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By J. L. Gillson

Historically, rock deposits and sand deposits of titanium minerals came into production about the same time, although there may be some argument as to what is meant by production. Beach de- posits of heavy minerals in India (Figs. 1-4) and Brazil (Figs. 5) were worked for monazite about the turn of century, but as there was then no market for titanium minerals, these were thrown away. The rock rutile deposits at Roseland, Va., Fig. 6, were worked to supply rutile for titanium chemicals and for coloring ceramics long before there was a titanium pigment business. The pigment industry started about the middle twenties, both in Europe and the U. S., and almost simultaneously the rock deposits at Ponte Vedra Beach near Jacksonville, Fla., were worked for titanium content. Since those days, production from both types of deposits has continued to grow at a rapid rate; many deposits of both types have been found, and reserves have grown to very large figures. In total tonnage of reserves, there is no doubt that the rock deposits are far ahead of the sand deposits; nevertheless there is a very large tonnage of commercial sands available. It is the quality of titanium mineral in the sand and the relatively lower costs of operating sand deposits that have kept them abreast, at least in annual tonnage produced, with the rock deposits.

Jan 4, 1959

By R. C. Wilcox, R. V. Lawrence, P. A. Calhoun

The V-Rh-Si, Nb-Rh-Si, and Cr-Rh-Si systems were investigated to evaluate the extent of solid solubility between binary Cr3O structures. All Cr3O components lie within the favorable atomic size range1 for the formation of the Cr3O structure. Previous studies indicated complete solid solubility between V3Si and V3Sn2 and no solubility between Sn and cr3si3 or Si and Nb3Rh.4 The Cr3O structure is not found in the Cr-Sn and Nb-Si binary systems. Powder compacts were are-melted under argon, homogenized in a vacuum at 1000°C, and water-quenched. Alloys containing greater than 15 at. pet Si were annealed 100 hr. X-ray diffractometer methods were used to study all systems utilizing copper radiation for the Cr-Rh-Si system and chromium radiation for the other two systems. V-Rh-Si System. The alloys prepared in the V-Rh-Si system and the measured lattice parameters for the Cr3O structure found in each alloy are listed in Table I. The characteristic Cr3O diffraction pattern was found in all binary alloys. The measured lattice parameter of V3Rh (VRS-1) is in agreement with the reported value5 while the value for V3Si (VRS-5) is only in fair agreement.' In

Jan 1, 1965

By Peter T. Luckie, Harold L. Lovell, E. R. Palowitch, A. W. Deurbrouck, James K. Kindig

PART 1: DENSE MEDIUM SEPARATION by E. R. PALOWITCH and A. W. DEURBROUK INTRODUCTION During 1965, 64.9 percent of the 512 million tons of bituminous coal and lignite produced was cleaned mechanically, of which 95 million tons was cleaned by dense medium processes.l The percentage of bituminous coal and lignite cleaned mechanically by dense medium processes rose from 7.0 to 28.5 percent from 1938 to 1965. Dense medium separations include those coal preparation processes which clean raw coal by immersing it in a fluid having a density intermediate between clean coal and reject. As there is a general correlation between ash content and specific gravity, it is possible to achieve the required degree of removal of ash-forming impurities from a raw coal by regulating the specific gravity of the separating fluid. Dense medium processes offer the following advantages over other coal cleaning processes : 1. Ability to make sharp separations at any specific gravity within the range normally required even in the presence of high percentages of the feed in the range of e 0.1 specific gravity units. 2. Ability to maintain a separating gravity that can be controlled with ±0.005 specific gravity units. 3. Ability to handle a wide range of sizes (up to 14 inches). 4. Relatively low capital and operating costs when considered in terms of high capacity and small space requirements. 5. Ability to change specific gravity of separation to meet varying market requirements. 6. Ability to handle fluctuations in feed both in terms of quantity and quality. HISTORY Sir Henry Bessemer patented the first dense medium process in 1858. Solutions of the chlorides of iron, manganese, barium and calcium were proposed as separating liquids; the separation was made in a cone-shaped separator. One large-scale plant using calcium chloride was erected in Germany but soon was abandoned. The Chance process, using a mixture of sand and water, was first

Jan 1, 1968

By R. F. Mehl, J. K. Stanley

THE recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are employed.1 Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystallization is not a heterogeneous reaction within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress .4,5† The theory of recrystallization is not in advanced state; if recrystallization data were obtained in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed .27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert measurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now

