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By R. J. Woody

Design of the most economic continuous counter-current decantation (CCD) circuit is based on selection of the number of stages and the wash volume that will give the minimum summation of the following items: 1) Capital and operating costs of the CCD circuit. 2) Capital and operating costs of the precipitation circuit. 3) Value of the dissolved product lost.

Jan 1, 1959

By J. Chipman

There is no better way of paying tribute to the memory of a scientist than by developing and carrying forward those ideas which he has contributed to science and which are for us the very essence of his immortality. For a lecturer who has not had the great privilege of stdying under Professor Howe or 'ven of knowing him in person, these ideas must be transmitted through the printed word. It is our great good fortune that Professor Howe left to us a rich heritage of publication, not only in his classic monograph on the "Metallography of Steel and Cast Iron" but in a wealth of earlier hooks and papers in the transactions of this Institute arid of other scientific and engineering bodies. An outstanding characteristic of this published record is the great breadth of interest and of vision which it portrays. His was riot a narrow specialization in only the scientific aspects of ferrous metallographg. On the contra1y many of his important contributions had to do with a far broader field of metallurgicial endeavor. He insisted that his students be well grounded in 1 he fundamentals underlying the whole field and not led into the narrow groove of specific applications. Among his first major publications we find papers on copper smelting, extraction of nickel, the efficiency of fans and blowers, thermic curves of blast furnaces, the cost, of coke, and the manufacture of steel. These are the papers of a metalhurgical engineer and it was among engineers that Henry Marion Howe made his early and well-merited reputation. These early engineering contributions display very clearly the strongly sctientific inclination of their author. The classic work on "The Metallurgy of Steel" published in 1890 contains a thorough and critical discussion of all that was known at the time concerning the alloys of iron and of what we would now call the physical metallurgy of steel. In addition it describes steel-making processes in use and some that had become obsolete, and points out in critical fashion the reasons for success and failure. Steel mill design and layout were included as well as some pertinent discussion of refractories. The book is indeed an embodiment of one of Howe's outstanding characteristics—breadth. It is both the science and the engineering of steel production as known in that day. One of Howe's earliest technical papers was entitled "What is Steel?" That was nearly seventy-five years ago when many new processes and new kinds of steel were being developed. The time was ripe for such a question and the answers which Howe was able to give were helpful in understanding the phenomena of heat treatment. Twenty-five years ago Professor Sauveur repeated the question as the title of the first Henry Marion Howe Memorial Lecture. It seemed to him that this question, "What is Steel?," had served as Howe's motto throughout the remainder of his life. Today I shall present for your consideration a question of another sort: "What is Sletallurgy?" Perhaps it is not too much to hope that in the answer we may obtain a clearer and possibly broader view of the nature of our science and our profession. The time is ripe for giving careful consideration to what we mean by metallurgy. If our Metals Branch is to become in fact an American institute of Metallurgical Engineers, it is essential that we understand what is meant by metallurgical engineering. I am convinced that the best interests of the profession have not been served by a narrow interpretation of these terms. We must now place emphasis on the breadth of metallurgy as a science and as an engineering profession. With its usual brevity and wit. Webster's dictionary definesmetallurgy as "the science and art of extracting metals from their ores, refining them and preparing them for use." I shall riot assume that the words "science" and "art" and "metal" are so well understood as to require no defining but others among our contemporaries are better qualified than either your lecturer or the dictionary to present the broad meanings of these terms. When we say that metallurgy is among the oldest of the arts we are not classing it with painting or sculpture or music but rather with the making of tools or weapons or the building of bridges or chariots or cathedrals. In short we are saying that metallurgy is among the oldest of the engineering professions. The question " What is metallurg ? " has been one of rather more than ordinary concern to those of us who have the task of developing a curriculum for the education of students in this field. This development has been going on in a number of universities over a period of some years. but there seems to be as yet no unanimity as to what such a curriculum should contain. I believe there is fairly complete agreement that it must be founded upon sound

