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CONTENTS PAGE BAIN, EDGAR C.-The Nature of Martensite. Discussed by Ancel St. John, Henry S. Rawdon, Jerome Alexander, Howard Scott 1 FEILD, ALEXANDER L.-Effect of Zirconium on Hot-rolling Properties of High-sulfur Steels and the Occurrence of Zirconium Sulfide. Discussed by Beram D. Saklatwalla, Bradley. Stoughton, Andrew M'Cance, George F. Comstock, Alexander L. Feild 12 SAUVEUR, ALBERT and KRIVOBOK, V. N.-Use of Sodium Picrate in Revealing Dendritic Segregation in Iron Alloys. Discussed by George F. Comstock, John H. Hall 17 KINNEY, C. L., JR.-Economic Significance of Metalloids in Basic Pig Iron in Basil Open-hearth Practice. Discussed by V. J. Pazzetti, George B. Waterhouse, C. L. Kinney, Jr 19 NEAD, J. H.-Absorption of Sulfur from Producer Gas in Open-hearth Furnaces.. Discussed by George B. Waterhouse, C. L. Kinney, Jr 26 PRIESTLY, WILLIAM J.-Effect on Steel of Variations in Rate of Cooling in Ingot Molds. Discussed by Emil Gathmann, Paul E. McKinney, George A. Dornin. 27 MONYPENNY, JOHN H. G.-Stainless Steel, with Particular Reference to the Milder Varieties (Stainless Iron). Discussed by P. A. E.-Armstrong, Beram D. Saklatwalla 33 ROYSTER, P. H., and JOSEPH, T. L.-Effect of Coke Combustibility on Stock Descent in Blast Furnaces. Discussed by Ralph H. Sweetser,. Richard Franchot, Sidney Cornell, T. L. Joseph 41 DAVIS, F. W., and BOLE, G. A.-Observations on Requirements of Refractories for Open Hearth. Discussed by C. L. Kinney, Jr., L. F. Reinartz, P. E. McKinney 46

Jan 5, 1924

By J. E. Forciea, O. E. Palasvirta, L. G. Hendrickson

AH pilot and commercial plants working with Mesabi Range taconite employ wet magnetic separation. Progress is being made with a dry magnetic process, but this has not yet been applied to taconite except in the laboratory and pilot plants. Flowsheets in all five plants are similar, including multiple stages of grinding, each followed by magnetic separation, which rejects a finished tailing. The flowsheet in Fig. 1 is used in the preliminary and commercial plants of the Erie and Reserve mining companies and in Unit C of Oliver's Pilotac plant. At Erie the desliming operation is omitted. In the Reserve plants two ball mills are used with each rod mill. Pilotac uses flowsheet 2 in Unit A-B and has also tested flowsheet 3. Principal differences in the three flowsheets are the number of grinding stages and the type of roughing. The terms open-circuit roughing and closed-circuit roughing are best defined by the diagrams. Special Test Data Given in Table I: For the Erie and Reserve commercial plants, Table I reflects routine conditions. Pilotac, the experimental plant, has been run with several flowsheets, including those followed at Erie and Reserve's commercial operations. Pilotac data for these last two flowsheets are similar to commercial plant results and are not repeated in Table I; statistics are given, however, for special test conditions. using other flowsheets. when the objective was to 'to extra-grade concentrate, Variations Among Taconites: Although crude ore tributary to these plants is generally classified as taconite, there are important differences in mineralogy and fineness of dissemination.

Jan 1, 1959

Institute of Metals Division SAM TOUR, Chairman J. R. FREEMAN, JR., Vice-chairman ZAY JEFFRIES, Past-chairman C. H. MATHEWSON, Vice-chairman WILLIAM M. COHSE, Secretary-Treasurer 810 Eighteenth Street, N. W. Washington, D. C. Executive Committee Until February, 1931 Until February, 1932 Until February, 1933 T. S. FULLER J. L. CHRISTIE W. M. W.M. PEIRCE G. E. JOHNSON ARTHUR PHILLIPS A. J. PHILLIPS W. A. SCHEUCH H. M. WILLIAMS GUY C. RIDDELL Research PAUL D. MERICA, Chairman S. SKOWRONSKI Data Sheet R. S. ARCHER, Chairman T. S. FULLER J. STRADSS C. H. MATHEWSON F. L. WOLF