Jan 1, 1942

By J. M. Locke

BRÜCKNER's revolving cylinders for roasting ores, etc., are now used at a number of the mills in Colorado and New Mexico, for the purpose of roasting and chloridizing silver ores, with highly satisfactory results, even from those cylinders of small size, erected before the many improvements of recent date. As examples of the larger improved cylinders, reference can be made to those erected at the Tennessee Reduction Works, Silver City, Grant County, New Mexico, and those which were built, in 1871, at the celebrated Caribou Silver Mill and Mines, Colorado, a mining enterprise which has proved so satisfactory as to have been lately sold to a Holland company for an enormous amount. These cylinders, as now constructed by Messrs. Lane & Bodley, of Cincinnati,, Ohio, are shown in Plate III, in which Fig. 1 is an elevation in perspective, Fig. 2 a longitudinal, and Fig. 3 a trans¬verse section. Fig. 4 is a sketch of a mill, with Brückner's cylinder. The exterior of the cylinder is a shell of boiler iron, 12 feet long by 5 feet 6 inches in diameter. The ends are partially closed with similar material, leaving in the centre a circular opening about 2 feet in diameter, bounded by a flange projecting several inches.. Upon one side is placed an opening closed by a hinged door. Upon the outside of the cylinder are bolted three bands, as shown in Fig. 1, in which the section of the first is square, and that of the third semi¬circular; the second, or middle band, is a strong spur gear. Passing through the cylinder are six pipes parallel to one another, in a plane at an angle of 15° to the axis of the cylinder; these pipes also lie in this plane at an angle of from 30° to 35° to the longitudinal, axis of the plane, as shown in Fig. 2, where the internal arrangement of the cylinder is seen, a perforated diaphragm being formed through part of the cylinder by means of perforated plates placed between

Jan 1, 1874

By W. B. Morrison

The principal factors influencing the total percent elongation of a lead-tin eutectic and several low-alloy steels which exhibit superplasticity were investigated. These factors are: a) Strain-rate sensitivity of the stress (m). b) Specimen geometry; in particular, diameter-to-length ratio (d0/l0), and surface irregularity (e.g. notches). A feature of the tensile deformation of a superplastic alloy is the early appearance of a neck which continues to extend throughout the test. As a result the total elongation is directly related to the diameter-to-gage-length ratio. The strain-rate sensitivity of the stress varies during extension, mainly because of microstruc-tural changes. A satisfactory correlation exists between the minimum strain-rate sensitivity and total elongation, as indicated in the equation shown below. Notches cause a considerable reduction in total elongation and their effect is greatest at high values of strain-rate sensitivity. An initial notch depth exists below which there is no appreciable effect on elongation. An equation relating elongation to strain-rate sensitivity and specimen geometry is proposed, THE total percent elongation of a tensile specimen is usually regarded as a measure of superplasticity. However, little attention has been given to the fact that total elongation is also a function of specimen diameter and gage length, even though the importance of geometry has long been recognized in the tensile testing of materials in which elongations are relatively small.* In the present study, the effect on superplas- tic extension of the ratio of specimen diameter to length was investigated and an analysis was made of strain distribution along the gage length. Superplastic alloys are characterized by having a flow stress sensitive to strain rate but relatively insensitive to strain.2"' In an earlier study,5 it was found that the strain-rate sensitivity of several low-alloy steels changed during the test and that the minimum value correlated best with total elongation. In the present study, the variation of strain-rate sensitivity during the straining of a lead-tin alloy was investigated. EXPERIMENTAL PROCEDURE Lead-tin eutectic alloy (32 pct Pb 68 pct Sn), made from high-purity lead and tin, was cast in the form of 1-in. diam rod. The rod was cold-rolled in stages to 0.25 in. diam and then swaged to 0.125 in. diam. Samples were cut from the rod at various stages of the mechanical working process. Tensile test specimens were then made by attaching threaded steel ends to the rods by an epoxy-base thermosetting adhesive which required a setting treatment of 2 days at room temperature. The rods were seated in the steel ends in holes approximately 0.01 in. oversize. The test pieces thus made were of various diameters and gage lengths. These were stored at a temperature of about -70°C (-94°F) until required for testing. The distribution of strain along the gage length of a specimen was determined at various stages of the tensile test. The lead-tin alloy was superplastic at room temperature and direct observations during testing were simple. The gage length was divided by reference marks into five initially equal units. These reference marks were made with ink and were reinforced during the test when the initial marks became faint. Photographs were taken, at intervals, of the deforming specimen and measurements of the elongation in each of the gage units were made on these photographs. Tests were also done on several superplastic low-alloy steels whose properties were described earlier.5 The chemical compositions of these steels are given in Table I. A diagram of the notched tensile specimen used in the steel tests is shown in Fig. 1. The specimens were tested at 900°C (1650°F) in a furnace through which a mixture of He + 2 pct H was continuously circulated.5 RESULTS Strain Distribution. Approximately 20 tests on lead-tin alloy specimens were conducted to determine the strain distribution during the test. An example is shown in Fig. 2 of the strain distribution in the gage

Jan 1, 1969

By C. H. Mathewson, P.W. Bakararian

The greatcr part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation. in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)' by geometrical analysis identified the plane in magnesium as the twinning plane. Schiebold and Siebel (1931) confirmed this twinning planc, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also rcported twin formation in a secondary role on the {IOI} plane. Schmid (1931)³ summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-—i.e., the critical resolved shear stress—were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C. at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the origince specimens of circular section had been

Jan 1, 1943

By C. H. Mathewson, P. W. Bakararian

The greatcr part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation. in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)' by geometrical analysis identified the plane in magnesium as the twinning plane. Schiebold and Siebel (1931) confirmed this twinning planc, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also rcported twin formation in a secondary role on the {IOI} plane. Schmid (1931)³ summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-—i.e., the critical resolved shear stress—were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C. at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the origince specimens of circular section had been

