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By Maurice Ewing, A. P. Craby, J. W. Peoples, J. A. Peoples

The purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data summarized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the opportunity for checking results so thoroughly is given. In the second place, the fact that recent commentatorsl,2,3 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1921, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected 'his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

MISCELLANEOUS U.S. 0,029,598 - Extraction of vanadium values from vanadiferous iron oxide ore. A pelletized mixture of ore, limestone and bentonite is roasted in an oxidizing atmosphere to form calcium vanadates, the calcine ground, the ground material leached with aqueous ammonium carbonate or sodium carbonate to produce a vanadium-rich solution while leaving an insoluble residue of calcium carbonate and/or calcium bicarbonate along with undissolved iron values, and the solution separated and treated for its vanadium content. This patent is a reissue of U.S. Patent No. 3,853,982, dated Dec. 10, 1974. C. B. Bare and J. W. Pasquali, assigned to Bethlehem Steel Corp. Mar. 28, 1978. 7 pp. (423-68). Filed: 3-3 1-77 (783,352).

Jan 1, 1979

US 4,135,913-Extraction of nickel values from iron-containing nickel sulfide ore, particularly pentlandite or nickeliferous pyrrhotite A mixture of raw ore, roasted ore, or iron powder, and coal as a reductant is heated to a temperature of 800- 1000° C in a nonoxidizing atmosphere to convert the bulk of the iron content to metallic iron while diffusing into the iron the bulk of the nickel, the mixture cooled, and the cool material separated into a magnetic fraction containing most of the nickel and a non-magnetic gangue fraction A Illis arid L S Renzoni, assigned to International Nickel Co, Inc Jan 23, 1979 7 pp (75-21) Filed 10-10-75 (621,343) Priority Canada, 10-27-72 (155,032) Same Canadian 981,910, dated Jan 20, 1976 Same British 1,389,145, dated Apr 3, 1975 US 4,135,917-In the recovery of gallium from a solution obtained by the digestion of bauxite or nepheline in an alkali solution for the production of alumina, the digestion solution is neutralized, the neutralized solution evaporated to an op¬timum caustic alkali concentration and adjusted to a ratio of alkali metal oxide to alumina of above 2, the corrected solu¬tion contacted with a gallium-aluminum alloy, arid high-purity gallium recovered from the solution by electrolysis or cemen¬tation K A Badaliants, et al Jan 23, 1979 6 pp (75-109) Filed 12-19-77 (862,201) Priority USSR, 12-22-76 (2,428,¬006) US 4,135,918-Extraction of copper from copper sulfide ore containing also one or more of the metals iron, nickel, arid cobalt Ore is roasted at a temperature of 750-800° C to expel sulfur, the sulfur-free calcine slurried in water containing a sufficient amount of sulfuric acid to supplement any sulfuric acid formed in situ, the slurry heated at 150-165° C in the presence of a reducing gas to form soluble sulfates of metals other than copper while reducing copper to elemental form, arid the slurry filtered to recover copper solids Any precious metals present in the ore will report with the copper solids V A Ettel, A P Devuyst, R Sridhar, arid C. E O'Neill, as¬signed to International Nickel Co, Inc Jan 23, 1979 5 pp (75-117) Filed 3-2-78 (882,610) Priority Canada, 5-13-77 (278,360)

Jan 1, 1980

By Fathi Habashi

At the Duisburger Kupferhütte plant in Germany, pyrite cinder is collected from the sulfuric acid manufacturers in that country and processed to recover the nonferrous metals contained in the cinder, before charging it to the blast furnace for iron recovery. A typical analysis of the cinder is given in Table 9-1. The pyrite cinder is mixed with NaCl and treated continuously in a multiple hearth furnace. The evolved gases are scrubbed with water to form a weak acid which is used for the leaching process. Each batch requires about 2 days for leaching. The concentrated leaching solution obtained in the first 15 to 20 hr is sent for copper recovery, while that subsequently obtained, being poor ill metal content, is recycled. The residue, called purple ore, now a high-grade iron ore (61-63 % Fe); is sintered and delivered to the blast furnace.