Jan 1, 1929

By Pierre I. Desré, Donald T. Hawkins, Ralph Hultgren

The torsion effusion method has been used to measure the vapor pressure of thallium over pure thallium in the temperature range 931" to 996'k The resulting 100 cal per g-atom is in excellent agreement with previous values. Vapor pressures of T1 above seven Ag-Tl alloys ranging from 33 to 90 at. pct T1 were measured at 979K. Calculated silver activities show a positive deviation from Raoult's law, approaching ideality near the liquidus. Measured thallium activities scatter less than previous measurements using the electromotive force technique. Values for the silver component were calculated by Gibbs-Duhem integration. This paper reports the results of a study of the liquid Ag-T1 system by the torsion effusion method. The method has been discussed in detail previously1 and will be only briefly summarized here. The sample is contained in a cell which is suspended on a torsion wire. Vapors effusing from orifices on opposite sides of the cell exert a torque on the wire. The torque is related to the vapor pressure by the following relation: where D is the torsion constant of the wire, 4 the angle of torque, fl and f2 the correction factors determined by Freeman and seamy2 to account for orifice length, a1 and a2 the areas of the orifices, and ql and q2 the distances of the orifices from the axis of rotation. By using the same cell for pure thallium and the alloy, it follows that: so that most systematic errors are eliminated in determining the activities. EXPERIMENTAL 99.999+ pct T1 was obtained from the American Smelting and Refining Co. and 99.999 pct Ag was obtained from Cominco American, Inc. Seven Ag-T1 alloys, ranging in composition from x^\ = 0.33 to 0.90, were prepared by melting together weighed amounts of the pure metals in sealed, evacuated Vycor tubes and quenching the melts in water. The apparatus and graphite cells were the same as those used by Hawkins and Hultgren3 in their study of the Pb-Sn system. RESULTS Ten measurements were made on pure thallium in the temperature range 931" to 996K, and the results are presented in Table I. Values of were calculated using tabulated Gibbs (free) energy functions.4 No dependence of on temperature or orifice size was found, indicating that equilibrium was attained. Data for the Ag-T1 alloys are shown in Table 11. Values were smoothed with respect to composition by a plot of where . DISCUSSION The value = 43,520 * 100 cal per g-atom for pure thallium (95 pct uncertainty limit) is in excellent agreement with previous investigations.4 In the Ag-T1 system, this study shows positive deviations from Raoult's law at all compositions. Fig. l gives the phase diagram according to Hansen, and Fig. 2 presents the activity values measured in this study as well as those from electromotive force measurements at 950°K by Terpilowski, Kundys, and slaby.'

Jan 1, 1969

By P. K. Leung, S. R. Allada, P. M. Dranchuk, D. Quon

The alternating direction explicit procedure (ADEP) makes use of the boundary conditions to reduce multi-dimensional problems to a series of one-dimensional problems. The method, previously applied to reservoirs containing only an under-saturated oil, has now been extended to cover the case of natural gas reservoirs. l his involves solving a non-linear partial differential equation, application of the procedure is straightforward and no calcuIational problems were encountered. INTRODUCTION There has been a growing interest in formulating mathematical models of petroleum and natural gas reservoirs — models which permit the engineer to examine and evaluate the physical and economic consequences of various alternative production policies. The tremendous reduction in the cost of solving such models in recent years has made possible their use as an almost routine management tool. This reduction is the result not only of improved computer hardware but also of the development of more efficient mathematical techniques. The present paper is concerned with the application of a recently proposed numerical method (ADEP) to two-dimensional gas reservoirs. STATEMENT OF THE PROBLEM Given a two-dimensional Region R, bounded by a closed Curve C (Fig. 1) such that the behavior on Curve C is known, the differential mass balance for each fluid phase in R, neglecting gravitational effects and assuming Darcy's law for fluid transport, can be written as:

Jan 1, 1967

By E. A. Gulbransen, W. S. Wysong

THE behavior of molybdenum and its surface oxides in oxidizing and reducing gas atmospheres and in high vacua at elevated temperatures is a question of scientific and technical importance The use of molybdenum as a metal or as an important component in alloys in oxidizing atmospheres at elevated temperatures has been limited because of the unprotective nature of its oxide film and the volatility of this oxide at moderate temperatures. This communication will present results of a vacuum microbalance study 1,2 of the following problems. (11) the oxidation kinetics in the temperature range of 250° to 450°C; (2) the reduction with pure hydrogen of thin oxide films formed on molybdenum; (3) the volatility of the thin oxide films, and (4) the vacuum oxidation of molybdenum at high temperatures. Molybdenum is an interesting metal to study for the following reasons: (I) although the oxide-to-metal-volume ratio is greater than one, the metal is not considered protective; (2) the metal oxidizes readily at temperatures of 250°C and higher; (3) the oxides of the metal are reduced at temperatures as low as 500°C by pure hydrogen; (4) the oxide MoO3 melts at 795°C; and (5) the oxides of molybdenum are volatile at moderate temperatures. The following variables are studied in the oxidation kinetics. time, temperature, pressure, surface preparation, surface area, concentration of inert gas in the lattice, cycling procedures in temperature, vacuum effect and high temperature vacuum oxidation The general interpretation of many of these factors has been previously discussed. LITERATURE The oxidation of molybdenum has not been studied critically. Although" many studies have probably been made on the kinetics of the oxidation process, none has been reported in the literature available to us. The crystal structures found in the oxidation of molybdenum have been studied by Hickman and Culbransen 4 Their results showed that MoO2 is the oxide which is stable in contact with the metallic subgtrate throughout the temperature range 300 to 700°C. As the film thickens in the low temperature range, MoO3 becomes predominant on the surface. Above 400°C, Mo03 is no longer observed, Mo02 being the only oxide found. Hagg and Magneli5 have shown from an X ray study that the a-phase, orthorhombic MoO3 is stable up to 1050°C. Two other phases, ß and ß', with compositions close to Mo02 90 are also obtained The formula for the ß phase is not given but that of the ß' phase is defined as Mo9026. The ß' phase is found to be built upon a monoclinic unit cell. A -?-phase is isolated from a preparation M00275 heated for 17 hrs at 670°C. This phase is