Jan 1, 1943

By Cyril Smith

A STUDY of the mechanical properties of the alloys of copper and silver led to the discovery that the solubility of silver in copper was greatly different from that generally supposed, therefore some work was done to determine the solubility with greater accuracy than had previously been achieved. After the work had been completed, two papers were published1 giving solubility figures which agreed closely with one another and with the work described herein. A detailed comparison of that work with the present will be given later. PREPARATION OF ALLOYS The copper used in making the alloys was electrolytic ingot of high purity. The silver was prepared by precipitation as chloride from nitric acid solution, followed by fusion of the washed precipitate with sodium carbonate and potassium nitrate. This method gives metal containing at least 99.99 per cent silver. The copper was first melted under charcoal in a small electric resistance furnace and the silver added as pure silver, it being unnecessary to make any intermediate alloys. After thorough stirring the metal was poured into a mold of suitable form. The alloys contained between 0.008 and 0.015 percent of oxygen. Small amounts of oxide were visible under the microscope, but it is not believed this would have much effect on the results. Copper-silver alloys are notorious for segregation, consequently a few experiments were carried out to find a form of casting with as little segregation as possible. A mold 6 in. long and 1/2-in. dia. was first used, and an alloy nominally containing 5 per cent silver was cast in it, while some of the same alloy was poured directly into water to obtain the maximum rate of cooling possible. Analyses were made both on this sample and on turnings from the top and bottom of the 1/2-in. dia. casting, the turnings being separated into three parts according to the position

Jan 1, 1931

By J. L. Huitt, J. L. Pekarek, D. K. Lowe

In a theoretical study of hydraulic jetting, the velocity of the abrasive material relative to the velocity of the fluid in the jet stream is analyzed as the jet stream moves through the convergent and straight sections of the nozzle and the region between the nozzle exit and target. The results revealed that the abrasive material exits from the jet nozzle at a lower velocity than the fluid. The exit pmticle velocity can be increased by increasing either the density of the fluid or the length of the nozzle, and/ or decreasing either the particle density or particle diameter. In the divergent jet stream, there exists a point after which the particle velocity exceeds that of the fluid. The relative velocities were considered in the derivation of an equation to predict cutting rate of a circumferential notch and maximum notch depth. Data of a general nature and data which substantiate the theoretical results were obtained experimentally. INTRODUCTION The use of a fluid containing an abrasive material has been an established technique for cleaning and cutting for many years. In the petroleum industry, the early effort to use this technique1 to perforate and/or to overcome wellbore damage met with only limited acceptance because of the short life of the jet nozzle. With the introduction of improved perforating techniques, and later, hydraulic fracturing, the use of hydraulic jetting as a well completion technique became even less appreciated. It was only in recent years that interest in hydraulic jetting was revived. Once this interest was revived, the results of surface tests stimulated the interest of the industry even more than the state of the technology probably warranted because many of the tests were not appropriate for down-hole conditions. However, because of the stimulated interest, the development of the jet nozzle progressed very rapidly to the point where the nozzle life was no longer a prob- lem. With this accomplished, the use of hydraulic jetting in well completion became an accepted practice in a short time. The purpose of this paper is to present a theoretical analysis of the hydraulic jet stream as it passes through the nozzle and travels to its target. With a better understanding of the jet stream and the effects of various parameters, the performance of the process can be predicted more accurately. Equations are presented for cutting rate as applied to circumferential wellbore notching that relate the jet stream make-up, notch configuration and formation material. Also, experimental data are presented on some factors pertinent to hydraulic notching that are not theoretically analyzed. RELATED STUDIES Most of the studiesl-5 reported in the recent literature have pertained to the more practical aspects of hydraulic jetting; i.e., the effects of certain parameters as interpreted from experimental results, and the application of hydraulic jetting in well completion. In reviewing the effects of various parameters, it is interesting to note the reported depths of penetration obtained under various imposed conditions. In general, the depths vary from a few inches to several feet; however, a depth of penetration of less than 6 in., as reported by Thompson,4 seems more realistic for the usual field practice of hydraulic jetting with sand in water for a period of 20 to 30 minutes. In addition to the practical aspects, the study of Brown and Loper5 included a theoretical approach to hydraulic jetting. Their study resulted in the development of a theoretical expression for the maximum depth of penetration if jetting were continued for an infinite time. An analysis of the equations presented reveals that the initial cutting rate is infinite. The equation expressing centerline velocity is that of Forstall and Gaylord,6 which is applicable for a jet stream exiting in a large stationary medium. Since practically all of the fluid pumped into a perforation (or cut) must flow back through the perforation prior to re-entering the wellbore, a description of the medium as finite and non-stationary seems more reasonable. Thus, in this