Jan 1, 1970

By P. G. Nahin, A. Grenall, R. S. Crog, W. C. Merrill

A progress report of an experimental investigation into the role of clay in reservoir performance is presented. The Paper gives some of the reasons for considering clay as a significant component and outlines the objectives of a broad field of stud) which it is intended to pursue. Descriptions of the analytical methods used are given; these include X-ray diffraction. elec tron miscroscopy, thin section petrography, infrared spec-troscopy, and cation exchange analysis. A suite of the more important clay minerals has been assembled and characterized l~y these methods for use as standards in core analysis. From the data obtained it appears that although no one method of analysis is diagnostic for all of the clay minerals the infrared technique shows considerable promise in this direction. For the present, one or more supplementary methods should be used to confirm the clay mineral identifications. The methods of analysis are applied to field cores taken from repesentative and widely differing strata especially as regards their susceptibility to damage by fresh water. well.; completed in the stevens and Gatchell zones in San Joaquin valley are I,articularly clear-cut examples of this behavior with stevens zone wells being more adversely affected by fresh water. cores from these zones have been studied and are discussed. It appears that differences in this behavior can be ascribed to differences in the nature of the contained clays. The value of the infrarecl spectra of the clay fractions in establishing the identity of the predominant clay minerals is given particular emphasis. INTRODUCTION It is a challenge to the technical resources of the petroleum industry that when the economic limit of production is reached, from 40 to 70 per cent of the oil in California reservoirs remains unproduced even by use of the best presently known methods of recovery. The magnitude of this abandoned volume of oil can be appreciated when it is considered that to 1950 in excess of 8 billion bbll has been produced from California reservoirs with estimated economically recoverable reserves in known fields and pools totaling nearly 4 billion bbl.24 If for every barrel of oil produced there is at least another barrel still in place, it is evident that the revenue obtained from the recovery of only a .few per cent of this volume would repay the cost of the required research manyfold. From well completion experience. production behavior, and a growing body of laboratory data it now appears certain that the mineral composition of a producing stratum has an important bearing on the productivity and ultimate yield. In addition to the organic component and water, the cores con,ist of gravel, sand. silt, and clay" in diverse variety of (a, composition and (b) texture. It is the composite effect of these two factors which is probably responsible in large measure for the way in which the oil flows to the well. The role of the clay and fine-size accessory minerals is not clear but there is a growing opinion, based on their physical and chemical properties, that it is a significant one. of particular importance are the prime facts: 1. The silt and clay fractions of the reservoir matrix possess the highest surface area per gram, and 2. The silt and especially the clay fractions are the most chemically reactive of the inorganic constituents present. Only within the last few years has the knowledge of clay mineralogy and the techniques of identifying the clay minerals reached such a stage as to enable reliable inquiry into the composition of argillaceous sediments.2,8,10,11,12,16,26 It is the purpox of this and succeeding papers to add to the fund of information on the role which these materials play in the production of petroleum from California formations by correlating their presence and associated properties with observed reservoir behavior. In the present paper attention is directed to their possible influence on damage by fresh water. OBJECTIVES The attack on this problem divides naturally into two broad phases: 1. Determination of the nature of the clays and their relationships to the other mineral components, and 2. Determination of the physico-chemical relationships between the clays and the interstitial fluids. In the work described in this paper the emphasis has been on phase 1, which stems logically from the necessity of identifying and understanding the materials to be dealt with in Phase 2. Based on the authors' present opinion that not all of the minerals which occur in oil-bearing formation are of equal importance in their effects on the flow and recovery of oil, it was decided to focus attention first upon the clay minerals content and then. later perhaps. work into the field of the normally larger size non-clay minerals and fractions. The