Jan 1, 1947

By Nicholas J. Grant, Noboru Komatsu

Metallographic and X-ray studies were made of oxide dispersion strengthened Cu-12 vol pet SiO2 and Cu-3.5 vol pet Al2O3 alloys following time exposures at temperatures approaching the melting. point of the matrix metal. Changes in hardness, oxide particle size and crystal structure were studied to determine the time-temperature stability of these alloys. An interpretation of the mechanism of oxide agglomeration is proposed. One of the most striking features of dispersion strengthened metal-metal oxide alloys is their stability at elevated temperatures, both with respect to recrystallization and maintenance of mechanical properties after exposure at high temperatures. A small amount of work has been done on the re-crystallization phenomenon in dispersion hardened metal-metal oxide alloys'l and several theoretical treatments have been advanced regarding the stability of these alloys by Lenel and Ansell,8 and by Grant and his co-workers.9, 10 This paper reports on metallographic and X-ray studies following various heat treatments of Cu-AI2D3 and Cu-SiO2 alloys at elevated temperatures and the effect of subsequent cold work on the recrystallizalion temperature. An interpretation of the recrystallization behavior of this type of alloy, based on the decomposition and agglomeration of oxides, is proposed. EXPERIMENTAL PROCEDURE Cast ingot bars of copper-1.59 pet Si and Cu-0.77 pet Al, 7/8 in in diam, were annealed in argon for 80 hr at 1000CC for homogenization. The homogenized rods were machined into fine chips and ball milled. Milled particles in the range minus 20 to plus 60 mesh were separated for internal oxidation. The internal oxidation was accomplished by the same method used by Preston and Grant,9 except that the oxidalion temperature for the Cu-Si alloy was 750°C, and for the Cu-A1 alloy was 800°C. These powders were then hydrogen-reduced at 450°C, compacted in a copper container, evacuated at room temperature to 0.04 µ, and sealed for extrusion. They were extruded at 1400°F (760°C) with a ram speed of 55 in. per min for an extrusion ratio of 15.6 to 1 to give a rod 0.38 in. diam by about 3 ft long.

Jan 1, 1962

By L. E. Tanner

A study was made of the transformation kinetics of the commercial titanium-base alloys, Ti-2.5Al-16V and Ti-4A1-3Mo-1V, using two different heat treatment cycles: 1) step-quenching to aging temperatures from a ß solution anneal and 2) water-quenching from an a+ß solution anneal followed by reheating to aging temperatures. Metallographic examination and hardness testing provided the major portion of the data, while electrical resistivity, dynamic elastic modulus, and X-ray diffraction techniques were also used to obtain critical or confirnzatory data. TTT diagrams were constructed from these results. The sheet alloys, Ti-2.5Al-16V and Ti-4Al-3Mo-lV, are of current interest to the Department of Defense. As an aid to the planning of their respective heat treatments, a program was carried out to determine the transformation kinetics of these alloys using ß and a + ß reference states. This paper presents the TTT diagrams constructed from data obtained by metallographic examination and hardness testing, as well as by X-ray diffraction, electrical resistivity, and dynamic elastic modulus determinations. EXPERIMENTAL PROCEDURE Materials—Sheets of the alloys were obtained from the producers in the "mill anneal'' condition and were tested prior to shipment to assure their meeting mill specifications. Chemical analyses were also supplied and are presented in Table I. Heat Treatment—The majority of the data presented in this study were obtained from hardness testing and metallographic examination. Sample coupons were cut from the alloy sheets and heat treated on a mass scale. The annealing cycles were operated in the following manner: 1) The ß solution anneals were carried out in a horizontal tube furnace with the bare samples protected by a dynamic helium atmosphere. Following this treatment, the samples were quickly transferred to lead, solder, or oil-bath furnaces for aging. After prescribed times at the various reaction temperatures they were water-quenched. 2) The second cycle simulated commercial practice, which requires the alloys be quenched to room temperature following the a + ß sotution anneal. This anneal was carried out in a muffle furnace with a dynamic helium atmosphere. The specimens were then reheated from room temperature to the reaction temperatures in lead, solder, or oil-bath furnaces, followed by water-quenching after prescribed times at these temperatures. Information concerning the critical temperatures of the alloys was obtained from the literature and solution treatments were based on these values. A summary of the solution annealing treatments is found in Tables II and 111. The aging temperatures for the (a - ß alloys ranged in 50°C intervals from 200°C (392oF) to approximately 50°C below the ß/a + ß transus in the first cycle and approximately 50°C below the a + ß solution temperature in the second. The transformations in these alloys were known to be rather rapid, and thus aging times started at 0.5 min and went to a maximum of 7000 min. Hardness Testing and Metallographic Preparation— Heat-treated samples were sheared and mounted in Bakelite with their cut edges exposed. After a flat surface was ground, the hardness was determined in Vpn on an Armstrong-Vickers machine utilizing a 20-kg load. Three to four impressions were made on each specimen. After this procedure, the hardness impressions were removed and the edge surfaces of the specimens were prepared for metallographic examination in the usual manner. The etchant was 20 pct HF and 20 pct HNO3 in glycerine. Electrical Resistivity—It has been shown that the isothermal reactions in titanium-base alloys can be followed by measuring the changes in e1etrical resistivity attending these transformations. As mentioned earlier, the reaction kinetics of a-ß alloys are rather rapid; thus, it would be expected that resistivity data obtained from these alloys would be more significant if measurements were made continuously at the respective aging temperatures. To accomplish this end a special apparatus, based on the current-potential principle, was assembled. Its design was derived from earlier devices constructed by Colner and zmeska1 4 and Levinson.5 The set-up provided for the heat treatment zof machined specimens (approximately 2 x l0-4in. in cross section by 3 in. in length) and the determination of their relative