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid cobalt and a number of dilute cobalt alloys Was measured in the temperature range 1550" to 1700°C at nitrogen pressures to 1 atm. At 1600°C and 1 atm nitrogen pressure, the solubility in pure cobalt is 0.0047 wt pct [3.8 cu cm (stp) per 100 g Co]. The standard free- energy change for the solution reaction 1/2 N,(g) = gout pct in Co) is iF - 10,000 + 5.24 T cal per g atom N. The alloying elements Cv, Cu, Mo, Nb, Tu, W, and V increase the nitrogen solubility, while Al, Fe, Ni, and Si decrease the nitrogen solubility. THE solubility of nitrogen in cobalt was studied previously by Sieverts, Busch and Dodd,2 and Schenck, Frohberg, and Graf.3 Sieverts investigated the solution below the melting point of cobalt, and Busch and Dodd worked with the liquid metal; however, neither study found any solubility for nitrogen in cobalt. Schenck et al, reported a solubility of 0.005 wt pct N in cobalt at 1600°C. Seagle et al. 4 reported residual nitrogen in cobalt after electron-beam melting, although no reasons were ventured for the presence of this interstitial impurity. This investigation was undertaken to clarify these inconsistencies, and to provide additional data on atomic interactions in dilute metallic solution. EXPERIMENTAL PROCEDURE This study was well-suited to the Sieverts' method, which has not changed significantly since its introduction by Sieverts. 5 The apparatus was of the same design as that described by Humbert and Elliott, 6 with a reaction bulb similar to that reported by Weinstein and Elliott. 7 The buret was not water-jacketed, but the measured gas volumes were corrected for small changes in room temperature. The melt temperature was measured by a disappear ing-filament optical pyrometer sighted through a prism onto the melt surface. Temperature calibration was made based on a measurement of the melting point of pure cobalt taken as 1495°C. The difference between the reciprocal of the observed and the true temperatures was assumed to be a constant, neglecting the changes in emissivity with small additions of alloying elements. The total error in gas-volume measurement caused by accuracy limitations in reading the mercury level in the buret, variation in ambient temperature, and variation in melt temperature was about 0.5 cu cm. This represents approximately 10 pct of the total solubility, and is a larger relative error than in previous studies6-' because of the small nitrogen solubilities encountered in the present investigation. The source and purity of the materials used are listed in Table IA. Recrystallized alumina crucibles were used throughout the investigation. Examination of the crucibles after solidification of the melts showed no reaction or penetration. Alloying of the cobalt melt was accomplished with the dropping technique described by Humbert. 6 The investigation was started using cobalt from African Metals Corp. in shot form, but this material was not of sufficient purity and did not yield consistent solubility results. Sherritt Gordon Mines Ltd. cobalt was then used throughout the investigation. In experiments involving alloying elements which could react with oxygen dissolved in the melt, the cobalt was further refined by annealing at 1400°C in a dry-hydrogen atmosphere. This treatment, described by Woolley and Pehlke, 8 markedly reduced the oxygen content. The oxygen and nitrogen analyses of the cobalt used in this study are presented in Table IB. RESULTS Hot Volume. The hot volume was measured prior to each run and was 50 to 55 cu cm (stp) at 1600°C. It increased linearly with increasing pressure and decreasing melt temperature. Pure Cobalt. Measurements of the solubility of nitrogen in pure cobalt and the temperature coefficient of solubility are summarized in Table 11. At 1600°C and 1 atm nitrogen pressure, the solubility was found

Jan 1, 1967

By M. A. Dayananda, R. E. Grace

Vapor-solid diffusion couples were employed in a study of ternary diffusion in the single-phase copper-rich corner of the Cu-Zn-Mn system Interdiffusion coefficients were measured at three different compositions corresponding to the intersections of diffusion paths determined at 850°C. Intrinsic diffusion coefficients were determined at two compositions by the Philibert-Guy method. New relations between the various intrinsic diffusion coefficients are also presented. MOST of the investigations of ternary diffusion have been made with "sandwich" couples formed by welding together two homogeneous solid solutions with or without markers placed at the interface. With such couples Kirkaldy and his coworkers1,2 have determined interdiffusion coefficients which describe ternary diffusion in the substitutional alloy systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy3 have reported intrinsic diffusion coefficients for Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.4 The use of semi-infinite diffusion couples, for example, vapor-solid couples, where the diffusing species are supplied from a vapor source in contact with a diffusion disk, has so far been confined to studies of binary diffusion. Balluffi et a1.5,6 have successfully determined the interdiffusion as well as the intrinsic diffusion coefficients in several binary metallic systems employing vapor-solid couples with markers initially placed at the vapor-solid interface. They have also discussed the general advantages and limitations of such couples. Vapor-solid diffusion couples can successfully be employed in ternary diffusion studies. The importance of such couples in ternary diffusion lies in the fact that inert markers lie close to the vapor-solid interface, and the composition of the marker plane is virtually known before experimentation begins. Another minor advantage is that the method of Philibert and Guy4 may be used with three alloys instead of four. Lastly, the diffusion paths need not be S-shaped, as pointed out by Meijering7 for "sandwich" couples. The Cu-Zn-Mn system is convenient for ternary diffusion studies because of the large single-phase field in the copper-rich corner. The vapor pressure of zinc above such alloys is known, and X-ray measurements indicate that the molar volume is nearly constant over a wide range of compositions.8,9 It is the purpose of this paper a) to extend the analysis of Balluffi and seigle5 to permit an evaluation of interdiffusion coefficients in ternary vapor-solid couples, b) to use the method of Philibert and Guy to determine intrinsic diffusion coefficients with such couples, and c) to present experimental data on both interdiffusion and intrinsic diffusion coefficients for the Cu-Zn-Mn system at 850°C. INTERDIFFUSION IN TERNARY VAPOR-SOLID COUPLES The analysis of Balluffi and seigle5 is extended in this section to a vapor-solid couple where two solutes diffuse from a vapor source into a ternary solid solution. To take into account the expansion of the diffusion disk caused by the absorption of mass from the vapor phase, the total fluxes are expressed on the basis of a coordinate system that moves with the velocity of the vapor-solid interface; thus. where D3ij are the intrinsic diffusion coefficients,4 v(x, t) is the local Kirkendall velocity of mass flow, and F(t) is the negative velocity of the vapor-solid interface (x = 0). Both these velocities are based on a fixed coordinate system far removed from the diffusion zone. Using the continuity relations and Darken's method1' for a ternary system in which components 1 and 2 diffuse from the vapor phase into a solid of negligible vapor pressure, one obtains