Jan 1, 1950

By M. C. Fuerstenau, D. W. Fuerstenau

Studies of the collection of alkali and ammonium halides utilizing vacuum flotation techniques and contact angle measurements show that ionic size controls the flotation of techniquesthese halides with amine salts measurementsas collector. Contact angles of air bubbles on sylvite in saturated brines were withaminemeasured salts asascollector.a function of such variables as collector addition, length of collector chain, and pH of the brine. No contact occurs between halite and an air bubble in brines containing dodecylammonium acetate as collector. LONG-CHAINED aliphatic amine salts have been used for the separation of sylvite (KCl) from halite (NaCl) by flotation.1,2 It is puzzling how these two minerals, which are so similar chemically and crystallographically, can be separated by this method. Gaudin" has postulated that the difference in floatability of halite and sylvite with salts of primary amines depends on ionic size: In the case of amine flotation, the cation would attach itself to the chloride. I have a speculation there, which I cannot prove, that the ammonium group, that is the —NH3 group in the amine, floats potassium chloride because the dimensions of this grour, as it has been measured in other compounds is almost identically the dimensions of the potassium ion, quite different from the sodium ion, and so it fits where potassium had been, in place of it and not attached to it. Apparently, because an aminium ion (RNH3+) is much larger than a sodium ion, it cannot fit into the lattice of halite. Taggart also has speculated that ionic size may control the floatability of sylvite.4 The object of this experimental investigation has been to test this hypothesis and to study what controls the adsorption of cationic collectors at the surface of sylvite. Since collection is to be approached from the viewpoint of ionic size, the ionic radii that are of interest in this work are presented in Table I. The values of the ionic radii of the ions listed in Table I, except NH4+, are those given by Pauling." Several different values for the radius of the ammonium ion have been given, but that of Goldschmidt6 seems to be preferred. The radius of the charged head of a dodecylammonium ion is assumed to be the same as that for the ammonium ion. Little experimental work has been reported in the technical literature concerning the separation of sylvite from halite by flotation. Guyer and Perren studied the separation by flotation of 50 pct binary mixtures of NaCl, KC1, NH,Cl, NaNO3, KNO3, K2SO4, and Na,SO, using either oleic acid or a sodium sul-fonate as collector.' It is possible to measure floatability under actual flotation conditions where all three phases, air- water-mineral, are present by vacuum flotation tests and contact angle measurements.9 Both of these techniques were used in the experimental approach in this paper. Experimental Method and Materials The vacuum flotation tests were run with glass-stoppered pyrex graduated cylinders. Twenty-five ml graduates were used to test the floatability of all salts studied except rubidium and cesium salts. For each test distilled water containing the desired collector concentration was saturated with the salt to be floated. Sufficient salt (—48 mesh) was added to leave about 2 ml of solids in the bottom of the graduate. After the graduate had been agitated several minutes to saturate the solution with air, a vacuum was applied. If the salt were floatable in the collector solution, the gas bubbles attached themselves to the particles, and the particles floated to the surface. In determining the floatability of the expensive Rb and Cs halides, the experiments were run in 10 ml graduates with about 11/2 ml of collector solution initially. Contact angles were measured in the usual manner except that the solutions had to be previously saturated with the mineral to avoid dissolution of the crystal. Solutions for studying contact angles were made by adding the desired amount of collector to a saturated brine, giving the collector concentration in molarity. The mixture was agitated until dissolution of the collector was complete, with the exception of those concentrations greater than about millimolar. At these high concentrations complete dissolution of the collector was impossible. The face of the mineral to be tested was a freshly cleaved crystal of halite or sylvite. The mineral was placed in the brine and conditioned with collector for at least 15 min, which was found to be long enough to obtain a maximum value for the contact angle. The temperature remained constant during each experiment. The experiments were run at 24°C ±2°C. For contact angle measurements, a crystal of halite from Carlsbad, N. M., was used. Several samples of sylvite were used in this work: a crystal of sylvite from Stassfurt, Germany; a crystal from Carlsbad, N. M.; and a crystal of chemically pure potassium chloride. Saturated brines were made from reagent grade chemicals and distilled water.

Jan 1, 1957

By C. W. Pollock

THAT a distressing explosion of some magnitude did not take place in the Berry No. 3 mine of the Ford Collieries Co. recently was solely because no source of ignition was present when the stage was set for such an occurrence. The mines of this company, which are in West Deer Township, Allegheny' County, Pa., have been operating in the double or thick Freeport seam since 1.909. During this entire period they have been classed as gaseous by the Pennsylvania Department of Mines, and some gas has been encountered from time to time almost entirely however in development work in the vicinity of clay veins or wants-and never to my knowledge on gobs or in rib work.

Jan 1, 1935

By T. F. Witherbee

It is proposed to give, first, a description of the works; second, a report of the first six months of the present blast; and third, such improvements as have been suggested by the practical working. The site selected for this furnace was, at the time of commencing work, October, 1872, entirely covered by the navigable waters of Lake Champlain. A coffer-dam was first built of cribs of round timber filled with stone, forming three sides, while the shore answered for the fourth. Considerable excavating was done with a steam-dredge, a hole being left for it to pass out. The opening was then built up, and the cribbing banked up with blue clay from the bottom of the lake, to render it water-tight and the dam pumped out; the remainder of the excavating being done by hand. All of the foundations, with the exception of the elevator-tower, and fifteen feet of the east side of hot blast, rest on the Potsdam sandstone, which forms the shore line, dipping into the lake at an angle of fifteen degrees. Owing to jogs in the formation, a much greater depth was found necessary than was at first anticipated, the foundation under the stack

By T. F. Witherbee

IT is proposed to give, first, a description of the works ; second, a report of the first six months of the present blast; and third, such improvements as have been suggested by the practical working. The site selected for this furnace was, at the time of commencing work, October, 1872, entirely covered by the navigable waters of Lake Champlain. A coffer-dam was first built of cribs of round timber filled with stone, forming three sides, while the shore answered for the fourth. Considerable excavating was done with a steam-dredge, a hole being left for it to pass out. The opening was then built up, and the cribbing banked up with blue clay from the bottom of the lake, to render it water-tight and the dam pumped out; the remainder of the excavating being done by hand. All of the foundations, with the exception of the elevator-tower, and fifteen feet of the east side of hot blast, rest on the Potsdam sandstone, which forms the shore line, dipping into the lake at an angle of fifteen degrees. Owing to jogs in the formation, a much greater depth was found necessary than was at first anticipated, the foundation under the stack