Jan 1, 1962

By H. T. Bowman

For more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the I860's it was recognized that the process would benefit by some type of instrumental contro1.l IIowever, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower's eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham,3 A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient menoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. Carbon-FeO Relationship In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by Mccutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per. cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a . different method than were those

Jan 1, 1942

By H. T. Bowman

For more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the I860's it was recognized that the process would benefit by some type of instrumental contro1.l IIowever, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower's eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham,3 A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient menoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. Carbon-FeO Relationship In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by Mccutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per. cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a . different method than were those

Jan 1, 1942

By Eric Jette

IN a recent article,1 the authors reported the results of an X-ray investigation on the range of solid solutions that occurs in the iron-oxygen system in the vicinity of the compound FeO, which frequently is called "Wüstite." The object of that investigation was primarily to study the unusual type of solid solution phenomena involved in this range. Briefly summarized the results were: 1. The NaCl type of lattice found by earlier workers was confirmed. 2. The lattice dimensions decrease rapidly with decrease in iron content. 3. No alloy that was a homogeneous single phase was ever found at compositions beyond 76.80 per cent Fe, while the theoretical iron content of FeO is 77.73 per cent Fe. 4. Measurements of the densities and lattice constants led to the conclusion that the form of substitution was complex, an FeO group being replaced by oxygen. Such a substitution, of course, is equivalent to removing an iron atom (or ion). The ideal unit cell of FeO can be con-sidered as containing four groups of FeO and, thus, when this type of substitution takes place, there remain in the unit cell three FeO groups and an oxygen, or a total of seven atoms with a gross formula of Fe304 instead of the original Fe404. 5. This was the only interpretation that would fit the experimental results and at the same time be consistent with (a) the previously deter-mined fact that the FeO lattice is ionic (i. e., consists of Fe++ and 0= ions) and (b) the chemical fact that as the oxygen content of the substance increases, ferrous iron becomes oxidized to ferric iron. The experimental results of this investigation are included in Fig. 1.

Jan 1, 1933

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By Frederic Benard

PRIOR to 1936, the Ontario Refining Co. received all incoming blister copper from The International Nickel Company's smelter in the usual form of 460-lb. cakes, or slabs. These were received in open cars in lots of 250 pieces. At the refinery the cakes were unloaded onto narrow-gauge cars, for convenient handling and pickup by charging cranes. In March 1936, an investigation was started on the feasibility of transferring converter copper in the molten state from the smelter to the refinery anode furnaces, a distance of 1 ¼ miles. Although common in steel practice, the transportation of blister copper in this form had not previously been attempted and a preliminary study of the various factors involved was therefore necessary. For this purpose, a series of experiments was made in which molten copper, removed at different stages during the furnace cycle, was held in a small portable holding furnace. This vessel was essentially a refractory-lined steel cylinder provided with ports for filling and emptying, heated by an oil burner. Dimensions of the steel shell were 3 ft. 10 in. diameter by 7 ft. 3 in. long, and thickness of refractories depended on the design and combination used for the particular experiment. The vessel was filled with approximately 2 ½ tons of copper at a predetermined temperature, the lining having been preheated to a definite point by means of an oil burner. All openings were well luted and temperature readings were made every 15 min. by means of an immersion-type thermocouple. In this manner the rate of heat loss resulting with different refractory design could be developed. The ratio of exterior surface to weight of metal was taken into consideration in comparing the experimental results with what might be expected for a full-sized unit, and observations were also made on type and degree of slag accretion. It was not possible to get as much information on this latter point as desirable, but all evidence showed that the problem would be control of slag build-up rather than attack on refractories. From the information derived, and in consultation with the engineering staff of the supplying company, an order was placed for the first