Jan 1, 1951

By W. C. Merrill, P. G. Nahin, A. Grenall, R. S. Crog

A progress report of an experimental investigation into the role of clay in reservoir performance is presented. The Paper gives some of the reasons for considering clay as a significant component and outlines the objectives of a broad field of stud) which it is intended to pursue. Descriptions of the analytical methods used are given; these include X-ray diffraction. elec tron miscroscopy, thin section petrography, infrared spec-troscopy, and cation exchange analysis. A suite of the more important clay minerals has been assembled and characterized l~y these methods for use as standards in core analysis. From the data obtained it appears that although no one method of analysis is diagnostic for all of the clay minerals the infrared technique shows considerable promise in this direction. For the present, one or more supplementary methods should be used to confirm the clay mineral identifications. The methods of analysis are applied to field cores taken from repesentative and widely differing strata especially as regards their susceptibility to damage by fresh water. well.; completed in the stevens and Gatchell zones in San Joaquin valley are I,articularly clear-cut examples of this behavior with stevens zone wells being more adversely affected by fresh water. cores from these zones have been studied and are discussed. It appears that differences in this behavior can be ascribed to differences in the nature of the contained clays. The value of the infrarecl spectra of the clay fractions in establishing the identity of the predominant clay minerals is given particular emphasis. INTRODUCTION It is a challenge to the technical resources of the petroleum industry that when the economic limit of production is reached, from 40 to 70 per cent of the oil in California reservoirs remains unproduced even by use of the best presently known methods of recovery. The magnitude of this abandoned volume of oil can be appreciated when it is considered that to 1950 in excess of 8 billion bbll has been produced from California reservoirs with estimated economically recoverable reserves in known fields and pools totaling nearly 4 billion bbl.24 If for every barrel of oil produced there is at least another barrel still in place, it is evident that the revenue obtained from the recovery of only a .few per cent of this volume would repay the cost of the required research manyfold. From well completion experience. production behavior, and a growing body of laboratory data it now appears certain that the mineral composition of a producing stratum has an important bearing on the productivity and ultimate yield. In addition to the organic component and water, the cores con,ist of gravel, sand. silt, and clay" in diverse variety of (a, composition and (b) texture. It is the composite effect of these two factors which is probably responsible in large measure for the way in which the oil flows to the well. The role of the clay and fine-size accessory minerals is not clear but there is a growing opinion, based on their physical and chemical properties, that it is a significant one. of particular importance are the prime facts: 1. The silt and clay fractions of the reservoir matrix possess the highest surface area per gram, and 2. The silt and especially the clay fractions are the most chemically reactive of the inorganic constituents present. Only within the last few years has the knowledge of clay mineralogy and the techniques of identifying the clay minerals reached such a stage as to enable reliable inquiry into the composition of argillaceous sediments.2,8,10,11,12,16,26 It is the purpox of this and succeeding papers to add to the fund of information on the role which these materials play in the production of petroleum from California formations by correlating their presence and associated properties with observed reservoir behavior. In the present paper attention is directed to their possible influence on damage by fresh water. OBJECTIVES The attack on this problem divides naturally into two broad phases: 1. Determination of the nature of the clays and their relationships to the other mineral components, and 2. Determination of the physico-chemical relationships between the clays and the interstitial fluids. In the work described in this paper the emphasis has been on phase 1, which stems logically from the necessity of identifying and understanding the materials to be dealt with in Phase 2. Based on the authors' present opinion that not all of the minerals which occur in oil-bearing formation are of equal importance in their effects on the flow and recovery of oil, it was decided to focus attention first upon the clay minerals content and then. later perhaps. work into the field of the normally larger size non-clay minerals and fractions. The