Jan 1, 1876

By W. F. Chiao

With the application of dislocation damping theory an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. A ductile steel was compared with a brittle stee1 by simultaneously measuring the ultrasonic attenuation and velocity during tensile test, and the density of free dislocations and their mean loop length were then calculated as a function of strain. The results showed that in the ductile steel there was always a large generation of dislocations and great extension of loop length occurring at some stage within the early plastic region. In contrast, the brittle steel showed very little or no such sudden changes in dislocation dynamic states after the onset of plastic deformation. Furthermore, a strong temperature dependence of dislocation dynamic states was also observed in the ductile steel and a hypothesis was suggested that a thermally activated process of dislocation rearrangement could occur at higher deformation temperatures. The activation energy of dislocation rearrangement at room temperature was estimated as about 2030 cal per mole.C. DUCTILITY is an indispensible property in the application of engineering materials, especially steel. During the past two decades the theoretical and experimental approach to the understanding of flow and fracture of metals has been constantly undergoing changes and progress." while the fracture behavior of metals can be influenced by many factors such as chemical Composition,3 second-phase particle mor-phology,4 and dislocation arrangement,5 it is now a general belief that the fundamental understanding of the ductile-brittle fracture phenomena of solid materials must stem from the study of dislocation dv-namics developed under stress conditions.6,7 Most of the traditional ductility tests, such as Charpy impact test, slow bend test, and tensile fracture test, cannot by themselves reveal directly the mechanisms of ductile to brittle transition of materials. In the experimental investigation of tensile ductility it would be ideal to be able to study directly the dynamics of dis-locations in a bulk specimen during the process of deformation. Since the ultrasonic pulse technique is the only satisfactory method for studying dislocations and the fine details of deformation characteristics in metals in the course of a tensile test, it would appear that a comparative study of ultrasonic attenuation changes during tensile tests of metallic materials exhibiting different ductility might be very informative. So far no work comparable to this study has appeared in the literature. Recent progress in both theory and experiment has indicated the feasibility of studying the dislocation mechanisms of ductility behaviors by ultrasonic measurements during tensile test. Granato and Lucke8 have developed a quantitative theory that enables the calculation of dislocation density and their average loop length from the measurements of ultrasonic attenuation and velocity, and several investigators, including Chiao and Gordon,9'10 have shown that simultaneous ultrasonic measurements can be successfully made during a tensile test. Furthermore, many investigators11-13 have repeatedly proposed in the past several decades that deformation and fracture are mutually self-exclusive, and that the ability or inability of a material to deform plastically, i.e., to generate dislocations, is a major factor in determining whether the material will be ductile or brittle. Thus, in the present work an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. This article is principally concerned with the study of the relation between the propagation of ultrasonic waves and tensile deformation in a steel series which displays quite different toughness at room tempera-turk. changes in attenuation and velocity of ultrasonic waves have been measured as a function of strain during the deformation process. The results have been interpreted in terms of the vibrating string model for dislocation damping as developed by Granato and Lucke, and it has been found that some of the more subtle predications of the model are in good agreement with the experiments. This would be especially meaningful because most of the previous experiments in testfying the model were carried out with single crystals of high-purity materials and little work has been done with polycrystalline steel alloys. EXPERIMENTAL PROCEDURES AND RESULTS Specimen Materials. The tensile specimens used throughout this experiment were of two compositions selected from a series of Fe-Mo-0.77 pct Mn-0.22 pct C steels prepared for a ductile-brittle fracture transition study. One steel contains 0.21 pct Mo and the other 1.03 pct Mo. These two compositions were chosen for the present study because they possess quite different toughness properties at room temperature. The 0.21 pct Mo steel is quite ductile while the 1.03 pct Mo steel is rather brittle, as measured by the standard Charpy impact test. The alloys had been prepared by vacuum induction melting and chill casting in steel molds. The ingots were hammer-forged into 1/2-in.-sq bars from which tensile specimen blanks were cut. These blanks were first normalized under argon atmosphere at 1700°F and then reaus-tenitized and isothermally transformed at 1050°F to a bainitic microstructure. The chemical compositions, heat treatments, hardness measurements, and Charpy transition temperatures of the two steels are listed in Table I.

Jan 1, 1970

By F. Habashi

Conclusive evidence is given showing that the dissolution of gold in cyanide solution follows mainly the over-all equation A similar equation can also be written for the dissolution of silver. Theoretical derivation of the velocity equation for this reaction has been obtained, which describes quantitatively the experimental facts. The equation is as follows: where [CN-] and [O2] = the concentrations (in moles/ml) of cyanide and dissolved oxygen, respectively. DcN- and Do2 = the diffusion coefficients of cyanide and dissolved oxygen; 1.83 x 10-5 and 2.76 x 10-5 cm2 sec-1, respectively. A = the surface area of the metal in contact with the aqueous phase, in cm S = the thickness of the boundary layer; varies between 2 and 9 x 10-3 cm, depending on the speed and method of agitation. Rate being expressed in g. equiv. sec-1. INTRODUCTION During recent years a number of papers have been published on the kinetics of dissolution of gold and silver in cyanide solution.1,6 The authors agree that the rate of dissolution is diffusion-controlled, but disagree regarding the mechanism of the reaction. Some authors'-3 support the Bodlander equations: The apparently conflicting results, when critically reviewed, are concordant and lead to the conclusion that the proper equation for the dissolution reaction should be only Eq. 1. This conclusion is based on the following facts: 1) For every 2.2 equivalents of metal dissolved one mole O2 was consumed. 2) For every 1 equivalent of metal dissolved, 2 moles of cyanide were consumed.' 3) Hydrogen peroxide is formed during the dissolution of gold or silver, and for every 2.2 equivalents of metal dissolved, one mole H2O2 was produced.1,2 The fact that Kudryk and Kellogg4 did not detect H2O2 during the dissolution of gold should not throw doubt on the many affirmative reports of other investigators. Lund2 has shown that depending on the crystalline nature of the silver surface, (e.g. method of etching the sample) H2O2 may undergo catalytic decomposition heterogeneously according to: Further Kudryk and Kellogg4 carried out their experiments in the presence of 0.5% KC1 to achieve a greater electrolytic conductivity, and Matsudaira7 has shown that H2O2 is catalytically decomposed (homogeneously) in the presence of C1- ion in alkaline solution. 4) Experiments carried out by Boonstra8 and Lund2 showed that the dissolution of gold and silver respectively in KCN + H2O2 in the absence of oxygen was a slow process. Thus the reaction takes place to a minor extent only. Further kinetic studies showed that: 1) The rate of dissolution depends on the surface area of the metal in contact with the liquid phase, thus indicating that the process of dissolution is a heterogeneous process. 2) The rate of dissolution depends on the speed of stirring,5,6 thus indicating that the process is controlled by a physical phenomenon.