Jan 1, 1938

By B. A. Wilcox

ThERE are several reports in the literature which indicate that both solid-solution hydrogen and hydride precipitates can promote low-temperature em-brittlement of tantalum.1-3 For example, Imgram et al.2 showed that hydrogen additions in the range of 140 to 580 ppm promoted a ductile-to-brittle transition at slightly above room temperature in both wrought and recrystallized tantalum. This contrasts with the observation that tantalum of norma1 purity is very ductile, even at liquid-nitrogen temperature. Imgram et al. also found that hydrogen additions caused a deterioration of notch tensile properties of tantalum. The purpose of this communication is to present some limited evidence that hydrogen can also cause fatigue embrittlement of tantalum. The material used in this investigation was wrought, stress-relieved (1000°C, 1 hr), are-melted tantalum rod (5/8-in. diameter) containing the following impurities in weight percent: 0.005 C, 0.007 02, 0.0005 H2, 0.003 N2, 0.08 Cb, 0.01 W, and 0.01 Fe. Hydrogen charging was done in an atmosphere of flowing dry hydrogen for 3 hr at 600°C, followed by an homogenizing anneal in purified argon for 15 min at 600°C, and cooling in an argon atmosphere. Typical micro-structures of the hydrogen-free and the hydrogen-charged materials are shown in Fig. 1(a) and Fig. 1(b), respectively. Fig. 1(b) shows the appearance of hydride precipitates which, in many cases, formed preferentially parallel to the rod axis. The hydride dispersion was uniform across the diameter of the specimen. The fact that the precipitate was a tantalum hydride was tentatively confirmed by X-ray diffraction on a metallographically prepared surface. After hydrogen charging, chemical analyses by vacuum fusion revealed the hydrogen content to be 0.0295 wt pct. In addition, the oxygen and nitrogen contents were slightly raised to 0.0095 O2 and 0.005 N2.

Jan 1, 1964

By H. A. Doerner, F. D. DeVaney, J.B. Clemmer

Production of magnesium metal in the United States during the past decade has increased from less than 600,000 lb. in 1928 to more than 4,800,000 lb. in 1938.1 The growing industry has stimulated interest in methods of production and in sources of raw material. All of the present domestic production is from brines. However, the availability of large tonnages of magnesite in the state of Washington, together with the possibility of cheap power, have created interest in the utilization of magnesite for the production of magnesium metal as well as for other purposes. Magnesite, the carbonate of magnesium (MgCO3), usually is associated with limestone (CaC03) and dolomite (MgCO3. CaC03). It occurs in crystalline and microcrystalline (sometimes termed amorphous) forms.2 The more common crystalline mineral is found in various shades of white, gray, yellow and brown, the colors being due to impurities, chiefly iron. Magnesite has a hardness of 3.5 to 4.5 and a specific gravity of 3.0 to 3.1. It forms rhombohedra1 crystals in the hexagonal system, having a vitreous, pearly luster. The quarries and mines of the Northwest Magnesite Co. near Chewelah, Wash., are large producers of magnesite for refractories. The deposits are extensive, some veins being hundreds of feet wide. The boundaries of the veins are indefinite, and the magnesite is interfingered with dolomite. Calcite, talc, serpentine, quartz and shale are disseminated through the deposits. The quality of the ore cannot be determined by appearance or by simple tests; chemical analysis is required. These features make it difficult to determine the boundaries or total quantity of workable ore.3 Only the higher-grade ores are mined, and a considerable proportion of the magnesite content is discarded by hand-sorting and log-washing methods. After calcining, the sorted product meets the specifications for usual refractory material, as it contains approximately 81 per cent MgO, 7 per cent SiO2, 6 per cent CaO and 6 per cent Fe203 + A1203. A sample of the reject material had the following analysis after calcining: 65.4 per cent MgO, 6.3 CaO, 21.1 SiO2 and 6.5 R2O3. The percentage reported as R2O3 includes compounds whose chlorides are acid-soluble but give precipitates in ammoniacal solution that are ignited and weighed. The more common constituents are Fe2O3, A1203 and TiO2. The sorted magnesite product is not the best grade. even for refractory purposes, and leaves much to be desired for a reduction process. The rejected material contains a large proportion of magnesite. It is apparent that an effective concentration method would yield a higher recovery and a better product. In general, the refractory grade is not suitably pure for other uses. Recent developments in the production of

