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By J. H. Jensen

Bromine is the intermediate member of the halogen family of elements between iodine, a solid: and chlorine, a gas. The name is derived from the Greek "bromos," meaning stench. Bromine is the only nonmetallic element that is liquid at room temperatures with a melting point of -7.2" C and a boiling point of 58.78" C. Reddish brown in color, it dissolves easily in water to yield a red solution. Bromine volatilizes at ordinary temperatures to a red vapor that is very irritating to the eyes, nose, and throat. Density of the liquid is 3.12 and gas weighs 7.59 gpl at standard conditions. As the element is highly active, it exists in nature only as bromide compounds. Bromine was discovered by Antoine Jerome Balard in seawater bitterns in 1826 and first prepared in quantity in 1860. Distribution Bromine is widely distributed in nature and compounds occur in solution in natural brines, in seawater, saline lakes, oil and gas well brines, and in evaporite chloride minerals. The concentration of bromine salts ranges from 60- 65 ppm in seawater to several thousand ppm in oil well brines and saline lakes. The distribution of bromine in marine evaporite minerals and in the solutions from which they crystallized was determined many years ago by H. E. Boeke (1 908). Theoretical aspects regarding the geochemistry of bromine have been published in numerous papers (Raup and Mite, 1969). Bromine occurs in solid solution in carnallite and sylvite associated in potash de- posits; in halite in salt beds; salt in oil shales; and in trona deposits. Its presence is useful as a guide in geochemical exploration. The analysis of small amounts of bromides in the presence of large amounts of chlorides is discussed by W. Schwerdtner (1963). Manganese, iron, and iodine may interfere with the determination. Other analytical methods are discussed at length in the literature (Stenger and Atchison, 1964). Sources and Reserves The sources and reserves of bromine, given in [Table 1], appear ample to meet present and foreseeable requirements in all producing countries. With the occurrence of bromine salts in sea-water and other brines, the potential for bromine production is worldwide. It has been estimated that 99% of all commercially recoverable bromine is in the ocean. However, actual subterranean brines having a higher bromine content than seawater will continue to be the preferred sources of bromine for the foreseeable future. Markets and Prices About 17% (1968) of bromine produced is used in its elemental form, with the balance consumed as bromides and bromates. The largest use for bromine is ethylene dibromide which, together with tetraethyl lead, are used as an antiknock additive in gasoline. Tetra-ethyl lead is the antiknock agent. Ethylene dibromide combines with the lead after combustion in the engine to form a volatile com- pound that escapes from the engine with the exhaust gases.

Jan 1, 1975

By D. P. Koistinen, K. E. Beu

THE application of the integrated intensity X-ray diffraction method to the measurement of retained austenite concentrations in hardened steels has been fully described.'-' In developing this particular method, the assumption was made that the samples used would have flat surfaces which were free from voids and in which austenite was homogeneously distributed. The original calculation procedure' was modified to include the constant factor G which relates the intensity of a given diffraction line to the concentration of the component giving rise to that line. In order to include A (0) in the constant factor G, it was further assumed that the geometrical conditions relating the X-ray beam, camera cylinder, and sample surface were precisely met.V has been demonstrated that these geometrical conditions can be met experimentally without difficulty in many cases;' however, for those samples which have irregular surfaces or where it is impossible to locate the sample in the proper position with respect to the X-ray beam and film cylinder, it is desirable to evaluate experimentally what effect these nonideal conditions have on the reliability of the austenite determination. This note decribes the results of such experiments. SAE 1095 bar stock was used throughout and all samples were heat-treated as follows: 1600°F for 1 hr in a neutral atmosphere, brine quench, and 300°F temper for 30 min. To control heat-treatment conditions as closely as possible, all samples were plated with 0.002 in. copper to protect the immediate surface from the heat-treating atmosphere. After heat treating, the samples were deplated electroly-tically so that only the copper was removed. The heat-treated surfaces thus obtained were nearly as bright and polished as the original surfaces before copper plating although no mechanical work was done on the samples after heat treating.

