that the starting texture has no influence on the deformation texture. More direct evidence was produced by Barrett and Levenson,3 who reported that iron single crystals of widely varying initial orientations all had a single <110> texture when cold-worked into wire. Thus <110> is a truly stable end orientation for iron and probably for other bcc metals as well. Under these circumstances attention was directed to the possibility of controlling the recrystallization texture. This texture is normally <110> in iron,4 just like the deformation texture. However, it is conceivable that this texture could be modified by a proper choice of the time, the temperature, and what might loosely be called the "environment" of the recrystallization heat treatment. In the present work the environmental factor studied was a magnetic field. The effect of heating in a magnetic field ("magnetic annealing") on recrystallization texture has been investigated by Smoluchowski and Turner.5 They found that a magnetic field produced certain changes in the recrystallization texture of a cold-rolled Fe-Co alloy. The texture of this material is normally a mixture of three components, and the effect of the field was to increase the amount of one component at the expense of the other two. Smoluchowski and Turner concluded that the effect was due to magnetostriction. With the applied field parallel to the rolling direction, the observed effect was an increase in the amount of the texture component which had <110> parallel to the rolling direction. In the Fe-Co alloy they studied, the magnetostriction is low in the <110> direction and high in the <100> direction. Thus nuclei oriented with <110> parallel to the rolling direction will have less strain energy than those with <100> orientations and will therefore be more likely to grow. In a later paper on the same subject, Sawyer and Smoluchowski6 ascribed the effect to magneto-crystalline anisotropy and made no mention of magnetostriction. In the papers of Smoluchowski et al. the intensity of the magnetic field was not reported but it was presumably large, inasmuch as it was produced by an electromagnet. In the second paper6 it is specifically mentioned that the specimens were magnetically saturated. But if magnetostriction has a selective action on the genesis of stable nuclei during recrystallization, that selectivity must depend only on differences in magneto-strictive strains between different crystal orientations and not on the absolute values of those strains. Thus the saturated state does not necessarily produce the greatest selectivity, because the relative difference in magnetostrictive strains between different crystal directions may be larger for partially magnetized crystals than for fully saturated ones.7 In the present work the specimens were subjected to relatively weak fields (0 to 100 oe) produced by solenoids. MATERIALS AND METHODS Armco ingot iron rod (containing 0.02 pct C and 0.19 pct other impurities) was swaged from 0.25 in. in diam. to 0.05 in., a reduction in area of 96 pct. The mechanical properties in tension and torsion were measured as described previously.&apos; Textures were measured quantitatively with chromium or iron radiation and an X-ray diffractometer,8,1 and

Jan 1, 1962

By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,&apos; metal purification,2&apos;3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10&apos;1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge&apos; or where melting is achieved, "dripping" from the charge is encountered.&apos;&apos; At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By Irving B. Cadoff, Ernest Levine