Jan 1, 1943

By J. B. Clemmer, F. D. DeVaney, H. A. Doerner

Production of magnesium metal in the United States during the past decade has increased from less than 600,000 lb. in 1928 to more than 4,800,000 lb. in 1938.1 The growing industry has stimulated interest in methods of production and in sources of raw material. All of the present domestic production is from brines. However, the availability of large tonnages of magnesite in the state of Washington, together with the possibility of cheap power, have created interest in the utilization of magnesite for the production of magnesium metal as well as for other purposes. Magnesite, the carbonate of magnesium (MgCO3), usually is associated with limestone (CaC03) and dolomite (MgCO3. CaC03). It occurs in crystalline and microcrystalline (sometimes termed amorphous) forms.2 The more common crystalline mineral is found in various shades of white, gray, yellow and brown, the colors being due to impurities, chiefly iron. Magnesite has a hardness of 3.5 to 4.5 and a specific gravity of 3.0 to 3.1. It forms rhombohedra1 crystals in the hexagonal system, having a vitreous, pearly luster. The quarries and mines of the Northwest Magnesite Co. near Chewelah, Wash., are large producers of magnesite for refractories. The deposits are extensive, some veins being hundreds of feet wide. The boundaries of the veins are indefinite, and the magnesite is interfingered with dolomite. Calcite, talc, serpentine, quartz and shale are disseminated through the deposits. The quality of the ore cannot be determined by appearance or by simple tests; chemical analysis is required. These features make it difficult to determine the boundaries or total quantity of workable ore.3 Only the higher-grade ores are mined, and a considerable proportion of the magnesite content is discarded by hand-sorting and log-washing methods. After calcining, the sorted product meets the specifications for usual refractory material, as it contains approximately 81 per cent MgO, 7 per cent SiO2, 6 per cent CaO and 6 per cent Fe203 + A1203. A sample of the reject material had the following analysis after calcining: 65.4 per cent MgO, 6.3 CaO, 21.1 SiO2 and 6.5 R2O3. The percentage reported as R2O3 includes compounds whose chlorides are acid-soluble but give precipitates in ammoniacal solution that are ignited and weighed. The more common constituents are Fe2O3, A1203 and TiO2. The sorted magnesite product is not the best grade. even for refractory purposes, and leaves much to be desired for a reduction process. The rejected material contains a large proportion of magnesite. It is apparent that an effective concentration method would yield a higher recovery and a better product. In general, the refractory grade is not suitably pure for other uses. Recent developments in the production of

Jan 1, 1943

By C. L. T. Edwards

In the preparation of this paper, the author has drawn upon experience with the operation of a blast furnace on Ioo per cent scrap burden, which he believes was the first operation of its kind in the country. It is the writer's further belief that much of the controversy attending discussions of this subject may be obviated by the presentation of a group of facts that should be known by blast-furnace men and open-hearth men alike. The following question has been raised: "Is iron made with scrap in the blastfurnace charge as good iron as that made without scrap—made with straight ore?" This question may he answered in part by the fact that the open-hearth men of the Bethlehem Steel Co. who used pig iron from a blast furnace that operated on Ioo per cent steel scrap found no difficulty in the processing of such iron other than that to be expected from the known analysis. Operation with ioo PeR Cent Steel Scrap During World War I, there was accumulated at the Bethlehem plant of the Bethlehem Steel Co. some 22,000 tons of alloy-steel turnings and borings. This scrap material was highly corroded and, like alloy-steel turnings of that period, were as a drug on the market. There was also a small tonnage of scale, rich in valuable metal. If this scrap could be worked up into pig iron, it would become readily available for use in the open hearth. In order that the pig iron should contain the maximum percentage of nickel, permission was obtained from the Management to try a Ioo per cent scrap operation. Accordingly, a blast furnace was swung over on July 25, 1919; the percentage of steel scrap increased more or less irregularly until July 29, when Ioo per cent steel turnings were charged. Except for occasional charges of nickel scale as an "cxtra," the operation continued uninterruptedly until Aug. 27, when the furnace was swung back to the regular ore—ore and scrap—operation. During this period, the furnace production ranged from a low of 568.60 tons to a maximum of 766.07 tons. At the swing-over from Ioo per cent scrap to the regular burden, the charge I hung up rather severely. While the latter condition has nothing to do with the object of the paper, a brief discussion of the experience will appear later because of the interest it may have for blast-furnace operators. In Table I, results of the first and last days of the ore charge are shown, July 25 and July 29. The last column shows a summary for the period of maximum scrap ' charge. The furnace employed had a hearth 16 ft. o in., bosh 22 ft. o in., stock line 15 ft. 6 in., bell 11 ft. 6 in., batter in., bosh angle 73' 27' and a Balrer-Neuman top, with gas-engine blowers. Analyses Range of material charged Gravel: SiO2, 64.40 to 70.54 per cent; A1203, 3.52 to 4.58; CaO, 7.27 to 9.49; MgO, 5.09 to 6.14; FeO, 1.67 to 3.34, ignition loss, 9.50 to 13.83. I