Jan 1, 1954

By H. L. Shergold, O. Mellgren

Concentration of fine quartz particles at the iso-octane/water interface has been investigated under different conditions of pH and dodecylamine concentration. The results obtained from the related studies on the effect of amine concentration and pH on the interfacial tension, adsorption density, electrokinetic potential, contact angle, and concentration of the various amine species in the system are presented. A good correlation was obtained between these different variables. It is well-known that very fine mineral particles are difficult to float in conventional flotation machines. Flotation rate studies have revealed that the rate of flotation of fine mineral particles is much smaller than that of coarser size fractions. The theories accounting for this behavior have been discussed by Arbiter and Harris1 and also Meloy.2 Theoretically, a hydrophobic fine particle might never make contact with a bubble because of the presence of an energy barrier in the vicinity of the air/water interface.' This energy barrier will have electrostatic, hydrodynamic, and Van der Waals force components. It was thought that by using an oil phase instead of air the energy barrier would be decreased so that fine particles could be concentrated at the oil/water interface more readily than at the air/water interface. The technique used involves dispersing the fine particles in water, containing the appropriate chemical reagents, and injecting a fine dispersion of iso-octane oil droplets into the pulp. After vigorous conditioning, the pulp is passed into a separating column where the oil droplets coated with a layer of mineral particles rise to the surface to form a separate layer. Air is introduced into the base of the separating column to ensure that heavy agglomerates of oil and particles report with the organic layer. This technique has been described previously4 and adopted by Lai and Fuerstenau5 who studied the alumina-dodecyl sulfonate system. The interfacial phenomena in the system composed of hematite, water, and iso-octane in the presence of sodium dodecyl sulfate have been studied and the results reported" earlier. This paper describes the results obtained from investigations into the interfacial phenomena in the quartz/water/iso-octane system in the presence of dodecylamine. The technique used in measuring the interfacial tension, electrokinetic potential, contact angle, and adsorption density were similar to those described previously? Materials Selected pieces of a high purity natural quartz, from the Isle of Man, were crushed in a laboratory jaw crusher and pulverizer. The — 52+72 mesh size fraction was retained and leached with successive washes of hot concentrated hydrochloric acid to remove iron impurities. When no iron was detected in the solution by ammonium thiocyanate, the quartz was washed thoroughly with distilled water until the conductivity of the wash water assumed that of the distilled water. Samples of 25 g of the —52+72 mesh quartz were ground for 5.25 min in an agate vibratory mill. The ground product was 100% —44 m and 57% —10 am, as determined by the Andreasen pipette. The specific surface area of the sample used for the adsorption and flotation tests was 0.94 sq m g-l. This corresponds to a mean particle diameter of 2.4 am. The —44 am quartz sample was stored under vacuum in the presence of silica gel crystals. For the contact angle determination between the three phases, quartz, iso-octane, and water, a piece of the natural quartz was ground into a block about 15 mm long, 15 mm wide, and 5 mm thick. One surface of the block was then polished by successively finer grades of silicon carbide "paper." The final polishing was conducted with alumina on a "hyprocel" paper. The polished quartz specimen was cleaned using nitric acid and ethyl alcohol followed by a wash with distilled water and then stored under distilled water. This pro-

Jan 1, 1971

The editorial expenses for the preparation of the manuscript of the second edition, as for the first, were provided by grants of the Engineering Foundation and the Open Hearth Steel Committee of the Iron and Steel Division, AIME ; the Seeley W. Mudd Memorial Fund again sponsored the publication of this volume. The companies and research or educational institutions with which the authors, reviewers, and editors are connected also contributed much to the writing and editing of this book through their generous donations of time and travel and office expenses. And finally, the authors and others have given countless hours of their own time with no recompense but the satisfaction of a job well done. In order to give credit to the companies or educational institutions which made it possible for the members of the Editorial Board to devote considerable time to the revision of this book, the names of these members and their affiliations are recorded here as follows : W. O. Philbrook, Carnegie Institute of Technology M. B. Bever, Massachusetts Institute of Technology H. B. Emerick, Jones and Laughlin Steel Corporation B. M. Larsen, United States Steel Company A number of individuals suggested desirable changes in the book before rewriting was started. Almost all manuscripts were gone over critically by reviewers, and the resulting criticisms led to the correction of errors and omissions and greatly contributed to the accuracy and completeness of the text. Other people have supplied additional data or illustrations or assisted in other ways. While some of these contributors must remain anonymous because they are not known to the Editors, the cooperation of the following individuals is gratefully acknowledged : R. D. Allen, Republic Steel Corporation, Chicago Isadore Amdur, Massachusetts Institute of Technology Mary Baeyertz, Armour Research Foundation S. P. Bahmer, Republic Steel Corporation, Massillon E. C. Bain and Associates, United States Steel Company, Pittsburgh C. W. Briggs, Steel Founders' Society of America H. W. Briske, Wisconsin Steel Works