Jan 1, 1967

By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n'ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.' recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author's laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969

By S. H. Williston

IT not often that bore hole surveys can be checked by actual. civil engineering methods. A recent Arizona survey was checked by normal surveying methods and the comparison of the results should be of value to both oil and mining men. During the summer of 1948 the Phelps-Dodge Corporation, at its Copper Queen property near Bis-bee, Ariz., drilled a 1245 ft, 8 in. diarn, churn drillhole in a mineralized area and cased part of it, intending to use it to transfer mill tailings for stope fill. The hole, as frequently occurs, was not straight, and, in endeavoring to locate the bottom in the underground workings, they found no evidence of the hole at the underground coordinates directly below the surface location. The noise of the drilling tools was reasonably clear, but the direction of sound was uncertain. Preliminary tests with available equipment were not successful in locating the bottom of the hole. Because of the mineralized character of the area and the fact there was some casing in the hole, any magnetic method of well surveying would give results of doubtful value. Sperry-Sun gyroscopic well-surveying instruments were finally used to locate the bottom of the hole. These instruments consist of a gyroscope to determine azimuth and either a pendulum or bubble inclino-meter. A multiple shot camera photographs both instruments on a single film and superimposes the photograph of a watch. Coordination of depth with time at the surface makes it possible to select the corresponding picture for any depth. After making several runs of the empty instrument housing from the top of the hole to the bottom to make sure there were no obstructions in the hole, three surveys on wire line were completed during the afternoon. The three surveys, in which readings were taken at different points in the hole on each survey, were computed and gave the following locations of the bottom of the hole in relation to the surface collar: survey No. 1—24.92 N, 30.30 W; survey No. 2—24.24 N, 31.11 W; survey No. 3—26.54 N, 27.72 W. Then the data from the three surveys were combined into a single set of calculations which gave a location for the bottom of the hole: combined surveys—24.27 N, 30.16 W. (Fig. 1.) Immediately upon the determination of the coordinates at the bottom of the hole, a drift on the 1300 ft level was started toward the indicated loca- tion some 38 ft northwest of the coordinates of the surface location, The bottom of the hole was located within the drift round in which it was expected, and the transit survey run to the actual location of the hole indicated N 27.18, W 29.71. This shows a discrepancy between the well survey and the transit survey of 0.45 ft in the westerly direction and 2.91 ft in the northerly direction. All surveys, both gyroscopic and transit, fell well within the width of an ordinary drift. While this is satisfactory for almost any and all mining requirements, a theoretical examination was made as to reasons for the discrepancy. A study of the course of the hole indicates that considerable right turn or spiral existed, and in all probability the surveying instrument was pulled out of alignment while traversing the turn by approximately 0.05 ft at the top and another 0.05 ft in the opposite direction at the bottom of the instrument. If such an allowance were to be made, the survey calculations would almost exactly correspond with those determined by transit. This sort of discrepancy would be minimized by the use of stabilizing guides. It is unfortunate that physical laws probably effectively prevent the use of gyroscopic instruments in EX and AX diamond drill holes. The directive power of a gyroscope falls off inversely at some rate between the third power and the sixth power of the diameter. Present instruments can be run in casing 53/4 in. ID or over and might be adapted to somewhat smaller diameters, but the difficulty of reducing these diameters to 11/4 in. or 2 in. is almost insurmountable at the present time. Acknowledgment The author wishes to express his appreciation to the Phelps-Dodge Corporation for permission to publish this article, and to the Operating and Engineering Departments for their cooperation on the survey; also to Donald Hering, of the Sperry-Sun Well Surveying Co., who actually made the survey and calculated the results.

Jan 1, 1951

By S. H. Williston

IT not often that bore hole surveys can be checked by actual. civil engineering methods. A recent Arizona survey was checked by normal surveying methods and the comparison of the results should be of value to both oil and mining men. During the summer of 1948 the Phelps-Dodge Corporation, at its Copper Queen property near Bis-bee, Ariz., drilled a 1245 ft, 8 in. diarn, churn drillhole in a mineralized area and cased part of it, intending to use it to transfer mill tailings for stope fill. The hole, as frequently occurs, was not straight, and, in endeavoring to locate the bottom in the underground workings, they found no evidence of the hole at the underground coordinates directly below the surface location. The noise of the drilling tools was reasonably clear, but the direction of sound was uncertain. Preliminary tests with available equipment were not successful in locating the bottom of the hole. Because of the mineralized character of the area and the fact there was some casing in the hole, any magnetic method of well surveying would give results of doubtful value. Sperry-Sun gyroscopic well-surveying instruments were finally used to locate the bottom of the hole. These instruments consist of a gyroscope to determine azimuth and either a pendulum or bubble inclino-meter. A multiple shot camera photographs both instruments on a single film and superimposes the photograph of a watch. Coordination of depth with time at the surface makes it possible to select the corresponding picture for any depth. After making several runs of the empty instrument housing from the top of the hole to the bottom to make sure there were no obstructions in the hole, three surveys on wire line were completed during the afternoon. The three surveys, in which readings were taken at different points in the hole on each survey, were computed and gave the following locations of the bottom of the hole in relation to the surface collar: survey No. 1—24.92 N, 30.30 W; survey No. 2—24.24 N, 31.11 W; survey No. 3—26.54 N, 27.72 W. Then the data from the three surveys were combined into a single set of calculations which gave a location for the bottom of the hole: combined surveys—24.27 N, 30.16 W. (Fig. 1.) Immediately upon the determination of the coordinates at the bottom of the hole, a drift on the 1300 ft level was started toward the indicated loca- tion some 38 ft northwest of the coordinates of the surface location, The bottom of the hole was located within the drift round in which it was expected, and the transit survey run to the actual location of the hole indicated N 27.18, W 29.71. This shows a discrepancy between the well survey and the transit survey of 0.45 ft in the westerly direction and 2.91 ft in the northerly direction. All surveys, both gyroscopic and transit, fell well within the width of an ordinary drift. While this is satisfactory for almost any and all mining requirements, a theoretical examination was made as to reasons for the discrepancy. A study of the course of the hole indicates that considerable right turn or spiral existed, and in all probability the surveying instrument was pulled out of alignment while traversing the turn by approximately 0.05 ft at the top and another 0.05 ft in the opposite direction at the bottom of the instrument. If such an allowance were to be made, the survey calculations would almost exactly correspond with those determined by transit. This sort of discrepancy would be minimized by the use of stabilizing guides. It is unfortunate that physical laws probably effectively prevent the use of gyroscopic instruments in EX and AX diamond drill holes. The directive power of a gyroscope falls off inversely at some rate between the third power and the sixth power of the diameter. Present instruments can be run in casing 53/4 in. ID or over and might be adapted to somewhat smaller diameters, but the difficulty of reducing these diameters to 11/4 in. or 2 in. is almost insurmountable at the present time. Acknowledgment The author wishes to express his appreciation to the Phelps-Dodge Corporation for permission to publish this article, and to the Operating and Engineering Departments for their cooperation on the survey; also to Donald Hering, of the Sperry-Sun Well Surveying Co., who actually made the survey and calculated the results.