The fracture path in a Cu-4 pct Ag alloy wet with mercury was found to he dependent on the heat treatment used prior to tensile testing. Both quenched and slow-cooled alloys were embrittled by the mercury.. For quenched alloys, which were single -phase, the crack path was intergranular. Slowly cooled alloys, which contained precipitate platelets, exhibited transgranular fracture. By comparing stress-strain data for these alloys with similar data on mercury -embyittled solid-solution alloys, it was found that the role of the precipitate and that of the grain boundary in the fracture process were equivalent . THE fracture path which results when metals are strained in a liquid environment appears to be dependent upon the nature of the specific system. Mixed transgranular and intergranular cracking has been observed in the 2024 T4 aluminum alloy when wet with a Hg-Zn amalgam.&apos; Transgranular fracture was induced in an A1-4 pct Cu alloy by masking off the grain boundaries from the liquid Hg-Zn amalgam.&apos; The embrittlement of solid-solution alloys of copper in mercury results in intergranular fracture.&apos; The effect of a precipitated phase on the fracture path in copper alloys is the subject of the present investigation. Cu-4 pct Ag was chosen so that its behavior could be compared with previous work on embrittlement of copper alloys. PROCEDURE High-purity copper (99.999 pct) was used as a base metal, along with 99.999 pct purity silver. Melting was carried out in graphite crucibles with manual agitation to get adequate mixing. The ingots were homogenized by means of vacuum annealing, chemically cleaned, and cold-rolled with intermediate vacuum anneals, to the desired thickness of 0.025 in. The rolled sheets were sheared to the final specimen size of 1 by 0.025 by 0.1 in. The specimens were then electropolished in phosphoric acid (concentrated) and heat-treated in an evacuated capsule at the solution temperature of 770°C. One batch was slow-cooled and the other quenched in water. The thermal etching which occurred during heat treatment was sufficient to permit grain boundary and precipitate delineation. Tensile tests were carried out in air and in mercury on a Table-Model Instron at a pulling speed of 0.2 in. per min. Wetting was accomplished by electro-polishing in phosphoric acid, rinsing in alcohol, and immersing in a pool of mercury. Once wet the coating was stable throughout the mechanical tests. In our studies it was found that wetting the surface or total immersion in mercury produced identical results. For convenience, the wetting technique was used for the experiments described. The crack pattern was observed directly on the surface by removing the mercury after testing. De-wetting was accomplished by flame heating the samples in a vacuum after testing and before observation of the surface. No etchant or polishing was used so as not to obscure the crack pattern on the surface. The mercury removal, however, resulted in a pitted surface but otherwise left the pertinent features visible. Photomicrographs were taken in this condition so as not to disturb the structure associated with the crack pattern. The average precipitate spacing was measured previous to coating the sample with mercury by use of an optical eyepiece micrometer. RESULTS The microstructure of the quenched specimens was single-phase while that of the slow-cooled specimens contained thin platelets of a second

Jan 1, 1964

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" &apos; and the heats of mixing of Pr-Nd solid solutions&apos; have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By A.S. Richardson

AIR conditioning, or air cooling, for the improvement of ventilation in the Butte mines has come into increasing use during the past 10 years. In part, the methods practiced have been described in previous publications of the Institute, but some improvements on earlier methods have been made and a number of new features have been developed. This paper is presented as a record of progress made, and for the sake of completeness describes all general features of the work. The need for air conditioning in the ventilation of mines in the district arises from the fact that the temperature of the ground and mine water has shown a very great increase with increase in mining depth, and has now reached a maximum of slightly over 130°F. The most difficult part of the ventilation problem is the maintenance of temperature and humidity of a satisfactory standard in the working places, especially on the lower levels. Although ordinary ventilation is adequate to maintain good conditions in most of the working places it is subject to a number of limitations at great depth. Most important among these limitations is that with increase in depth the air becomes heated before it reaches the working places, both by compression from increase in atmospheric Pressure and by heat transferred to it from rock at high temPerature, so that its capacity for lowering temperatures is greatly reduced before it reaches the operating zone. Increasing depth of mining also increases the distance traveled by the air in its passage through the mine, and this causes a corresponding increase in resistance to air flow, so that there is greater difficulty in maintaining even the same volume in circulation. Thus, in the face of a demand that the ventilating system have a very much greater capacity to remove heat from the mine, the tendency is for that capacity to diminish. The only evident alternatives were (I) the opening of additional air shafts to increase the volume of air in circulation, (2) an extension of the existing system that would be subject to the same limitations, or (3) the adoption of an entirely different method such as air cooling. Fortunately for an economic solution of the problem, the mean annual temperature of the surface atmosphere at Butte is about 40°F., with very low relative humidity in summer, so that there is unlimited natural cooling power at a temperature range adaptable to air-conditioning methods. Methods Two similar methods of air conditioning are used, as necessitated by service requirements and dependent upon the equipment available. In one, which is the more important and has the greater cooling capacity, water is circulated in a closed circuit, and, alternately, first absorbs heat from warm mine air and then dissipates it in the surface atmosphere by cooling at a cooling tower. The second