Jan 1, 1964

The editorial expenses for the preparation of the manuscript of the second edition, as for the first, were provided by grants of the Engineering Foundation and the Open Hearth Steel Committee of the Iron and Steel Division, AIME ; the Seeley W. Mudd Memorial Fund again sponsored the publication of this volume. The companies and research or educational institutions with which the authors, reviewers, and editors are connected also contributed much to the writing and editing of this book through their generous donations of time and travel and office expenses. And finally, the authors and others have given countless hours of their own time with no recompense but the satisfaction of a job well done. In order to give credit to the companies or educational institutions which made it possible for the members of the Editorial Board to devote considerable time to the revision of this book, the names of these members and their affiliations are recorded here as follows W. O. Philbrook, Carnegie Institute of Technology M. B. Bever, Massachusetts Institute of Technology H. B. Emerick, Jones and Laughlin Steel Corporation B. M. Larsen, United States Steel Company A number of individuals suggested desirable changes in the book before rewriting was started. Almost all manuscripts were gone over critically by reviewers, and the resulting criticisms led to the correction of errors and omissions and greatly contributed to the accuracy and completeness of the text. Other people have supplied additional data or illustrations or assisted in other ways. While some of these contributors must remain anonymous because they are not known to the Editors, the cooperation of the following individuals is gratefully acknowledged: R. D. Allen, Republic Steel Corporation, Chicago Isadore Amdur, Massachusetts Institute of Technology Mary Baeyertz, Armour Research Foundation S. P. Bahmer, Republic Steel Corporation, Massillon E. C. Bain and Associates, United States Steel Company, Pittsburgh C. W. Briggs, Steel Founders' Society of America H. W. Briske, Wisconsin Steel Works

Jan 1, 1951

By Charles Barrett

METALLURGISTS are making use of the stereographic projection to a steadily increasing extent. In the last five years no less than 20 papers in American metallurgical journals alone have employed the stereographic projection; recent books on physical metallurgy, plastic deformation, X-rays and their applications, and crystal structure use it. Mineralogists have used the stereographic projection for many years in the description of symmetry classes and crystal planes, for it presents an accurate, easily understood plot of any angular relations in crystals with all unessential features eliminated (such as the accidentally deter-mined size and shape of crystal faces). In metallography and physical metallurgy the projection is much used for the analysis of markings appearing on polished grains: slip lines, twins, cracks, structures formed by precipitation, magnetic-powder patterns, etch pits, etc. Data from certain types of X-ray photograms are most conveniently analyzed by its use, particularly those for determining the orientation of single crystals or the preferred orientation of grains in an aggregate. Calculations of how to tilt or cut a crystal parallel to a certain crystallographic plane or to reflect X-rays from a certain plane are rapidly carried out. It has been adopted almost universally to the exclusion of other methods by those studying the deformation of metallic crystals, save where the accu-racy required is greater than a few tenths of a degree. Any directional property in a crystal or polycrystalline material can be shown on a stereo-graphic projection; for example, the modulus of elasticity, yield point, etc. It has been repeatedly called to our attention that there is need of all elementary explanation of the principles and methods of stereographic projection, covering all the, common applications in the field of metal-lography and physical metallurgy. The following contribution is an attempt to fill this need. The description of each method is supplemented with references to publications in which the method has been used. For convenience to the reader, these illustrative references are chiefly in American journals, particularly the publications of the American Institute of Mining and

Jan 1, 1937

By J. F. Myers, F. M. Lewis

C. G. McLACHLAN*-I have read this paper with considerable interest and wish to congratulate the authors on the care with which they carried out their experiments and for the detailed sizing data they have presented. 011 the other hand I do not feel that these data establish their contention that "with other factors the same, the work accomplished in a fine crushing rod mill is directly proportional to the rotating speed." My reason for making this statement is that their conclusion is based on the percentage of minus 65 mesh material produced at each of the speeds at which their tests were run. The rod mill is, however, not a fine grinding machine and therefore figures based on minus 65 mesh production are figures outside the range at which it operates to best advantage. Further, if rod mill performance is to be judged on the production of such material it should have been established that a rod mill will produce it as effectively as a ball mill. To check this last point I have gone over some of the rod and ball mill grind-ing figures for our Waite-Atnulet operation and find that the ball mill at that property produces more minus 65 mesh material per horsepower than the rod mill. Moreover, this comparison is even more favorable to the ball mill if it is limited to minus 100 mesh production. It therefore seems to me that the most satisfactory basis on which to try to com-pare the performance of the rod mill in the present case is by taking a weighted average of all the new surface produced per horsepower. W. H. Coghill3 has published data which can be applied to the sizing figures presented by the authors, and if this is done the units of new surface per horsepower produced in the Tennessee tests are as follows: Admittedly the increment of increase in new surface per horsepower shown in the foregoing figures is not great, but its trend is nevertheless definitely in favor of slower speed operation, for the conditions under which these particular tests were run. I also feel that some information regarding liner contour should have been given as I think it will be found that a mill which is equipped with liners which lift the rod load can be run at a slower speed than a mill in which the liners are comparatively smooth. J. F. MYERS and F. M. LEWIS (authors' reply)—The position taken by Mr. McLachlan is to be respected even though we are all aware of the faults of surface considerations. As he points out. the increment of increase is very small. It is so small in fact that for all practical purposes it does not conflict with the conclusions of the paper. The authors appreciate Mr. McLachlan's comprehensive study of the data.