Jan 1, 1951

By Edward Martinez

The reactions occurring in the copper segregation process were studied by heating mixtures of chryso-colla, salt, and a reducing agent. The techniques used in this investigation were differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). The initial chloridizing of the oxide copper occurs below 500°C and cupric chloride may be the compound formed. Volatilization and reduction of the copper chloride take place above 550°C, although these reactions do occur to some extent below 550°C. A difference in the distribution of the metallic copper in the reducing agent was found when sodium chloride was used compared to magnesium or calcium chloride. Segregation was obtained with mixtures of cupric oxide, salt, and charcoal with no quartz or silicate present. Preliminary tests indicate that segregation may occur even in the absence of water vapor. The DTA and TGA techniques were found to be of great value in studying these reactions. The copper segregation process is a method for treating oxide copper ores. The ore is heated, most commonly in a kiln, with a reducing agent and a halide salt, generally sodium chloride, to approximately 700°-750°C and held for 30 to 60 min. The addition of the salt results in the migration and reduction of the oxide copper to metallic copper on the surface of the reducing agent rather than in the original mineral structure. The metallic copper can then be recovered by a subsequent leaching or flotation step.1-4 Experimental work in 1923 on oxide copper ores from the Sagasca mines in Chile led to the discovery of the reduction process. It was found that during the reduction of the copper mineral with coal, at about 700°C, the copper migrated to the surface of the coal instead of remaining disseminated in the ore. The unusual behavior of the copper, which caused it to migrate from the ore particles to the coal, was traced to the presence of a small quantity of sodium chloride occurring in the ore. Further experiments with oxide copper ores proved that the presence of a halide, either occurring naturally or admixed with the ore, caused the copper to migrate from the ore particles and to segregate in the charge. The ratio of salt to reducing agent may vary somewhat, but in general 0.5% to 1.5% sodium chloride and 0.5% to 1.0% coal or coke have been mixed with the ore. Less than stoichiometric amounts of salt are required to convert all the oxide copper to a chloride, so that a cycle of reactions appears to be occurring. Several investigations reported in the literature have proposed reactions to explain the mechanism of the process.5-10 There appears to be general agreement that water is necessary for the reactions to occur; that once the sodium chloride reacts with silica or silicates in the ore, the hydrochloric acid formed will convert the cupric oxide in the mineral structure to cuprous chloride. However, there appears to be a conflict of opinion on the reactions involved in the reduction of the cuprous chloride to metallic copper on the surface of the carbon. Rey has indicated that salt, water vapor, and

Jan 1, 1968

By E. S. Fisher, L. C. R. Alfred

The elastic anisotropy factors, c4,/c6,, c3,/cll, and c12/cl,, for hcp metal crystals vary significantly among the dgferent unalloyed metals. Significant variations with temperature are also found. The effects of elastic anisotropy on the dislocation in an elastic continuum with hexagonal symmetry have been investigated by computing the elasticity factors for the self-energies of dislocations in fourteen different metals at various temperatures where the elastic moduli have been reported. For most of the metals the effects of the orientation of the Burgers vector, dislocation line, and glide plane are small and isotropic conditions can be assumed without significant error. Significant effects of anisotropy are, however, found in Cd, Zn, Co, Tl, Ti, and Zr. The elasticity factors have been applied in the calculations of dislocation line tensions, the repulsive forces between partial dislocations, and the Peierls-Nabarro dislocation widths. It is predicted that the increase in elastic anisotropy with temperature in titanium and zirconium makes edge dislocations with (a), (a + c), and (c) Burgers vectors unstable in basal, pyramidal, and prism planes, respectively. The probability of stacking faults forming by dissociation of Shockley partials in basal planes also decreases with increasing c4,/c6, ratio, when the stacking fault energy is greater than 50 ergs per sq cm. The widths of screw dislocations with b = (a) in titanium and zirconium increase very significantly in prism planes and decrease in basal planes as c4,/c6, increases. The effects of elastic anisotropy on various dislocation properties in cubic crystals have received considerable attention during the past few years. In the case of cubic symmetry the departure from isotropic elasticity depends entirely on the shear modulus ratio, A = 2c4,/(cl, —c12); i.e., the medium is elastically isotropic when A = 1. Foreman1 showed that an increase in the ratio A produces a systematic lowering of the dislocation self-energy for a given orientation and Poisson's ratio. ~eutonico~, has shown that large anisotropy can have a marked effect on the formation of stacking faults by the splitting of glissile dislocations in (111) planes of fcc and (112) planes of bcc crystals. ~iteK' made similar calculations for (110) planes of bcc metals. Both studies of bcc metals showed that the large A values encountered in the alkali metals tend to reduce the repulsive forces between Shockley partial dislocations. In fcc metals, however, A does not vary over the large range encountered in bcc metals; consequently, the effect of A on the forces between Shockley partials is masked somewhat by the differences in Poisson's ratio between metals. The effect of A on the line tension of a bowed out pinned dislocation has also been investigated for cubic crystals, first by dewit and Koehler5 and more recent- ly by Head.6 In both cases the line energy model is applied and the core energy is not taken into account, thus making the conclusions somewhat tenuous with regard to the physical interpretation. Nevertheless, the fact that a large A decreases the effective line tension is clearly evident and the tendency for large A to produce conditions that make a straight dislocation unstable (negative line tensions) also seem evident. Head, in fact, shows visual microscopic evidence that stable V-shaped dislocations occur in 0 brasse6 For hcp metals the definition of elastic anisotropy is more complex and, furthermore, significant deviations from an isotropic continuum are found among a number of real hcp metals, especially at higher temperatures. The present work was carried out to survey the effects of elastic anisotropy on the elasticity factors, K, that enter into the calculations of the stress fields around a dislocation core. Some isolated analytical calculations have previously been carried out for several hcp metals but they are restricted in the dislocation orientations and temperature.8'9 The present computations are based on single-crystal elastic moduli that have appeared in the literature and consider various orientations requiring numerical computations. The results are then applied to survey the effects of temperature on the dislocation line tension and dislocation splitting in hcp metals. PROCEDURE Anisotropy Factors. The degree of elastic anisotropy in hcp crystals cannot be described by a single parameter, such as the A ratio in cubic crystals. The following three ratios must be simultaneously equal to unity in order to have an elastically isotropic hexagonal crystal: The magnitudes of these ratios at several temperatures, as computed from the existing data for the elastic moduli of unalloyed hcp metals, are given in Table I. There are no cases of complete elastic isotropy, but the large anisotropy ratios encountered in the cubic alkali metals are also missing. There are, however, several significant differences among the hcp metals, the most notable being the relatively small A and B ratios in zinc and cadmium and the differences in the magnitudes and temperature dependences of A. It has been noted that the temperature dependence of A has a consistent relationship to the occurrence of the hcp — bcc tran~formation. For cadmium, zinc, magnesium, rhenium, and ruthenium, A is less than unity at 4'~ and, with exception for rhenium, decreases with increasing temperature. In the case of rhenium, A has essentially no temperature dependence between 923' and 1123"~, so that it is clear that A does not approach unity at higher temperatures. Cobalt is similar to the above-mentioned group of metals in that it also does