Jan 1, 1943

By A. S. Richardson

AIR conditioning, or air cooling, for the improvement of ventilation in the Butte mines has come into increasing use during the past 10 years. In part, the methods practiced have been described in previous publications of the Institute, but some improvements on earlier methods have been made and a number of new features have been developed. This paper is presented as a record of progress made, and for the sake of completeness describes all general features of the work. The need for air conditioning in the ventilation of mines in the district arises from the fact that the temperature of the ground and mine water has shown a very great increase with increase in mining depth, and has now reached a maximum of slightly over 130°F. The most difficult part of the ventilation problem is the maintenance of temperature and humidity of a satisfactory standard in the working places, especially on the lower levels. Although ordinary ventilation is adequate to maintain good conditions in most of the working places it is subject to a number of limitations at great depth. Most important among these limitations is that with increase in depth the air becomes heated before it reaches the working places, both by compression from increase in atmospheric Pressure and by heat transferred to it from rock at high temPerature, so that its capacity for lowering temperatures is greatly reduced before it reaches the operating zone. Increasing depth of mining also increases the distance traveled by the air in its passage through the mine, and this causes a corresponding increase in resistance to air flow, so that there is greater difficulty in maintaining even the same volume in circulation. Thus, in the face of a demand that the ventilating system have a very much greater capacity to remove heat from the mine, the tendency is for that capacity to diminish. The only evident alternatives were (I) the opening of additional air shafts to increase the volume of air in circulation, (2) an extension of the existing system that would be subject to the same limitations, or (3) the adoption of an entirely different method such as air cooling. Fortunately for an economic solution of the problem, the mean annual temperature of the surface atmosphere at Butte is about 40°F., with very low relative humidity in summer, so that there is unlimited natural cooling power at a temperature range adaptable to air-conditioning methods. Methods Two similar methods of air conditioning are used, as necessitated by service requirements and dependent upon the equipment available. In one, which is the more important and has the greater cooling capacity, water is circulated in a closed circuit, and, alternately, first absorbs heat from warm mine air and then dissipates it in the surface atmosphere by cooling at a cooling tower. The second

Jan 1, 1943

By A. C. Heath, E. H. Dix

The importance of aluminum-silicon alloys in thc light alloy field is now generally recognized. Where silicon was once considered detrimental to the properties of aluminum, useful alloys now contain as much as 13 per cent. Furthermore, silicon is present as an impurity in aluminum of even the purest grades. Iron is another important impurity in aluminum and likc silicon is found in small quantities in the purest aluminum available today. The manner of occurrence of iron and silicon in commercially pure aluminum and many of its alloys exerts a very pronounced influence upon their properties. The effect of large quantities of iron in aluminum-silicon alloys is so detrimental that it has been found necessary to limit the allowable maximum percentage to as low a figure as is consistent with quantity production and satisfactory physical properties. The intimate relation existing between iron and silicon in aluminurn and alurninum alloys makes necessary a more complete knowledge of this ternary system. This paper is divided into two principal parts, dealing respectively with aluminum-silicon solubility equilibria and the constitution of aluminum-iron-silicon alloys. Part I.—Aluminum-silicon Alloys The early work on this system was largely confined to determining the general form of thc diagram and in this respect the results are in good agreement. Briefly, alulninunl and silicon form a simple eutectifcrous series without compounds. Until recently the solid solubility of silicon in aluminum had not been accurately determined. Ipraenkell (1908) stated that aluminum will retain 0.5 per cent. silicon in solid solu-t&apos;ion. Rosenhain, Archbutt and Hanson2 gave the maximum solubility as about 1.50 per cent. and added that "this solubility docs not appear