Jan 1, 1950

By Fuad S. Maayeh, Robert J. Evans, Paul M. Yavorsky

A description and capabilities of the Mine Roof Simulator at the Pittsburgh Mining Technology Center is illustrated for testing longwall roof support equipment. This unique Mine Roof Simulator has the capacity to exert 3 million lbs. of compressive force vertically and 1.6 million lbs. of force horizontally to simulate loads on hydraulic supports typically found in longwall mining. The supports that undergo testing are instrumented with strain gauges and photoelastic coatings such that critically strained areas become readily apparent. These critically strained areas are redesigned or retrofitted with appropriate reinforcement and retested. A data base will be accumulated from several support designs that will lead to an optimized design that will have the potential to reduce downtime by malfunctions of supports and thus increase productivity. A typical test procedure and analysis is given for a two leg 350 ton shield along with a description for placement of strain gauges, displacement gauges, and hydraulic pressure monitors for critical sites.

Jan 1, 1982

By W. W. Stephen, J. P. Walsted, W. J. Kroll

FOR the production of carbides, various furnace types are available, especially those using arc, resistance, and high-frequency heating. Selection of a specific means of heating depends primarily on the material to be treated and the physical properties of the carbide produced. In the present case, zirconium carbide had to be prepared on an industrial scale as a raw material for the production of anhydrous zirconium chloride. Considering that a rather expensive pure oxide was to be used, the arc-furnace treatment recommended for zircon sands in a previous publication' was ruled out because of the considerable volatilization and dust losses caused by the blast of the arc. For this reason, either high-frequency or resistance heating seemed to offer more promise. Since there was not enough capacity of the former available, resistance heating was chosen. It was first thought that the Acheson silicon carbide furnace would be suitable for the present purpose, but the voltage in such a furnace, in which the current passes through the batch, varies from 220 to 75 v from the start to the end of a run. This variation is so great that a special tap transformer would have been required. Trouble was also expected by local melting of the carbide. Pure zirconium carbide melts at about 3527°C, but the melting point is brought down to 2427°C, according to Agte,2 when an excess of 6 pct C is present in the carbide. This we found confirmed by experiments in a high-frequency furnace. Excess carbon is needed in the batch to obtain a complete reduction. Fusion of the charge would cause great difficulties in an Acheson-type furnace because of the good electrical conductivity of the carbide as compared with that of the loose batch. Also, fused carbide is much more difficult to chlorinate than the spongy product that can be made in the radiation furnace described below. It was apparent that, to obtain a good-qual-ity zirconium carbide, the heat input would have to be well-controlled. The hairpin-resistor principle seemed to offer possibilities in this regard, and a furnace of this type was therefore developed. The advantages of the hairpin-resistor radiation principle have been discussed in previous publications, and a split-tube graphite-resistor furnace," now increasingly used in various laboratories, as well as a centrifugal quartz melting furnace4 of this type, has demonstrated the usefulness of this heating method. The hairpin-heater element has the following definite advantages over a straight resistor of the type used, for instance, by Georges:5 Its resistance is four times greater; it can expand freely; it is sturdier because of the larger diameter, and it has a larger radiation surface; there are no hot contacts that might wear out or overheat; only one clamp is used which permits assembling all electrical leads at one side of the furnace, making the other sides easily accessible to the operator. The shorter element and its larger diameter permit greater concentration of heat. The furnace developed is shown in fig. 1. The box (I), made of 2 1/2-in. graphite plates, has inside dimensions of 23x17x16 in. It contains the briquet-ted batch (2). The box is embedded in lampblack (3) up to the cover plate. The cover plate contains an opening for the gas escape (4) and for the observation hole (5), which permits measuring the temperature with an optical pyrometer. The cover plate is embedded in charcoal (6). The lampblack is contained in the insulating brick lining (7), held in the 1/4-in. sheet steel box (8). The graphite box is set on two rows of triangular graphite bars (9). The hairpin-heater element (10), the dimensions of which are given below the main drawing, extends horizontally in the graphite chamber and radiates freely on the batch. A graphite tube (11) keeps the lampblack from falling into the slot. The split electrode, which in reality is turned 90" against the drawing, is so arranged that the slot is vertical. The water-cooled packing gland (12) is insulated by an airgap from the heater element. A thin pipe (13)