Jan 1, 1969

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,'-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By Chas. A. R. Lambly

In the extreme northeast corner of the State of Washington, on the Canadian border, lies the Metaline mining district. This district is old in history, but young in production. Geology The Metaline district is a zinc-lead area of the replacement type in dolomite and limestone. The ore bodies of the Josephine horizon are in many ways similar to the ore bodies of the famous Tri-State zinc fields. The beds are faulted and folded and have varying low dips in varying directions, and underlie large areas of the district. History Production started in 1927 on a very limited basis. The property is now mining and milling 700 tons per day. The mine is opened by adit tunnels and a vertical shaft. As the ore horizons gained depth, it was necessary to sink inclines to follow the ore horizon (see Fig 1). From 1927 to date, approximately 600,000 ft of diamond drill was put down This work indicated that suficient tonnage existed to justify a redesigning of the whole operation, surface and underground. After four years of general study, the following program was planned: 1. A new mine entrance, which would be an incline, that could follow the ore body down at whatever pitch was necessary. The incline will be equipped with conveyors for the moving of ore and waste to the surface and with tractor-type locomotives for man and supply transportation. 2. The new incline also required a new type of mining which was developed and is now in use. It is called contour mining and will be described in a future paper. 3. The new incline exit would necessitate the moving of the mill and mine shops across the Pend Oreille River. This part of the program is now underway. The Incline The sinking of the incline was to start as soon as World War II ended and was as follows: The first leg of the incline was to be sunk from the surface 1600 ft on a 17" slope. The collar and first level at elevation 2180 ft, the second level at elevation 2000 ft, the third level at elevation 1875 ft, and the fourth level at elevation 1700 feet. From the 1700 ft elevation the incline was to flatten out to 12" for 400 ft to give the necessary depth for the ore pockets below the 1700 ft level and the necessary clearance for future sinking (see Fig 1 and 2). Due to lack of manpower in 1946, the program was changed and was as follows: A drift was driven from the old mine workings on the 1700 ft elevation in an easterly direction. At 1300 ft the drift was turned N 50" E and at this point a raise was driven 180 ft on a 50" slope. This raise intersected the Josephine horizon and commercial ore was encountered. At the 2000 ft mark, a main raise was driven, 245 ft on a 50" slope, and the 1875 ft elevation was cut. Exploration drifts were started on this level and production followed on a limited basis. The main drift at the 2500 ft point was turned N 35" E and ran parallel to and 10 ft east of and under the proposed incline line. At the proposed intersection of the drift and incline on the 1700 ft elevation, it was planned to raise the incline to intersect the 245 ft raise and to continue on to the surface, a distance of 1600 ft. When this proposed intersection point was reached, a heavy flow of water, approximately 800 gpm, was encountered and all work on the main drift face was stopped. This water flow flooded the main pump station in the old mine and the two lower levels with approximately 20,000,000 gal of water. The water was controlled and finally drained from the cave areas and lower levels after six months of pumping. After the heavy flow of water was encountered in the main heading, it was decided that the incline would have to be started from the surface, as originally planned, so that too much time would not be lost. The surface overburden had to be removed, a total of 6000 yards. A temporary dry house for 6 men was built. An 8 in. churn drill hole was intersected in the first raise driven from the 1700 foot elevation tunnel. Air and water lines were placed in this hole, and air and water were delivered to the collar of the incline from the mine working. The incline started down at 15 ft wide and 7 ft high through the Leadbetter slates. After sinking 4 sets, it was