Jan 1, 1965

By C. S. Smith

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhard Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Post-President; John Chipman, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretory. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Chairman- Dennis Carney John Chipman J. C. Fulton J. H. Hollomon H. H. Kellogg, A. E. Lee, R. Moddin, J. D. sullivan, and D.' Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: T. B. King, Chairman; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr., and P. T. Stroup. lnstitute of Metals DM lion: Robert Maddin, Chairman. F. Lincoln Vogel, Jr.. Vice chairman. W. A. Backofen R. W. Boliuffi J. H. Bechtold' M. B. Bever R: S. Busk C 6. Goetzel poul Gordon C. D. Grobom, Jr., Robert F. Hehe-mann R. I. Joffee F. i. Joumot Jr. lrvin R. Kromer, A. J. Leno. Horold Morgolfn, C. J. McHargue, Russell A. Meussner, J. B. Newkirk, H. W. Paxton, G. E. Pellissier, I. S. Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman. T. B. King, F. C. Laogenberg, W. O. Philbrook, and T. 0. Winkler. Publishod bimonthl by the American Institute of Mining Metollurgicol and Petroleum Engineers Inc., 29 West 39th Street, New York 16, N. Y. Telephone: PEonylvanie 6-9220. Subscription $20 par yew for non-AIME members in United States and North, South and Control Americo $25 foreign; $5 for AIME members. Single copies, $4.00, single copios foreign $5,00. The AIME is 1958 by the Amarican mode or opinion axpressed in it* publications ... Copyright by the Amarican lnstitute of Mining, MataIlurgicol, and Petrolum Engineers, Inc,. . . Reg. istered cable address AIME New Yark ... Indexed in Engineering Inderx, Industrial Arts ...Index and Chemicol Number5. Absrtracis . . . Second class postage paid at New York,Indor. N. Y., Industrialond Ann Arbor, Mich.

Jan 1, 1959

By M. J. Saarivirta, P. P. Taubenbla

This paper presents some high-temperature properties of copper-zirconium conductor alloy compared to copper-chromium alloy. Definite superiority of the copper -zirconium alloy over the copper-chromium alloy at high temperatures is shown. RECENT investigations have shown that cold-worked copper-zirconium alloy possesses good room-temperature strength, ductility, and conductivity and maintains most of its strength at temperatures up to 450°C (840°F). As a result, this alloy is now used for many applications, such as commutator segments, resistant welding wheels and tips, rectifier bases, electrical contacts, and so forth. Early investigations1-3 have shown that the maximum solid solubility of zirconium in copper is close to 0.15 pct and the alloy containing Cu-0.10-0.15 pct Zr exhibits the optimum mechanical and physical properties. Results2 have also shown that the alloy has better elevated temperature strength and ductility than copper-chromium and copper-silver alloys. The present investigation was undertaken to learn more about the elevated temperature properties of copper-zirconium alloy and to compare these properties with those of the copper-chromium alloy. WORK PROCEDURE The commercial copper-zirconium alloy, Amzirc was selected for this investigation. Because this alloy is composed of oxygen-free high-conductivity copper and 0.10-0.15 pct Zr, it was believed that possible disturbance from impurities would thus be negligible. Copper-chromium alloys used in this investigation contained 0.40 and 0.70 pct Cr and balance copper. The Cu-0.40 pct Cr alloy was a commercial brand, whereas the Cu-0.70 pct Cr alloy was made from OFHC copper and Cu-5 pct Cr master alloy. It was made in a graphite crucible under argon gas cover and cast. In the preparation of specimens, all three alloys were treated to give the optimum properties; thus the Cu-0.15 pct Zr alloy was solution annealed at different temperatures to determine the desirable solution annealing temperature. It was then cold worked and aged at 375" to 400°C (705" to 750" F). A solution annealing temperature of 1000°C (1830°F) was selected for the copper-chromium alloys because this temperature is widely used in commercial practice. The same alloy was aged at 450°C (840°F) after solution annealing and cold working. It was found that the maximum precipitation hardening of the copper-chromium alloy occurred at this temperature. When aged after solution annealing, the aging temperature was 500°C (930"F) for both alloys. The following properties were determined: 1) Tensile properties as a function of temperature. 2) Effect of solution annealing temperature on high-temperature tensile properties. 3) Stress to rupture strength at 350° and 400°C (660"to750°F). 4) Impact strength. 5) Electrical conductivity and resistivity as function of temperature. 6) Thermal expansion.