Jan 1, 1951

By P. Greenfield, C. C. Smith, A. M. Taylor

The Mg-Zr alloy ZA and Mg-Mn alloy AM503(S) are shown to have a markedly improved resistance to creep deformation after suitable heat treatments. This improvement makes them suitable for certain stress-bearing fuel element components in nuclear reactors. The extent of strengthening is described and an explanation of the behavior of both materials is given, based on a combination of strain-aging and grain growth. The increase in operating temperatures of fuel element components in Calder Hall type nuclear reactors has necessitated the development of magnesium base alloys with a very high resistance to creep at temperatures up to 500°C. Such alloys are not required for fuel element cans, which require high-creep ductility rather than strength, but for can supporting and stabilizing components, which are needed to support the imposed loads without deforming more than about 1 pct in times of up to 40,000 hr. The amount and type of alloying addition made to magnesium for these parts is limited by the necessity of keeping the cross-section to thermal neutrons as low as possible. The alloys must also possess a high resistance to oxidation in CO2. Alloys which have been developed for this application include ZA, an alloy of magnesium with 0.5 to 0.7 pct Zr and AM503(S), an alloy of magnesium with 0.5 to 0.75 pct Mn. In the as-extruded condition these alloys are very weak and ductile in creep but it has been found that they can be strengthened to a significant extent by heat treatment. This paper describes the method of developing a high-creep resistance in ZA and AM503(S), the extent of the strengthening produced and discusses the probable mechanisms of strengthening. TEST MATERIALS Specimens were taken from typical casts of ZA and AM503(S) alloys extruded into 2 1/4-in.-diam bars, supplied by Magnesium Elektron Ltd. Typical analyses of the bars were as follows: The as-extruded mean grain diameter was 0.001 to 0.002 in. for the ZA alloy and 0.003 in. for the AM503(S) alloy. EXPERIMENTAL METHODS Extruded bars of ZA alloy, 2 1/4 in. in diameter and 9 in. long, were heat treated in electrical resistance furnaces in an atmosphere of flowing CO2 containing 50 to 300 ppm water, thereby reducing the extent of oxidation compared with that which would have occurred in air. Heat treatments were carried out at 600oc for times of 8, 24, 48, 72, and 96 hr and material was subsequently both furnace cooled and water quenched. In order to measure the effect of time of heat treatment, specimens were creep tested at 400°C and 336 psi for about 1000 hr. Subsequently, the behavior of material heat treated for 96 hr at 600°C and furnace cooled was tested at a variety of stresses from 200° to 500°C. Tests were also conducted at 200o and 400°C on material in the as-extruded condition for comparative purposes. With the AM503(S) alloy, only the effect of heat treatment at 565°C for 4 hr was examined. It has been shown1 that such a heat treatment produces marked strengthening in this alloy. Tests on this material were conducted at a variety of stresses at 200°, 300°, and 400oc with comparative tests on as-extruded material at 200o and 400°C. The creep tests were carried out on machines using dead-weight loading and direct micrometer strain measurements on specimens 5 in. long and 0.357 in. diameter. At temperatures of 400° C and below, the creep tests were conducted in air, but at higher temperatures an atmosphere of CO2 was used. Grain size measurements were made on ZA in the extruded and heat treated states and on each specimen after creep testing. This was done by a line count of a minimum of 20 grains in two or three random fields in the longitudinal and transverse directions. The same method was used for measuring the grain size of as-extruded AM503(S), but the grain size of the heat treated material was so large that this method could not be employed. For heat-treated AM503(S) the large grained characteristics (between 0.1 and 1 in.) were confirmed by the measurement of individual grains. In the case of the ZA alloy, specimens taken from various stages in the program were analysed for hydrogen by a combustion method. Material in various states was also analysed for the soluble and insoluble zirconium content by dissolving in dilute hydrochloric acid. This technique has been useda for the determination of amounts of zirconium present