By W. A. Wood, W. H. Reimann

A study is made of the creep that can be induced in armco iron at room temperature by superposing small amplitudes of alternating torsion on a tensile creep load. It is shown that the creep differs from that in comparable tests on copper in being trmsient only. At the same time, though transient, the creep can produce extensions of some 10 pct under creep loads less than the tensile yield stress of the material. The creep can be largely suppressed b$ applying cyclic strain of suitable amplitude before applying the creep load and the metal thereby stabilized. At room temperature, plastic flow in a metal under steady load is normally limited by strain-hardening processes. However, if a small cyclic stress is superposed on the steady load these processes may be more or less neutralized and, as shown in recent investigations,&apos;-4 plastic flow may continue. In this way annealed copper, for example, can be induced to creep continuously to fracture under loads as small as 1 tsi. Dislocation mechanisms possibly responsible for this room-temperature creep have been usefully reviewed by Feltner.But discussion so far has been based mainly on creep as it is found in close-packed metals initially in the annealed state, and their behavior may not be general. In fact, recent work shows that the form of creep in annealed copper is different from that even in cold-worked copper;7 the creep thus depends on the dislocation pattern already in a metal as well as on the metal itself. This paper describes the creep in annealed armco iron, tested in the same way as the above-mentioned copper. One object was to see how creep in a typical bcc metal compared with that in the annealed close-packed metals. Another object was to utilize the fact that a bcc metal like iron has a more pronounced elastic range than close-packed metals like copper and to find to what extent the creep load or superposed cyclic stress had to exceed their re-

Jan 1, 1964

By N. A. Stockett

Southeast Missouri is the largest and oldest lead-producing district in the United States. For the year 1941, the statistical picture of pig-lead production, stated in short tons (partly estimated by the Engineering and Mining Journal) is as follows. Tons World production................. 2,000,000 United States Production .........- 460,000 Southeast Missouri production..... 142,000 The consumption of primary lead in the United States in 1941 was approximately 900,000 tons, or almost double the country&apos;s production. The largest previous year&apos;s in in the United States was 718,000 tons, in 1926. The largest quantities of lead are used for cable sheathing, storage batteries and white lead. During 1941 tetraethyl lead for auto and aviation gasoline consumed 50,000 tons of lead. The entire lead production of Southeast Missouri is now mined by the St. Joseph Lead Co., whose dominant position as the largest producer in the United States of lead directly from ores is best shown by the fact that in 1941 it produced approximately 31 per cent of the lead production of the United States from its mines in southeast Missouri, where 22,000 tons of ore, averaging over 3.00 per cent lead, is mined per working day. It is known that lead was mined at Mine La Motte, Madison County, Missouri, by Renault in 1723. Other white men and Indians probably did some mining prior to that time. Since 1865, the recorded production to Jan. I, 1942, shows that the St. Joseph Lead Co. and the various other companies that have operated in St. Francois County mined lead ore, which, after milling and smelting losses produced 5,980,000 short tons of pig lead. • About 95 per cent of the present lead production of Southeast Missouri is mined in St. Francois County. The northern part of this area is 60 miles south of st. Louis. The remainder of the lead is obtained at Mine La Motte, about 25 miles southeast from the center of the producing area in st.Francois county, Prospecting In this district, most of the ore is discovered by surface and underground diamond drills and by prospect drilling underground with rock drills. Each 2-ft. length of the cuttings from these Jack-hamer prospect holes is assayed for lead. These holes are marked and the records are entered on maps. It has been found that close drilling—100-ft. centers of holes, and sometimes less—is necessary in order to locate most of the smaller commercial ore bodies, many of which previously had been missed by drilling the areas with holes spaced 200-ft. centers or more. To date, geophysical and other methods of prospecting, apart from diamond and Mining Practices of the St. Joseph Lead Company in Southeast Missouri