Jan 1, 1951

By Herman Dykstra, R. L. Parsons

A numerical method for solving partial differential equations in steady state fluid flow is described. This method, known as the "relaxation method," has two advantages over analytical methods: (1) practically any problem can be solved, and (2) a solution can be obtained quickly. A disadvautage is that the solution is not general. The method is applied to core analysis and relative permeability measurement to calculate constriction effects and to calculate the true pressure drop measured by a center tap in a Hassler type relative permeability apparatus. Further applications are suggested. INTRODUCTION Many problems in fluid flow cannot be solved analytically because of the nature of the boundary conditions. For many problems, however. an exact answer is not necessary because boundary conditions are not exactly defined or the parameters describing the porous medium are not accurately known. The relaxation method can be used to obtain an approximate answer easily and quickly for the flow of incompressible fluids in porous media. The method can also be used for other types of problems, such as determining the stress in a shaft under load. or the temperature distribution during steady state heat flow. In this discussion only calculations concerned with the flow of fluids in porous media will be considered. The method was introduced by R. V. Southwell in 1935.' THEORY The treatment given here follows that given by Enimons.2 Consider a porous medium to be replaced entirely by a net of tubes of equal length and uniform cross-sectional area as shown in part in Fig. 1. Assume that the net of tubes behaves exactly like the porous medium which it replaces; that is, the net can be made fine enough to reproduce exactly the porous medium. Assume also that Darcy's Law can be used to calculate the flow from one point to another point through these tubes. The flow from point 1 to point 0 is KA . ------ P-P) .......(11 where a is the distance between points: K is the "permeability" of a tube; A is the cross-sectional area of a tube; is the viscosity of the liquid in the porous medium; and (P1 — P0) is the pressure difference between point 1 and point 0. In like manner the flow can be calculated from points 2, 3, and 4 to point 0. The net flow into point 0 is Qo = KA/µa (P1 + P2 + P33 + P4-4P0) . . (2) MB For an incompressible fluid the net flow into point 0 will be zero or, Q. = 0. This says that at point 0 fluid is neither being accumulated nor depleted. 'Therefore. P1 + P2 + P3 + P4 - 4P0 = 0 .... (3) . If. now. with specified boundary conditions. the pressure i.; known at a finite number of points in a given region, as at the points shown in Fig. 1, Equation (3) will be satisfied at every point. If, on the other hand, the pressure is not known, the pressure can be guessed at these points. Then. unless the guess is perfect. Equation (3) will not be satisfied at all of the points. When Equatiol~ (3,) is not satisfietl. let d = P1 + I?, + P, + P, - If' .,....(4) where 6 is an apparent error and is called the residual at point 0. Equation (4) shows how much the pressure guess is in error at point 0 with respect to the surrounding points. A positive residual means that the pressure is too low, and a negative residual means that the pressure is too high. To bring the residual, 6. to zero in order to satisfy Equation (3). it is necessary to make changes in the pressure guesses. Equation (4) shows that a +1 change in Po will change the residual at point 0 by -4. A +1 change in the pressure at any of the four surrounding points will change the residual at point 0 by +l. Thus it can be seen that a change at any point will affect the residual at that point and the four surrounding points. By changing the pressure from point to point, all of the residuals can eventually be brought nearly to zero and the problem will be solved. This procedure is the essence of relaxation methods and is used to relax the residuals so that Equation (3) is satisfied at every point. The procedure can be most easily explained in detail by solving a simple problem. as Southwell says, "To explain every detail of a practical technique is to risk an appearance of complexity and difficulty which may repel the reader. A