Jan 1, 1962

By D. C. Seidel, E. F. Fitzhugh

The cementation of nickel from acidic solutions by metallic iron is discussed. The cementation is carried out in pressure vessels at temperatures above 100°C. The results from bench scale studies on variables such as retention time, temperature, and solution pH are presented. A continuous processing flowsheet is proposed. Cementation is one of the oldest known hydrometal-lurgical reactions. The cementation of copper on iron was recorded by 'Paracelsus the Great' in about 1500,1 and by 1600 the technique was being used to recover copper at the Rio Tinto operations in Spain.2 At least one early author felt that cementation may have been one of the primary reasons for the alchemists' belief in the transmutation of metals.' The early writings state that when iron was placed in the clear waters from some mountain springs, the iron disappears and copper is found in its place. To the alchemists this may well have been one of the most convincing proofs that transmutation could and did occur. Since these early times the recovery of copper from acidic solutions by cementation has been practiced in plants throughout the world. Probably the cementation technique in some form has been common to more copper mining and milling operations than any other single recovery process. During current hydrometallurgical extraction studies, which were sponsored by the Republic Steel Corp. at the Colorado School of Mines Research Foundation, Inc., it was found that under the proper conditions, metallic nickel could be cemented from acidic solutions by powdered iron. The reactions are apparently similar to those that occur during the cementation of copper, but the nickel cementation had not been anticipated because iron and nickel are nearly adjacent in the electromotive series. The potential difference between iron and copper is approximately 0.78 v, while the potential difference between iron and nickel is less than 0.21 v. The cementation of nickel with iron at room temperature is almost negligible, but when the reaction is carried out in a closed vessel at temperatures in excess of 100°C, the nickel can be cemented almost quantitatively. The part played by this discovery in a practical method of nickel recovery is set forth in a separate paper.3 The following paragraphs are a discussion of experimental studies that were made to investigate this cementation reaction. The technique has been designated the HTC or High Temperature Cementation procedure. The cementation work was part of a study on hydrometallurgical techniques for the extraction of nickel from the garnierite or silicate type nickel ores. A hydrothermal extraction procedure had been developed, and this technique produced an acidic pulp or solution that contained both nickel and appreciable amounts of magnesium.3 Small quantities of ferric and ferrous iron were also present along with cobalt, manganese, and chromium. The potential for recovering the nickel from these acidic solutions by ion exchange or solvent extraction did not appear to be promising because of the relatively high magnesium content. The Ni ++ and Mg++ have nearly identical ionic dimensions and tend to be co-absorbed or extracted during ion exchange or solvent extraction treatments. Preliminary tests indicated that the nickel could be precipitated as a sulfide when using the high pressure H2S precipitation technique developed for the Moa Bay operations of the Freeport Nickel CO.4 This technique gave good recoveries, but the nickel sulfide product requires considerable additional processing before a marketable form of nickel is realized. The process also requires clarified feed solutions, and the solids-liquid separations on the garnierite residues are difficult. A program was initiated to investigate alternate procedures that might shorten the route to a marketable nickel product, and hopefully also permit bypassing the difficult solids-liquid separation steps required for the H2S precipitation technique. It was during these studies that the nickel cementation reaction with iron was encountered. EXPERIMENTAL EQUIPMENT AND PROCEDURES The bench scale precipitation tests which were conducted during this experimental program were made in 2-liter stirred autoclaves.* A photograph showing the form and arrangement of the autoclave

Jan 1, 1968

By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly i00 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi¬tion is accompanied by a change in volume of as much as S per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potters have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to g0 per cent Mn. is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to ½ in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By N. K. Chen, R. Maddin

Columbium single crystals were deformed in tension and compression. Reorientation by X-rays and stereographic projections of slip traces indicate that plane of slip may be considered as (110). The plastic behavior is shown to be quite similar to the deformation of molybdenum single crystals. STUDIES on the crystallography of the deformation process in body-centered cubic metals have been renewed recently with investigations of iron single crystals1-" and molybdenum single crystals.4 It is now apparent that too many exceptions to the rationalization based upon the ratio of absolute testing temperature to absolute melting point by Andrade5 exist to permit more serious discussion of this type of analysis. The considerations of resolved shear stress utilizing only planes of the type {ll0}, {112), and {123)³,6 permit analysis of the deformation only on the basis of those three types of planes. The suggestions made by Elam7 and by Greninger8 in which the slip process is envisioned as a composite slip on two nonparallel {110) planes can be illustrated schematically in Fig. 1. It may be seen that an unresolved trace on any plane containing a <111> direction may be accomplished by varying the number of atoms participating in the composite process. By further varying the number of atoms in each plane but keeping the ratio of participating atoms constant, jogs could be obtained in the traces and hence wavy slip lines could be produced. Vogel and Brick&apos; studied the behavior of a iron single crystals in which they suggest that the plane of glide is "non-crystallographic" and may be predicted from the intersection between the great circle joining the slip direction and specimen axis with the great circle whose zone axis is the slip direction. In a more recent investigation on iron single crystals, Steijn and Brick" suggest that the slip mechanism may be considered as made up of a type of composite slip occurring on {110} and {112} planes. Evidence for a possible composite nature of the slip process has been presented for the case of molybdenum in the form of analysis of asterism and specimen axis rotation." Definite proof of a composite slip process must, however, await good electron microscopic resolution of the individual traces making up the unresolved optical trace used in determining the acting slip plane. The present investigation was undertaken to study the behavior of columbium single crystals not only in tension but also in compression since the specimen axis migration should indicate the plane or planes of glide in the same manner that the specimen axis migration in tension indicates the direction of glide. The orientations of eleven crystals investigated are shown in Fig. 2. Specific orientations are missing (those in the vicinity of [Ill] and [001] and consequently the effect of orientation on the crystallography of deformation could not be considered. Experimental Procedure The 1/8 in. rods (7 in. long) were subjected to an axial tension in vacuo while at temperatures in the vicinity of 2000°C for 2 to 4 hr. This treatment resulted in large cylindrical grains (about ½ in. long) occupying the entire cross section. A number of these rods were used for the tension studies by observing the behavior of the individual grains. For the compression studies, single crystals approximately % in. long by 1/8 in. in diameter were cut from the rods; the ends were ground parallel. All specimens were polished electrolytically in a solution of 15 cc HF(48 pct) and 85 cc H2SO4 (concentrated) using a platinum cathode, a current density of 0.04 amp per sq cm and a temperature between 25" and 60°C.10 Orientations were obtained using a Laue back-reflection method (3 cm film to specimen distance) with a ½ mm collimator 9 cm long. For the compression specimens, a reference mark was scratched on one of the compression sur-