Jan 1, 1950

By T. A. Rickard

A knowledge of the principles of punctuation is essential to effective and intelligible writing, for the ease and pleasure of the reader, and even his understanding, may depend upon the choice and the placing of punctuation marks. To 'punctuate' is to mark with stops or points; the word comes from the medieval Latin punctuare (punctuatus), which in turn is derived from the Latin punctum, a point. The purpose of punctuation is to show the manner in which the writing is to be understood; to indicate the relations between parts of a sentence and between successive sentences. To some extent "it does for the eye what vocal stress does for the ear", but especially it marks logical relations. Some punctuation marks, such as those indicating admiration, exclamation, and interrogation, are rhetorical as well as grammatical, but most of the common ones are logical, or grammatical. My discussion will be confined to grammatical punctuation in ordinary writing. .'The problem of punctuation in text matter", as George Summey * says, "is to employ words, points, and paragraph breaks in such a way as to achieve at the same time clearness; proper distribution of emphasis, and the desired kind of movement." The criticism of the punctuation of a sentence or of a group of sentences is not final until the context, within the paragraph, is read. A paragraph is a sentence or a group of sentences forming an independent unit of the composition; it represents a unit of thought. A multiplicity of paragraphs produces a choppy effect; 'on the other hand, paragraphs of. excessive length are tiresome, because the belaboring of one unit of thought wearies the reader. The aim should be to

Jan 1, 1931

By S. R. Goodman, Hsun Hu

A detailed study of texture developmenf in poly crystalline copper atzd 70-30 brass has been completed. Textural changes as a function of deformation are shoum by pole jigmres and by intensity measurements oF- various rejlectiotzs from the rolling plane and the rolling direction. These examinations were accompanied by measurements of stacking fault frequency, hardness changes, and microstructure. Some of the results were briefly presented earlier. Additional results reported here are consistent with the idea that deformation faulting or slip by partial dislocations is of primary importance in the formation of deformation textures in fcc metals. lo examine the idea that deformation faulting is of primary importance in determining whether the texture is the copper type or the brass type an extensive study of the development of polycrystalline textures in copper and 70-30 brass was initiated. Besides the determination of complete pole figures, the intensities of the various reflections from both the rolling plane and the plane perpendicular to the rolling direction, the peak shifts due to deformation stacking faults, and the hardness of the rolled specimens were examined at various reductions from 10 to 99 or 99.5 pct. Mi-crostructures were examined by transmission electron microscopy. Some of the results were briefly presented in an earlier publication.' Since then, additional information has been obtained. This is given in the present paper. EXPERIMENTAL PROCEDURE Material and Specimen Preparation. The material used was a commercial electrolytic copper bar 1i in. wide and 2 in. thick and a 70-30 brass bar la in. wide and 1i in. thick. Chemical analysis indicated a purity of 99.97 pct for the copper, with 0.025 pct 0 as the major impurity. The 70-30 brass was of higher purity with 0.0016 pct 0 as the major impurity. Extreme care was taken in the preparation of the starting material to insure uniformly fine grains with a nearly random initial texture. The two bars were first cold-forged and then annealed to eliminate any original texture. The grains were then refined by several cold rolling (approx 30 pct reduction) and annealing treatments. The + -hr anneals were carried out in a salt bath at 390" to 440°C for copper and at 490°C for brass. The resulting penultimate grain size was 0.06 mm for copper and 0.03 mm for brass, and both showed very little preferred orientation. The number of prior cold rolling and annealing cycles was such that the final thickness after various final reductions of 10 to 95 (for brass) or 99 (for copper) pct was the same (0.020 in.). These annealed strips were rolled in two directions by reversing end for end between passes according to the following schedule: 0.006 in. per pass to 0.100 in., 0.003 in. per pass to 0.050 in., 0.002 in. per pass to 0.025 in., 0.001 in. per pass to 0.020 in. Texture Determination. The development of rolling textures was studied by examining complete pole figures determined from the (111) reflection. Specimens thinned from one face of the strip to half thickness (0.010 in.) were used to obtain the central portion of the pole figures, while specimens thinned from both faces to 0.003 in. were used to obtain the peripheral portion. The reflection and transmission techniques have been described previously. In addition to X-rav pole figures, texture development was also studied b; examining the intensity variation of the (Ill), (200), (2201, (311), (331), (420), and (442) reflections from the rolling plane and from the plane normal to the rolling direction, as a function of deformation. The same specimens used for the central portion of the pole figures were used for the intensity measurements of the various reflections from the rolling plane. For intensity measurements from the plane normal to the rolling direction, composite specimens were prepared by mounting sections cut parallel to the transverse direction of the strip. An epoxy resin was used to bond these sections together, and the entire composite was then mounted in a cold-setting resin to facilitate subsequent polishing and etching to remove distorted metal at the cut. The intensities were expressed in units of the integrated intensities measured from an annealed copper specimen having almost no preferred orientation. Stacking Fault Frequency Determination. Following the analysis of Warren: the stacking fault frequency, a, was determined from the change in the peak separation (A%) of two neighboring reflections of a deformed specimen, as compared with the normal peak separations of a fully annealed specimen. To obtain sufficient intensities for the second-order reflections, (222) and (400), composite specimens were prepared from parallel sections cut from the strip at 30 deg to the rolling direction for copper and 25 deg for the brass.* From texture data, these sections are known to contain a large population of both (111) and (200) planes. Since residual stresses can also cause X-ray line shifts (the direction of line shifts depends upon the sign of the stress), the use of composite specimens consisting of sectioned planes should help compensate for these effects as the residual stresses change sign from the surface to the central section of a rolled strip. Since the amount of peak shift is almost un-measurable in brass rolled 15 pct and in copper rolled