Jan 1, 1942

By C. L. T. Edwards

In the preparation of this paper, the author has drawn upon experience with the operation of a blast furnace on Ioo per cent scrap burden, which he believes was the first operation of its kind in the country. It is the writer's further belief that much of the controversy attending discussions of this subject may be obviated by the presentation of a group of facts that should be known by blast-furnace men and open-hearth men alike. The following question has been raised: "Is iron made with scrap in the blastfurnace charge as good iron as that made without scrap—made with straight ore?" This question may he answered in part by the fact that the open-hearth men of the Bethlehem Steel Co. who used pig iron from a blast furnace that operated on Ioo per cent steel scrap found no difficulty in the processing of such iron other than that to be expected from the known analysis. Operation with ioo PeR Cent Steel Scrap During World War I, there was accumulated at the Bethlehem plant of the Bethlehem Steel Co. some 22,000 tons of alloy-steel turnings and borings. This scrap material was highly corroded and, like alloy-steel turnings of that period, were as a drug on the market. There was also a small tonnage of scale, rich in valuable metal. If this scrap could be worked up into pig iron, it would become readily available for use in the open hearth. In order that the pig iron should contain the maximum percentage of nickel, permission was obtained from the Management to try a Ioo per cent scrap operation. Accordingly, a blast furnace was swung over on July 25, 1919; the percentage of steel scrap increased more or less irregularly until July 29, when Ioo per cent steel turnings were charged. Except for occasional charges of nickel scale as an "cxtra," the operation continued uninterruptedly until Aug. 27, when the furnace was swung back to the regular ore—ore and scrap—operation. During this period, the furnace production ranged from a low of 568.60 tons to a maximum of 766.07 tons. At the swing-over from Ioo per cent scrap to the regular burden, the charge I hung up rather severely. While the latter condition has nothing to do with the object of the paper, a brief discussion of the experience will appear later because of the interest it may have for blast-furnace operators. In Table I, results of the first and last days of the ore charge are shown, July 25 and July 29. The last column shows a summary for the period of maximum scrap ' charge. The furnace employed had a hearth 16 ft. o in., bosh 22 ft. o in., stock line 15 ft. 6 in., bell 11 ft. 6 in., batter in., bosh angle 73' 27' and a Balrer-Neuman top, with gas-engine blowers. Analyses Range of material charged Gravel: SiO2, 64.40 to 70.54 per cent; A1203, 3.52 to 4.58; CaO, 7.27 to 9.49; MgO, 5.09 to 6.14; FeO, 1.67 to 3.34, ignition loss, 9.50 to 13.83. I

Jan 1, 1942

By A. E. Chute

The shortage of sulfur is not only continuing but appears to be worsening, attended by steadily rising prices. At the same time emphasis on air-pollution abatement is also increasing. These two factors, a rising market and the growth of environmental attention, have encouraged producers to carefully review all possible sulfur sources. As a result, production of sulfur from hydrogen sulfide occurring in petroleum is receiving greater attention than ever before. Until about a decade ago, the practice of recovering sulfur from hydrogen sulfide separated from gases (either found naturally or generated in desulfurization of liquid petroleum) was wide1y recognized but contributed little to total free-world sulfur production. However, during the past ten years, the production of sulfur from this source has increased so rapidly that it now accounts for a substantial portion of total production. This trend shows no signs of slackening, and current forecasts predict that recovered sulfur may become the dominant source of supply within ten years, exceeding mined sulfur production. This paper is intended to list sulfur sources and relationships, and to discuss the potential of producing sulfur from petroleum. The processing involved, in addition to product storage and transportation will also be discussed along with important economic aspects of sulfur recovered from hydrogen sulfide. For many years, most of the world's elemental sulfur has been produced from salt domes, predominantly by the Frasch process. During the past decade, however, another production source has developed so quickly that it is expected to surpass the Frasch production sources within a short time. This new source lies in the petroleum gases and liquids from which dramatically increasing quantities of elemental sulfur are being recovered. In the phraseology of the trade, the sulfur so obtained is know as "recovered sulfur," a term which does not, as one might expect, include sulfur recovered from other sources such as smelter gases. The growth rate of recovered sulfur compared to that of Frasch sulfur, total elemental sulfur, and total Free World sulfur in all forms is shown in Fig. 1 Since 1963, sulfur consumption has exceeded production,with the natural result that the price of sulfurhas continually increased. The posted price reported for f.o.b. Port Sulphur, La., has risen from as low as $18 per ton in 1962 to $32.50 per ton in mid-1967. With freight and other charges, delivered prices have of course run much higher, amounting to $45 or $46 per ton on the east and west coasts. In some cases, spot sales for as much as $60 have been reported. Although it is playing an ever-increasing role in the sulfur market, recovered sulfur was originally a by-product of the removal of hydrogen sulfide from natural and petroleum refinery gases. Today, however, it is often the most valuable product of a multi-product processing facility. Since there are two major sources of recovered sulfur—production and refining processes —natural gas is included with liquid petroleum for purposes of this discussion. Sulfur from these sources is produced in the form of gaseous hydrogen sulfide which is removed from a gas stream and converted to elemental sulfur. Gases in which hydrogen sulfide occurs naturally are natural gas and the gas produced from a high=pres-sure crude=oil or condensate field.