Jan 1, 1943

By N. A. Stockett

Southeast Missouri is the largest and oldest lead-producing district in the United States. For the year 1941, the statistical picture of pig-lead production, stated in short tons (partly estimated by the Engineering and Mining Journal) is as follows. Tons World production................. 2,000,000 United States Production .........- 460,000 Southeast Missouri production..... 142,000 The consumption of primary lead in the United States in 1941 was approximately 900,000 tons, or almost double the country&apos;s production. The largest previous year&apos;s in in the United States was 718,000 tons, in 1926. The largest quantities of lead are used for cable sheathing, storage batteries and white lead. During 1941 tetraethyl lead for auto and aviation gasoline consumed 50,000 tons of lead. The entire lead production of Southeast Missouri is now mined by the St. Joseph Lead Co., whose dominant position as the largest producer in the United States of lead directly from ores is best shown by the fact that in 1941 it produced approximately 31 per cent of the lead production of the United States from its mines in southeast Missouri, where 22,000 tons of ore, averaging over 3.00 per cent lead, is mined per working day. It is known that lead was mined at Mine La Motte, Madison County, Missouri, by Renault in 1723. Other white men and Indians probably did some mining prior to that time. Since 1865, the recorded production to Jan. I, 1942, shows that the St. Joseph Lead Co. and the various other companies that have operated in St. Francois County mined lead ore, which, after milling and smelting losses produced 5,980,000 short tons of pig lead. • About 95 per cent of the present lead production of Southeast Missouri is mined in St. Francois County. The northern part of this area is 60 miles south of st. Louis. The remainder of the lead is obtained at Mine La Motte, about 25 miles southeast from the center of the producing area in st.Francois county, Prospecting In this district, most of the ore is discovered by surface and underground diamond drills and by prospect drilling underground with rock drills. Each 2-ft. length of the cuttings from these Jack-hamer prospect holes is assayed for lead. These holes are marked and the records are entered on maps. It has been found that close drilling—100-ft. centers of holes, and sometimes less—is necessary in order to locate most of the smaller commercial ore bodies, many of which previously had been missed by drilling the areas with holes spaced 200-ft. centers or more. To date, geophysical and other methods of prospecting, apart from diamond and Mining Practices of the St. Joseph Lead Company in Southeast Missouri

Jan 1, 1943

By B. H. Kear, S. M. Copley

Stress-stvain curves are presented for Ni3Al (y&apos;) cvystals in several ovientations, deformed in tension and compression at constant displacement rate, at temperatures from 70° to 2000°F. Both the yield stress and wovk havdening increase with temperature, with the magnilude of the effect dependent on ovientation. The yield stress maximum occurs at 1500°F in [001], at 1400°F in [011], and at 1200°F in [111]. The suppression of the yield stress peak in [011] and [111] orientatiorzs is due to the onset of cube slip, rather than octahedval slip, a1 elerated temperatures. The temperature and orientalion dependence of work hardening in nominal single slip orientations corvelates with changes in the CRSS ratio for octahedral slip and cube slip, in agreement with a model for work hardening based on pinning of screw dislocalions by cross slip from an octahedral plane into a cube plane. It is concluded that the unique plastic properties of y&apos; have a decisive influence on both ductility and strength characleristics of y +y&apos; nickel-base superalloys. It has long been recognized that the strength of y + y&apos; nickel-base superalloys depends on the precipitation of the y&apos; phase [basically Ni3(Al,Ti)]. This paper presents new data on the strength characteristics of single crystals of simple y&apos; (Ni3Al), and forms the first step in a systematic program aimed at elucidating the mechanisms of hardening in the complex commercial alloys. 1) EXPERIMENTAL PROCEDURE Single crystals of off-stoichiometric NiA1 were grown from the melt under vacuum by a modified Bridgman method. The melt was poured into a preheated alumina mold and crystal growth was promoted from one end by gradient cooling. The crystals were homogenized by annealing in hydrogen at 2400° F for 72 hr followed by furnace cooling. Chemical analysis of samples taken from several crystals gave an average composition of 88.2 wt pct Ni. Spectrographic analysis gave as the principal impurities in weight percent— Si (0.02), Mg (0.01), Fe (0.02), Ti (0.002), Cu (0.008), and Co (0.03). Tensile specimens with specifications as in Fig. 1 were prepared by a series of operations involving electrical discharge machining, precision grinding, and electropolishing. Compression specimens with dimensions 1/4 by 1/4 by -3/4 in. were prepared in a similar manner, except for the initial shaping operation using a precision cut-off wheel/two-circle goniometer unit to give selected crystal orientations. Specimens were deformed in a Baldwin-Wiedemann testing machine with furnace attachment, using a strain rate of 5 x 10-4 sec-1. The strain measuring device consisted of extension arms attached to the tensile grips (or compression plattens) at one end and leading out of the furnace to an LVDT at the other. Temperature was controlled by a thermocouple placed in contact with the specimen. According to the known phase diagram for the Ni/A1 system,&apos; when an alloy of the specified composition is cooled from the melt, primary y (nickel solid solution) dendrites grow at the expense of the liquid phase, which becomes enriched in aluminum. At the eutectic composition the remaining liquid freezes as a two-phase mixture of y + y&apos; (Ni3Al). Upon further cooling, a solid state transformation occurs, involving the precipitation of y&apos; in the primary dendrites, and the complete transformation of the eutectic mixture to massive y&apos;. The as-cast structure consists, therefore, of y + y&apos; dendrites with interdendritic regions of massive y&apos;, i.e., transformed eutectic, Fig. 2. 2) DISCUSSION OF RESULTS 2.1) Stress-Strain Curves. Fig. 3 shows tensile stress-strain curves for crystals in orientations close to [001] deformed at temperatures from 70° to 2000°F. Both the yield stress and total elongation are strongly temperature-dependent. At 70°F, easy glide is absent, and the work hardening coefficient BIT - G/300. At T > 1500°F, the negative slope of the stress-strain curves is due to pronounced necking in the crystals. The yield stress maximum at 1500° F corresponds with a minimum in the ductility, Fig. 4. The extensive duc-