Jan 1, 1954

By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies&apos;-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday&apos;s law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5&apos;= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By J. L. Snoek

[ ] DISCUSSION J. L, SNOEK*-Stress-induced preferential diffusion in cubic body centered metals in the annealed state provides us with a powerful tool for determining the mobility of interstitially solved atoms as well as their location in the lattice and the exact nature of the distortion brought about in the lattice by their presence. Calculations given by D. Polder31 show that the distortion of the lattice, besides being proportional to the applied stress P, is also proportional to [VC, RT + xVCo] where T, V and Co are the temperature, molar volume of the solvent and molar concentration of the solute respectively and x is a constant describing the mutual interaction energy of the dissolved particles. This calculation obviously is no longer valid if x is negative and the abso¬lute value of xVCo surpasses that of RT. The lattice may then be expected to become tetragonal spontaneously. Such a spontaneous tetragonality seems to have been observed by W. Klemm and L, Grimm for the case of oxygen solved in vanadium.32 Measurements of the internal friction in cold worked iron containing carbon or nitrogen should provide us with information on the mobility as well as the preferential location of these particles in the iron lattice in the cold worked state. The work by T&apos;ing-Sui Kê is a valuable contribution to this problem, The data obtained by T&apos;ing Sui Kê and myself on cold worked samples of iron seem to indicate that carbon and nitrogen in these samples are found either in the normal (1/2 , 0, 0) interstices or in a new preferential position created by the cold working. The latter positions in my opinion can hardly by anything else but the edges of the dislocations. The observed larger distances of diffusion might be explained by assuming that the carbon atoms when freed from a certain dislocation by thermal agitation must diffuse over several atom distances before being caught in another dislocation. The theory however needs working out and no doubt will be much more complicated than the one valid for the annealed state. T&apos;ING-SUI KÊ (author&apos;s reply)-It is highly encouraging to read the written discussion given by Dr, Snoek who initiated the theory of stress-induced preferential diffusion in cubic body centered metals in the annealed state, Since the presentation of this paper, the author has done more experimental work on this subject which seems to be able to settle several of the points raised by Dr. Snoek. It has been found that such stress-induced preferential diffusion occurs also in the solid solutions of carbon,33 oxygen,34 and nitrogen35 in tantalum which has a body centered cubic structure. Analysis of the shape of the observed internal friction. peaks indicates that the inter-

Jan 1, 1948

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

Discussion of the paper of R. H: Sweetser,. presented at the Cleveland meeting, October, 1912, and printed in Bulletin No. 71, November, 1912 pp. 1327 to 1334. See also Bulletin 11 No. 72, December, 1912, pp. 1561, 1562. J. J. HOWARD, Dover, N. J. (communication to the Secretary*) :-No doubt there are as many different methods of starting a blast-furnace as there are men who assume that responsibility. Having blown-in a furnace a few years ago in a manner similar to that outlined by Mr. Sweetser, things went along so well at the start that I had time for a little reflection on what was going on inside the furnace. I saw the wood turned to charcoal practically, and it occurred to me, why should I use wood when I could put in the charcoal in the. first place, and thus save a lot of time, and also eliminate the dangerous gas from the wood, which is the cause of most of the accidents in starting up a furnace. I had a furnace out for repairs and decided to use no cord-wood in blowing in. I put in about a carload of charcoal and used no wood except some shavings and oily waste at each of the tuyeres. The furnace had 16 tuyeres and was 100 by 22 by 14.5 ft. Hot rods were put in each tuyere&apos; and the blast started immediately at 11 a.m. Within 5 mill. the air was all driven out of the stack and the gas lighted of its own. accord at the top of the furnace. It was allowed to burn for 5 min. longer and then the bell was closed and the gas taken to the last stove and the last boiler on the gas-main. It was all clone so quietly that it was hard to realize that the gas was down. The tuyeres were as bright as if the furnace had been in blast for a long time. I have learned since that others have used the same method, but they had not passed the good advice along.