Jan 1, 1969

By Carl J. McHargue

Mechanical twins were produced in electron-beam melted columbium by high-speed impact at room temperature and by slow or fast compression at -196°C. The composition plane of the twins was { 112} and the shear direction was <111>. Notches in the twin bands often corresponded to traces of {110) of the matrix and appeared to be untwinned regions. Markings within the twin bands were interpreted as resulting from {110} slip in the twins. THERE has been much work in recent years concerning plastic deformation by glide, and the dislocation theory relating to glide has reached a relatively high degree of development. On the other hand, there have been fewer studies of deformation by mechanical twinning, and understanding of this process is far from satisfactory. This method of deformation is of interest for at least two reasons. First, it provides a mechanism in addition to glide for the relief of stresses, and, in the bcc and hexagonal close-packed metals may result in significant amounts of plastic flow. Secondly, there is the possibility that twins may act as barriers for dislocation movement, resulting in pile-ups which could nucleate cracks. As might be expected, the bulk of the literature on mechanical twinning in the bcc metals is concerned with iron. A good summary of the work done prior to 1954 is contained in the book by all.&apos; Recently the refractory bcc metals have become increasingly important. Limited studies have shown that tantalum,2,3 molybdenum,4,5 vanadium,6,7 tungsten,&apos; and columbium9-11 deform by mechanical twinning under some conditions. Alloys of molybdenum with rhenium and tungsten with rhenium show extensive deformation by twinning at room temperature.I2-l4 Most of these studies have dealt primarily with mechanical properties at low temperatures or have shown the existence of twins, and there is only a small amount of information concerning the conditions under which they form. The subject of the present paper is the formation of twins under stress in columbium with a consideration of their morphology. EXPERIMENTAL PROCEDURE The material used for these studies was taken from an ingot of columbium which had been melted twice by the electron-be am-method. The analysis of the ingot was (in ppm): B < 1, C = 10, Fe < 100, The cast ingot contained very large grains, and it was possible to obtain single-crystal prisms which measured from ¼ to 3/4 in. on a side. A few experiments were conducted on polycrystalline plate which was prepared by rolling material from the same ingot at room temperature and annealing at 1000 in a dynamic vacuum of 10-6 mm Hg. This gave a plate in which the grains had an average diameter of 3 mm. After the specimens were cut from the ingot, the six faces were metallographically polished and elec-tropolished to remove all traces of cold work. Most of the observations were made on the surfaces of the deformed specirllens without further treatment. Occasionally, etching after deformation was desirable. In these cases, an etchant of the composition 50 parts H2O, 5 parts HNO3 25 parts HF, and 10 parts H2SO4 was found to delineate the twins very well. Unless considerable care was taken to ensure the removal of all disturbed metal left by the mechanical polishing, etching failed to reveal many of the features discussed in this; paper. The specimen&apos;s were deformed either by impact or slow compression at 77°K (liquid-nitrogen coolant), 198°K (dry ice and acetone coolant), and 298°K. The impact load was delivered by a hammer except in one case where the load was delivered by a bullet. Slow compression was carried out on a hydraulic testing machine equipped with a chamber to hold the coolant. EXPERIMENTAL RESULTS It has been generally believed that the conditions favoring the formation of deformation twins are large grains, low temperature, and impact loading. In fact, Barrett and Bakish2 found twins in tantalum only after impact deformation at 77°K, and Adams, Roberts, and Smallman10 observed twins in columbium only at 20 For these reasons, the initial experiments of this study used impact loading. Hammer blows caused many bands resembling twins in single crystals a.t 77" but not at 198°K. Only a few slip lines were observed on any of the single-crystal specimens of this study—essentially all the deformation occurred by twinning. The appearance of the twins on the as-deformed surface is shown in Fig. 1. Although both Figs. 1(a) and l(b) are photomicrographs of twins taken at the same magnification and from the same crystal, they are startlingly different in appearance. Fig. 1(a) was taken from the crystal face approximately perpendicular to the shear direction, whereas Fig. 1(b) was taken from

Jan 1, 1962