Jan 1, 1968

By A. W. Schlechten, R. P. Abendroth

Equilibrium H2S/4 ratios were determined as functions of temperatunz and composition in a hydrogen recirculation apparatus. A high-temperature solid solution exists in the range two-phase regionfrom TiS 1.96, to TiS1.30, Various thermodynamic quantities were calculated from the data. COMPOUNDS in the titanium -sulfur system have not receiyed much attention in the past, probably because they do not occur naturally in the earth&apos;s crust. However, titanium-sulfur compounds have been used in various metallurgical processes. The U.S. Bureau of klines&apos; studied the formation of ti- tanium-sulfide mattes from charges composed of rutile, pyrite, and carbon, with the resulting sulfide matte being chlorinated to form titanium tetrachlo-ride. Fishel, Roe, and Ellis&apos; investigated the de-sulfurizing action of titanium in steels, and Schwarz and Koster studied the preparation of metallic titanium from the sulfide using aluminum and magnesium reduction. The thermodynamic properties of some of the compounds present in the titanium-sulfur system may prove to be of some use in the consideration of future processes using these sulfides, and would

Jan 1, 1960

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible&apos; and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By J. L. Gillson

In a brief summary of the many occurrences of fluorspar in our western states, it is not possible to go into detail in regard to the geology, mining and milling methods, and reserves about individual deposits. Rather a broad review is made of the occurrences and an analysis of how the western deposits may fit into our future domestic economy is presented. General Statement on Fluorspar Situation Fluorspar has been used for years as a flux in the manufacture of basic open-hearth steel, in foundry cupolas for melting pig iron, in the manufacture of opalescent glass and in the preparation of hydrofluoric acid. In 1880 the annual production of fluorspar in the United States was around 4000 tons per year. By 1900 it was up to 21,656 tons and between 1902 and 1908 it averaged about 40,000 tons annually. Prices were then so low, by present standards, that it seems impossible to believe now that mining could have been performed profitably at the price levels then prevailing. In 1890 fluorspar sold at the mines for $6.70 per ton, in 1901 for $5.81, in 1916 for 85.92. When the United States entered World War I, flyorspar production and price skyrocketed; the production reached 263,817 tons in 1918, with prices above $20.00 per ton, and prices were even higher in 1919 and 1920. After 1920, the domestic production fell from the 1918 level to about 125,000 tons annually and the average price dropped back to about $18.00 per ton. By 1935 the average price had fallen to $15.00, but in 1940 with a rising demand the average price of all grades had gone back up to $20.31. Today it is 75 per cent higher than in 1940 and presumably the price of acid grade at .least would be even higher if it were not for price ceilings. The first subsequent year that the domestic production exceeded that of 1918 was 1941, and the 1944 production is expected to exceed 400,000 tons, or over one and a half times that of 1918. In five-year periods, average production and imports were as are shown in Table I. Many people concerned with the consumption of fluorspar believe that the postwar period ahead will show a repetition of price trends of the last such period. They believe that imports will be again an important factor in the available supply and the price will fall back gradually toward the prewar level. The following basic factors are pertinent in analyzing this conclusion:

Jan 1, 1948