Jan 5, 1913

By A. S. Venkatadri, H. B. Bell

The equilibrium sulfur distribution between molten iron and Ca0-Mg0-Al203 slags containing iron oxide was investigated at 1550°C. The results were used to derive the iron oxide activities at low iron oxide concentrations in the slag by combining the sulfide capacity data obtained from gas-slag work with the free energies of both the sulfur solution in iron and the iron oxide formation in slag. The derived ferrous oxide activities were compared with values based on Tem-kin&apos;s kin&apos;s and Flood&apos;s ionic models. One difficulty in using these models is that the nature of the aluminate ion in slag is uncertain. Nevertheless, such indirect methods, in particular, those described in the present paper, are of value because of the difficulty of measuring small amounts of oxygen in liquid iron in equilibrium with slag. It is shown that these methods confirm the consistency of thermodynamics data on liquid iron and slags. It is well established that decreasing the iron oxide activity in the slag increases the desulfurization of molten iron at constant slag basicity. This effect is most pronounced at the very low iron oxide activities, characteristic of blast furnace slags. Yet a precise quantitative determination of the significance of low iron oxide contents in slag in blast furnace desulfuri-zation is not possible for the following reasons: a) difficulty of separation of iron "shots" from the slag, and b) errors in chemical analysis of small amounts of iron oxide in slags. In view of these obstacles, one must resort to indirect methods of calculating iron oxide activities. EXPERIMENTAL TECHNIQUE The apparatus for providing the sulfur equilibrium data has been described previously1 and was similar to that used by ell&apos; in connection with the study of slag-metal manganese equilibrium. The procedure consisted of: a) melting about 50 g of Armco iron in a magnesia crucible in a platinum furnace, b) adding a mixture of about 15 g of lime-alumina slag and varying amounts of Fe2O3 and CaS, and c) maintaining the temperature at 1550°C for more than an hour in an atmosphere of argon to enable the sulfur equilibrium to be attained. Several melts were made using lime-alumina slags with basic composition 55, 50, and 45 pct lime. During the experiment the temperature was controlled manually using a Pt/10 pet Rh-Pt thermocouple. After the experiment, the Power was shut off and the flow rate of argon was increased to freeze the melt as quickly as possible. The analysis of sulfur in the metal was carried out by the oxygen combustion method3 using uniform drillings from the top and bottom of the metal button. After crushing and grinding and removal of any iron particles with the aid of a hand magnet, the slag was analyzed for sulfur by the CO2 combustion method.4 The E.D.T.A. method was employed for the analysis of lime5,6 and magnesia,= the ceric sulfate method7 for the analysis of slag iron oxide, and the perchloric acid dehydration method5 for the analysis of silica. The remaining amount was taken to be Al2O3 precipitation with ammonium hydroxide in several preliminary melts had confirmed the propriety of using this simple procedure. RESULTS The activity of iron oxide in binary, ternary, and more complex slags has been the object of numerous investigations, and the two experimental methods for its determination are: 1) Equilibrating the metal with the slag in question and measuring the oxygen content of the metal. The ferrous oxide activity is then given by aFeO L%OJSat where [%0]sat is the oxygen content of the metal in equilibrium with pure iron oxide slag. This method was used by Chipman et al.8,9 2) Equilibrating the slag in iron crucibles with known partial pressures of H2/H2O or CO/CO2 mix-tures.10-12 This method is limited to temperatures between 1265" and 1500°C. The very low oxygen content of the melts in this investigation made it impossible to derive the ferrous oxide activity by the first of these methods. Therefore, the iron oxide activities were computed by means of: Sulfide capacity data from the gas-slag work" Temkin&apos;s concept14 Flood&apos;s approach15 a FeO from Sulfide Capacity. The method of calculating the aFeO involves the sulfide capacity of the slag (c,), the sulfur distribution coefficient (Ls), the free energy of dissolution of sulfur in iron, and the free energy of formation of iron oxide in the slag. Bell and Kalyanram13 have investigated the sulfur absorption characteristics of lime-alumina slags containing magnesia by the Carter-Macfarlane method16 (based on comparing the sulfide capacity of the slag in question with that of a standard slag of unit lime activity) and have derived lime activity values. The relation between sulfide capacity and their lime activity a&apos;CaO is given by: Cs= 3—: Xa&apos;CaO at 1500°C

Jan 1, 1970

By Ernest R. Dickie

IN 1945 the Bagdad Copper Corp. decided to change from block caving to open-pit mining. By early 1948 the conversion was completed and production was increased from 1500 tons per day to 4000 tons per day. Open-pit mining costs decreased approximately 40 pet from the cost of producing ore by the underground method. At present one P & H model 1400 all-electric 4 1/2-yd shovel and one P & H model 1055 Diesel 3-yd shovel are used continuously for stripping. One 21/2yd North- west shovel handles the ore. Delivery of a new P & H 1055 electric shovel for stripping is expected this month. Blasthole drilling is performed with two Bucyrus model 22 and two Bucyrus model 27 churn drills.

Jan 9, 1951