Jan 1, 1961

By R. W. Fountain, J. F. Libsch

ONSIDERABLE time and effort have been ex- pended recently in research designed to provide a better understanding of the solid state transformations leading to the permanent magnet qualities of many commercial alloys. The knowledge derived from these investigations has resulted in the development of new magnetic materials as well as improvements in some of the older materials. The permanent magnet qualities of the newer alloys having high residual inductions and high coercive force values, have been attributed to the precipitation of a second phase or an order-disorder transformation in a solid solution. The ternary Co-Fe-V alloys provide an interesting group of magnetic materials having a wide range of magnetic properties. The low vanadium alloys' possess soft magnetic properties similar to the binary Co-Fe alloys, while at higher vanadium contents (about 10 pct) interesting permanent magnet properties are obtained.2,3 Previous work by Nesbitt' on the ternary Co-Fe-V permanent magnet materials, resulted in the conclusion that the precipitation of a second phase, ?, was responsible for the permanent magnet qualities of these alloys. However, unlike the conventional precipitation hardening alloys, the ? phase, which is stable at high temperatures, is precipitated in the low temperature a phase upon aging. Recent work by Geisler and Martin"." has established that the order-disorder reaction inherent in the binary Co-Fe alloys is also present in the ternary Co-Fe-V alloys. On the basis of their investigation, it was proposed that ordering of the a phase is also a possible explanation of the mechanical and magnetic hardening in these alloys. Thus, it appears that the Co-Fe-V alloys are rather unique in that two solid state transformations are taking place which may account for the properties of these alloys. In view of these facts, the present investigation was undertaken to study the mechanism of mechanical and magnetic hardening in the 10 pct V-Co-Fe alloy with particular reference to the role of the ? phase; and to correlate the results of this study with other magnetic properties. In addition, the influence of increasing vanadium contents on the transformation of Co-Fe alloys was also undertaken to supplement the main objective of the investigation. Experimental Procedure The Co-Fe-V alloys used for study consisted of: 1—a commercial lot of Vicalloy I, a 10 pct V alloy, and 2—alloys prepared by powder metallurgy and containing 52 pct Co and 0 to 14 pct V, balance iron. The commercial alloy was received in the cast and forged condition and was used primarily for the detailed study of hardness, electrical resistivity, and magnetic properties of the 10 pct V alloy. The powder metallurgy alloys were prepared from electrolytic iron, commercial cobalt, and ferro-vanadium powders. The processing cycle was as follows: 1—Elemental powders were weighed and mechanically mixed for 24 hr. 2—Mixed powders were pressed at 60,000 psi into the form of bars 5/8 x 5/8 x 5 in. 3—Bars were sintered in an atmosphere of purified dry hydrogen for 24 hr at temperatures ranging from 1380" to 1340°C, depending upon the vanadium content. The as-sintered bars were cut in half; and one half was machined to 7/16 in. diam for thermal analysis. The remainder of the bar was hot forged to approximately 0.050 in. for X-ray diffraction analysis. Additional details of sample preparation are presented subsequently according to the type of test performed. Thermal Analysis Measurements One of the simplest and most widely used tools for determining phase relations as they change with temperature and composition is to study the rate of change of temperature of a material as heat is supplied or extracted at a constant rate. The thermal analysis method used in this investigation is the inverse-rate method described by Smith.'

Jan 1, 1954

By J. H. Henderson, J. Naar

The displacement of a wetting fluid from a porous medium by a non-wetting fluid (drainage) is now reasonably well understood. A complete explanation has yet to be found for the analogous case of a wetting fluid being spontaneously imbibed and the non-wetting phase displaced (imbibition). During the displacement of oil or gas by water in a water-wet sand, the porous medium ordinarily imbibes water. The amount of oil recovered, the cost of recovery and the production history seem then to be controlled mainly by pore geometry. The influence of pore geometry is reflected in drainage and imbibition capillary-pressure curves and relative permeability curves. Relative permeability curves for a particular consolidated sand show that at any given saturation the permeability to oil during imbibition is smaller than during drainage. ' Low imbibition permeabilities suggest that the non-wetting phase, oil or gas, is gradually trapped by the advancing water. This paper describes a mathematical image (model) of consolidated porous rock based on the concept of the trapping of the non-wetting phase during the imbibition process. The following items have been derived from the model. 1. A direct relation between the relative permeability characteristics during imbibition and those observed during drainage. 2. A theoretical limit for the fractional amount of oil or gas recoverable by imbibition. 3. An expression for the resistivity index which can be used in connection with the formula for wetting-phase relative permeability to check the consistency of the model. 4. The Iimits of flow performance for a given rock dictated by complete wetting by either oil or water. 5. The factors controlling oil recovery by imbibition in the presence of free gas. The complexity of a porous medium is such that drastic simplifications must be introduced to obtain a model amenable to mathematical treatment. Many parameters have been introduced by others in Iprogressing" from the parallel-capillary model to the randomly interconnected capillary models independently proposed by Wyllie and Gardner3 and Marshall4. To these a further complication must be added since an imbibition model must trap part of the non-wetting phase during imbibition of the wetting phase. Like so many of the previously introduced complications, this fluid-block was introduced to make the model performance fit the observed imbibition flow behavior. THE IMBIBITION MODEL ASSUMPTIONS The following assumptions are common to many two-phase models previously described. 1. The wetting characteristics of the medium are clearly defined. 2. When two fluids co-exist in the medium, the wetting phase will fill the smaller pores and the non-wetting fluid the bigger ones. 3. The pores have a circular cross section. 4. Apparent pore radii are related to the capillary pressure (drainage) by