Jan 1, 1951

By R. L. Parsons, Herman Dykstra

A numerical method for solving partial differential equations in steady state fluid flow is described. This method, known as the "relaxation method," has two advantages over analytical methods: (1) practically any problem can be solved, and (2) a solution can be obtained quickly. A disadvautage is that the solution is not general. The method is applied to core analysis and relative permeability measurement to calculate constriction effects and to calculate the true pressure drop measured by a center tap in a Hassler type relative permeability apparatus. Further applications are suggested. INTRODUCTION Many problems in fluid flow cannot be solved analytically because of the nature of the boundary conditions. For many problems, however. an exact answer is not necessary because boundary conditions are not exactly defined or the parameters describing the porous medium are not accurately known. The relaxation method can be used to obtain an approximate answer easily and quickly for the flow of incompressible fluids in porous media. The method can also be used for other types of problems, such as determining the stress in a shaft under load. or the temperature distribution during steady state heat flow. In this discussion only calculations concerned with the flow of fluids in porous media will be considered. The method was introduced by R. V. Southwell in 1935.' THEORY The treatment given here follows that given by Enimons.2 Consider a porous medium to be replaced entirely by a net of tubes of equal length and uniform cross-sectional area as shown in part in Fig. 1. Assume that the net of tubes behaves exactly like the porous medium which it replaces; that is, the net can be made fine enough to reproduce exactly the porous medium. Assume also that Darcy's Law can be used to calculate the flow from one point to another point through these tubes. The flow from point 1 to point 0 is KA . ------ P-P) .......(11 where a is the distance between points: K is the "permeability" of a tube; A is the cross-sectional area of a tube; is the viscosity of the liquid in the porous medium; and (P1 — P0) is the pressure difference between point 1 and point 0. In like manner the flow can be calculated from points 2, 3, and 4 to point 0. The net flow into point 0 is Qo = KA/µa (P1 + P2 + P33 + P4-4P0) . . (2) MB For an incompressible fluid the net flow into point 0 will be zero or, Q. = 0. This says that at point 0 fluid is neither being accumulated nor depleted. 'Therefore. P1 + P2 + P3 + P4 - 4P0 = 0 .... (3) . If. now. with specified boundary conditions. the pressure i.; known at a finite number of points in a given region, as at the points shown in Fig. 1, Equation (3) will be satisfied at every point. If, on the other hand, the pressure is not known, the pressure can be guessed at these points. Then. unless the guess is perfect. Equation (3) will not be satisfied at all of the points. When Equatiol~ (3,) is not satisfietl. let d = P1 + I?, + P, + P, - If' .,....(4) where 6 is an apparent error and is called the residual at point 0. Equation (4) shows how much the pressure guess is in error at point 0 with respect to the surrounding points. A positive residual means that the pressure is too low, and a negative residual means that the pressure is too high. To bring the residual, 6. to zero in order to satisfy Equation (3). it is necessary to make changes in the pressure guesses. Equation (4) shows that a +1 change in Po will change the residual at point 0 by -4. A +1 change in the pressure at any of the four surrounding points will change the residual at point 0 by +l. Thus it can be seen that a change at any point will affect the residual at that point and the four surrounding points. By changing the pressure from point to point, all of the residuals can eventually be brought nearly to zero and the problem will be solved. This procedure is the essence of relaxation methods and is used to relax the residuals so that Equation (3) is satisfied at every point. The procedure can be most easily explained in detail by solving a simple problem. as Southwell says, "To explain every detail of a practical technique is to risk an appearance of complexity and difficulty which may repel the reader. A

Jan 1, 1951

By J. E. Harris

The metallic elements, beryllium, calcium, cerium, lithium, manganese, titanium, vanadium and zirconium are used in metallurgical practice in relatively small percentages for the purpose of improving the physical properties of various alloys. No important uses for any of these elements have thus far been developed either in the pure form or in alloys of which they constitute the major constituent.

Jan 1, 1935

INTERNATIONAL ENGINEERING CONGRESS, 1915.. Announcement. In connection with the Panama-Pacific International Exposition which will be held in San Francisco in 1915, there will be an International Engineering Congress, in which engineers throughout the world will he invited to participate. The Congress is to be conducted under the auspices of the following five National Engineering Societies: American Society of Civil Engineers, American Institute of Mining Engineers, The American Society of Mechanical Engineers, American Institute of Electrical Engineers, and The Society of Naval Architects and Marine Engineers. These societies, acting in co-operation, have appointed a permanent Committee of Management, consisting of the Presidents and Secretaries of each of these Societies, and eighteen members resident, in San Francisco. Thus constituted, the personnel of the Committee 'is as follows:

Jan 9, 1913

By E. A. Gulbransen, J. W. Hickman

Recent work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution type over the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions~i In order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where cu+ is o.,,6-,4 and ~i++ is o.,oh;, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with elec-trans. This in in the copper- nickel alloys corresponds to 40 at. pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is flied at 60 at. Pet Or or 4O at. pct nickel. Matt and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel has the configuration: 3ds 4s2 and copper: 3 dl0 4s) then at 60 at. pct copper or 40 at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. Survey OF Literature The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1949