Jan 1, 1969

By A. Simkovich, R. W. Lindsay

The possibility of using sodium sulfide slags to remove copper from ferrous alloys has been investigated by Jordan1 and by Langenberg.2, 3 In these studies, such slags were determined to be capable of removing copper and sulfur from the melt. The present work represents additional effort to clarify the effects of temperature on copper removal. The experiments were performed in a 17-lb induction furnace. Graphite crucibles contained the melts and kept the baths saturated with carbon. Temperatures were measured with a calibrated optical pyrometer and were controlled by manipulation of power input to the furnace. Estimated accuracy of temperatures in this investigation is ± 10°C (18°F) for measurements prior to slag additions, and + 20°C (36°F) after slag formation. The procedure consisted of melting 800 g of electrolytic iron. During this step, powdered graphite covered the exposed iron surface. After a predetermined temperature was reached, copper shot was added. A sample of the molten alloy for chemical analysis was then aspirated into a silica sheath. Next, a slag-forming mixture of sodium sulfite and graphite was added instantaneously to the melt. The sodium sulfite amounted to one-tenth the charge weight of iron; sufficient graphite was added to combine with oxygen in the sodium sulfite, assuming formation of carbon monoxide and reduction of the sulfite to sulfide. Subsequent to the slag addition, the molten alloy was sampled periodically, with the exception of heat A in which no intervening samples were taken between the slag addition and the end of the run. The iron was poured into a graphite mold, and the ingots sectioned and drilled for samples. Results of selected heats are presented in Table I. Analyses of samples drawn from the iron prior to slag addition are listed under zero time. Two samples from heat D were reported with copper contents greater than the initial concentration in the bath. Owing to the gradual but complete disappearance of slag during this heat, it is believed copper momentarily became more concentrated in the upper portion of the bath while reverting from the slag. This is the region from which samples were drawn. It should be noted that analysis of the ingot was equal to the copper content at the time of slag addition. The terminal temperatures of heats D and E, and the initial sulfur content of heat A are also to be noted. Because of the large temperature drop which occurred when slag was formed in heat D, power input to the furnace was increased in heat E after the slag addition, causing a higher terminal temperature. In heat A, the initial sulfur concentration was relatively high as compared to heats B through E owing to contamination by some slag remaining in the crucible from a previous heat. It is evident from Table I that copper was removed at the onset of slag formation. Roughly 30 pct of the copper was taken into the slag, with the exception of heat D, which had approximately 50 pct removed. For a comparatively short time of slag-metal contact, it appears that no gain is to be made in copper removal through use of high or low temperatures. If the slag initially formed remains in contact with the iron for an extended period, temperature has a marked effect upon copper removal, as can be seen by studying results for the two extremes in temperature. At about 1425°C, the copper level remained relatively constant after the initial removal by the slag. However, in the region of 1670°C, a definite reversion of copper occurred. Reversion was incomplete in heat D, and complete in heat E. The final temperatures of heats D and E differed by about 75°C. This temperature difference is thought to be the reason for only partial copper reversion in heat D. It is believed the effects of temperature noted above are related to the evolution of a white fume, which appeared in every run except heat A. (In the case of heat A, the fume was practically indiscernible.) After each slag addition, a yellow flame formed for about 5 sec. When the flame subsided, a white fume appeared. Upon contact with surrounding cooler surfaces, this fume deposited as a white solid. In the experiments made at 1425°C, evolution of fume continued unchanged to the end of the runs. However, heats D and E exhibited a different behavior. A very noticeable decrease in fume evolution from heat D was observed. Furthermore, this heat had much less slag remaining than did runs A through C when the experiments were terminated. No slag remained at the end of heat E; evolution of fume from this heat ceased prior to pouring. Spec-trographic analysis of the white deposit indicated sodium to be the major metallic element, with the maximum concentration of iron and copper as 0.1 and 0.01 pct, respectively. It is supposed the white fume observed in these experiments is principally sodium oxide (Na2O), formed by oxidation of sodium in the slag and subsequent sublimation. (Sodium oxide is a white to gray substance in the solid state; at 1275oC, it sublimes.4) According to this mechanism, elevated temperatures would accelerate removal of sodium from the slag, sulfur pickup by the

Jan 1, 1961

By Charles Luner

ALTHOUGH the kinetics of the atmospheric oxidation of tin have been studied,1-3 the kinetics in pure oxygen have not been reported. This note presents some results of the kinetics of the oxidation of tin foil in pure oxygen. The tin foil used in this investigation was 99.78 pct pure, the two major impurities being Pb (0.17 pct) and Sb (0.024 pct). The foil was degreased and air-dried prior to oxidation. The air-formed film was estimated by coulometric reduction4 of the surface oxides to be about 25A. The samples, which were in strip form and had a total geometric surface area of about 300 sq cm, were first evacuated at room temperature in an oxidation bulb to 1 X 10 -5 mm Hg and subsequently degassed for 1 hr at the temperature of the experiment. Spectroscopically pure oxygen was then introduced into the bulb. The rates of oxidation were measured by following the rate of pressure change due to oxygen consumption in a closed system, the volume of which was sufficiently large so that the pressure change during an experiment was 10 to 15 per cent of the total pressure. An oil-mercury manometer,5 with a sensitivity of 3 X x mm Hg (which corresponds approximately to 5 X 10 -7 gm of oxygen) was used to measure the pressure change. The oxidation bulb was heated by an oil-bath and controlled to within -10.3 C. The reproducibility of the rates was good, as determined by the coincidence of rates at 190oC for duplicate experiments. Fig. 1 shows the oxidation curves in the temperature range 168 to 211.5oC at 8 mm Hg pressure. The effect of pressure on the rate of oxidation at 190°C is also shown. The rate of oxidation was not markedly affected by changes in pressure in the range 4 to 9 mm Hg, except perhaps at the lowest pressure, 4 mm Hg, where after about 70 min there appeared to be a decline in the rate, as compared with the rate at the higher pressures. At the lower tem- perature, 168oC, and for short reaction times, it is difficult to distinguish between a linear relationship and a slight curvature in the oxidation rate. However, for longer times, there was a somewhat larger indication of curvature. The samples after oxidation were gold-colored in appearance. The oxide that was formed at 170°C was identified as a-SnO by reflection electron diffraction. This is in agreement with results obtained by other workers.6, 7 The rate data best fitted the logarithmic-oxidation rate law, w = K1n ln(1 + -t/to) [1] where w is the weight of oxygen consumed, t is the time, and K In, and to are constants. First estimates to were obtained according to the method of Taylor Thon8 and were then employed to obtain the best simuItaneous estimates of to and K In, that would fit the logarithmic expression. These estimates were found numerically, so that the residual variance could be minimized. The calculations were performed on an

Jan 1, 1961