By E. T. Turkdogan

The activity of sulfur was determined as a function of composition of ferrous sulfide by equilibrating with hydrogen sulfide-hydrogen gas mixtures at 670° , 800°, and 900". The present results supplement the available data over the composition range from 36.6 to 39.5 pct S. The X-ray lattice spacing measurements made are in accord with the available data and indicate that the limiting composition FeSl.008 may be taken for the iron-iron sulfide equilibrium. The growth rate of ferrous sulfide on iron was measured by reacting iron strips or blocks in hydrogen sulfide-hydrogen gas mixtures. Owing to the slow approach to equilibrium between the gas phase and the surface of the sulfide layer, The sulfidation experiments were carried out for several days. It is shown that the growth rate ullimately proceeds in accordance wilh the parabolic rate law. From the parabolic rate constants and the thermodynamic data on iron sulfide the self-difiusivity and chemical diffusivity of iron in ferrous bisulfide are evalualed. The self-diffusivity of iron thus derived zs found to increase with increasing sulfur content. THE ferrous sulfide known as "pyrrhotite" is a non-stoichiometric phase having a wide composition range from about 50 to about 58 or 60 at. pct, depending on the sulfur activity. RosenQvistl studied the thermodynamics of this phase over wide ranges of temperature and composition. Hauffe and Rahmel' and Meussner and ~irchenall~ studied the parabolic rate of sulfidation of iron in sulfur vapor. By using markers, these investigators showed that the iron cations were the predominant diffusing species in iron sulfide. This is confirmed decisively by the self-diffusivity measurements of condit4 who showed that the self-diffusivity of sulfur in ferrous sulfide is several orders of magnitude lower than the self-diffusivity of iron. Although much has been learned from these studies about the Fe-S system, further research on this subject was considered desirable for better understanding of the physical chemistry of iron sulfide. This work was confined to the study of the kinetics of sulfidation of iron in hydrogen sulfide-hydrogen gas mixtures. The results of this study are given in two consecutive parts. Part I, the present paper, is on the parabolic rate of sulfidation of iron and the diffusivity of iron in ferrous sulfide. The second paper, Part 11, is on the kinetics of the surface reaction between hydrogen sulfide and ferrous sulfide. EXPERIMENTAL Three types of experiments were carried out: i) equilibration of ferrous sulfide with gas of known E. T. TURKDOGAN, member AIME, is Manager,Chemical Metallurgy Division, Edgar C. Bain Laboratory for Fundamental Research, U. S. Steel Corp., Research Center, Monroeville, Pa. Manuscript submitted March 6. 1968. ISD sulfur potential; ii) X-ray studies of ferrous sulfide; and iii) measurements of the parabolic rate of sulfidation of iron. Equilibrium Studies. About 1 g of iron powder or foil. contained in a small recrystallized alumina crucible ind suspended from a calibrated silica spring, was reacted with a hydrogen sulfide-hydrogen mixture of known ratio until no further change in weight was observed. %hen the gas composition was changed and the new state of equilibrium was established after several hours of reaction time. The composition of the sulfide was obtained from the initial weight of the sample and the weight after equilibration. X-Ray Studies. The lattice parameters of some of the equilibrated samples were determined using the General Electric XRD-5 diffractometer with a cobalt tube (no filter) set at 40 kv apd 10 ma; the CoK, radiation was taken as 1.79020A. Observed 220 and 311 diffraction peaks of silicon served as an internal comparison standard to correct for possible misalignment of the goniometer. The lattice parameters of the sulfide phase were calculated from the corrected Bragg angles of the 110 and 102 peaks. Rate Studies. In the initial experiments attempts were made to measure the parabolic rate of sulfidation by measuring the gain in weight of a thin iron strip, -0.05 cm thick, suspended from a silica spring in the reacting atmosphere. The preliminary experiments showed that this technique was not reliable for the measurement of the parabolic growth rate of the iron sulfide layer. In the subsequent experiments the data on growth rate were obtained by measuring, on a microscope stage, change in the thickness of the sample after reaction for a specified time in a hydrogen sulfide-hydrogen mixture of known sulfur activity. For each reaction time a new sample was used. Precision-machined iron blocks, 0.5 by 2 by 5 cu cm, were de-greased and annealed in hydrogen for several hours prior to the sulfidation rate measurements. The experiments were carried out at 670°, 800°, and 900°C in gas mixtures having the ratios, and 1.0 for periods of times from a few hours up to 8 days. Apparatus and Materials. A vertical globar tube furnace with a 3-in.-long uniform temperature zone was used. The glass tube fittings were fused on the zircon reaction tube, 1.5 in. diam. The temperature was measured with a Pt-10 pct Rh/Pt thermocouple placed in the hot zone of the furnace inside the reaction tube (an alumina thermocouple sheath was used). A separate thermocouple was used for the temperature controller which maintained the furnace temperature constant within about 2°C. Anhydrous liquid hydrogen sulfide and oxygen-free dry hydrogen from gas tanks were used in preparing the gas mixtures by the constant head capillary flow-meters. In all cases volume flow rate was 1000 cu cm per min at stp, corresponding to a linear velocity of about 6 cm per sec at 800°C; under these conditions

Jan 1, 1969

By W. G. Matteson

The origin of the salt domes of the Gulf coastal plain has been investigated by many of the most able geologists, but the problem cannot be said to have been satisfactorily solved. Since 1860, numerous theories have been presented, only to be discarded, at least in part, as more complete infomation revealed their fundamental weakness. Real progress toward solution dates from 1902, when Hill1 advanced the theory of secondary deposition of the domal materials from saturated solutions of hot saline waters ascending from great depths under hydrostatic head along structural lines of weakness. Shortly thereafter, Harris,² using Hill's hypothesis as a basis, explained the doming and pronounced uplift associated with these salt cores as the result of forces exerted by growing salt crystals. This was a marked advance over the ideas of Coste3 and Hager,4 since no evidence of igneous intrusives, as they assumed to explain the uplifts, had been found associated with the domes. Harris5 developed his theory until it offered such apparently plausible explanations of so many details of dome phenomena that his hypothesis and conclusions received widespread acceptance, despite some serious objections, and today his theory, somewhat modified, is considered by many able investigators to be the best explanation of the origin of these domes. The immense production of oil per acre, the recognition of the high lubricating quality of the oil, the development and recognition of the efficiency and advantages of oil-burning vessels, with the subsequent exceptional demand for fuel oil, and the resultant advance in the price of coastal crude, have been responsible for a prospecting and develop- 1 Robert T. Hill: Beaumont Oil Field with Notes on Other Oil Fields of the Texas Region. Jnl. Franklin Inst. (1902) 164, 143. 2Gilbert D. Harris: Rock Salt in Louisiana. Louisiana Geol. Survey Bull. 7 (1907) 76. ³E. Coste: Volcanic Origin of Natural Gas and Petroleum. Jnl. Canadian Min. Inst. (1903) 6, 73. 4Lee Hager: Mounds of the Southern Oil Fields. Eng. & Min. Jnl. (July 28, 1904) 78,137, 180. 6Gilbert D. Harris: Geologicel Occurrence of Rock Salt in Louisiana and East Texas. Econ. Geol. (1909) 4, 12.

Jan 1, 1921

By Alwyn Birchmore Cox, Ian William Wark

Sodium sulfide is used extensively to increase the recovery of oxidized copper and lead minerals by flotation, particularly when using xanthates as collectors. It is generally assumed that the sodium sulfide converts a film of the oxidized mineral to the sulfide, and that the xanthate, while not a very effective collector for the oxidized minerals, is a good collector for the sulfide. On the other hand, Taggart and his collaborators1 claim that unless sulfide minerals are oxidized they cannot adsorb xanthates and do not float. Gaudin2 states that amyl xanthate, used in conjunction with sodium sulfide, gives better results than ethyl xanthate. Rabone3 and Mayer-Schranz4 agree that excess of sulfide functions as a depressant. Owing to the greater solubilities of the oxidized minerals than of the sulfides, the consumption of sodium sulfide is greater than that of most other flotation reagents, up to 10 lb. per ton of ore being used in some plants. Luyken and Bierbrauer5 recommend a water washing to remove soluble heavy metal salts; by this means sulfide consumption may be reduced. It was desirable to determine the limits of the sulfide concentrations between which contact is possible at surfaces of anglesite and cerussite in xanthate solutions. Similar determinations were desirable for the sulfide minerals with which the oxidized minerals are usually associated, since conditions should be chosen, if possible, so that the two types of mineral will float together. Because of the formation, especially in acid solutions, of hydrogen sulfide and of the hydrosulfide ion (HS-), the permissible limits of sulfide addition are obviously dependent upon the pH value. Sphalerite responds to ethyl xanthate only in the presence of an activator; for example, copper sulfate. It was necessary, therefore, to determine whether sodium sulfide interferes with the activation of sphalerite by copper sulfate. The combined effect of sulfide and copper sulfate was determined also for galena, chalcopyrite and pyrite.

Jan 1, 1939

By Ian William Wark, Alwyn Birchmore Cox

Sodium sulfide is used extensively to increase the recovery of oxidized copper and lead minerals by flotation, particularly when using xanthates as collectors. It is generally assumed that the sodium sulfide converts a film of the oxidized mineral to the sulfide, and that the xanthate, while not a very effective collector for the oxidized minerals, is a good collector for the sulfide. On the other hand, Taggart and his collaborators1 claim that unless sulfide minerals are oxidized they cannot adsorb xanthates and do not float. Gaudin2 states that amyl xanthate, used in conjunction with sodium sulfide, gives better results than ethyl xanthate. Rabone3 and Mayer-Schranz4 agree that excess of sulfide functions as a depressant. Owing to the greater solubilities of the oxidized minerals than of the sulfides, the consumption of sodium sulfide is greater than that of most other flotation reagents, up to 10 lb. per ton of ore being used in some plants. Luyken and Bierbrauer5 recommend a water washing to remove soluble heavy metal salts; by this means sulfide consumption may be reduced. It was desirable to determine the limits of the sulfide concentrations between which contact is possible at surfaces of anglesite and cerussite in xanthate solutions. Similar determinations were desirable for the sulfide minerals with which the oxidized minerals are usually associated, since conditions should be chosen, if possible, so that the two types of mineral will float together. Because of the formation, especially in acid solutions, of hydrogen sulfide and of the hydrosulfide ion (HS-), the permissible limits of sulfide addition are obviously dependent upon the pH value. Sphalerite responds to ethyl xanthate only in the presence of an activator; for example, copper sulfate. It was necessary, therefore, to determine whether sodium sulfide interferes with the activation of sphalerite by copper sulfate. The combined effect of sulfide and copper sulfate was determined also for galena, chalcopyrite and pyrite.

Jan 1, 1939