By E. A. Gulbransen, J. W. Hickman

DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may Occur to such a degree that oxides may form in the body Of the film and On the outer surface which are different from those that would normally form if the additional elements were not present. The use Of transmisson electron diffraction may aid us in jnterpreting these phenomena. UP to the Present time all Of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physica1 state of the "alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the remova1 of carbon by Oxygen in a decar-burization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with lifetime tests carried

Jan 1, 1949

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

The reaction of carbon in solid solution in a metal with the surface oxide fim on many metals may be inferred from thermo-dynamic calculations for high vacua and high temperature conditions. Holm has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. considerable work has been described in the literature on the de-carburization reaction. Several general references may been 2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides on strips of various types Of chrome-nickel alloys. Some of the early experiments On the behavior Of '3 pct chrome-iron in vacua of the order of 5 X lo' mm and at a temperature Of 600°C have been reported.5 These experi-merits showed a 'low reaction with the residual Oxygen Or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600' C pure enough to reduce Crz03 formed On the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome- iron and Nichrome V has been investigated in the thin film range by Gulbransenr Phelps and Hickman,' and shown to be "203. It Was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pet nicke1 and 20 pet chromium was heated to 850°C in a high vacuum, the specimen lost weight. The rate Of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. Type Reactions Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type, They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: 1. Metal . (gas) F? metal + gas — degassing of the metal 2. zM(s) + y }i Oi(g) M MIOu(s) -oxidation

Jan 1, 1949

By E. V. Potter, E. T. Hayes, H. C. Lukens

Large volumes of hydrogen are liberated at the cathode during electrolytic precipitation of manganese. Most of the gas escapes from the electrolyte, but a considerable amount may be entrapped in the manganese plate. Gas has been observed to escape from manganese melts in puffs that bite at the surface. It has been reported that castings made with electrolytic manganese tend to rise in the molds; for this reason the manganese is often treated to remove hydrogen before the melt is made or it is premelted and used as cast manganese in making the alloys. The effect of hydrogen on the properties of manganese and its alloys is not known, but its effect on iron and iron alloys has been studied extensively.l.2 The close relationship between iron and manganese suggests that hydrogen may have a similar effect on the properties of manganese and its alloys. The purpose of this investigation was to determine the amount of hydrogen or other gases in typical commercial electrolytic manganese sheet and to investigate ways of removing it most conveniently. Apparatus The apparatus used is shown schematically in Fig. I. It consists of a chamber A in which the metal sample is placed, a vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The specimen chamber was made of two concentric quartz tubes. The outer one, a, connects with the closed gas system and is surrounded by the furnace G. A second tube, b, fits closely inside a and has a small end that projects into the space for the specimen and holds the thermocouple for measuring the temperature of the sample. The inner tube is joined to the outer tube outside the furnace, with rubber tape and sealing wax, to prevent gas leakage into or out of the closed system. This type of specimen container is loaded very easily and can be used several times if molten metal does not come in contact with the quartz. An ordinary mercury manometer B is used to measure the pressure in the system. The volume gauge C is essentially another mercury manometer, but the volume of the column is much larger than normal and the height of the mercury can be varied by raising or lowering the well H. In this apparatus the tube had a volume of IOO C.C. for a 60-cm. length. For larger changes in gas volumes, auxiliary containers F were used to increase the volume of the system by known amounts. Valves were arranged so that these auxiliary containers could be filled from the system and evacuated by the pump as often as necessary to accommodate the increases in the volume of gas in the system. The furnace G, used to heat the samples, was equipped with an automatic temperature controller, which maintained the desired temperatures within ± 5°C.

Jan 1, 1945

By J. O. Mack, J. B. Russell

In recent years, solders containing 20 per cent tin with no bismuth or cadmium have been developed by a few companies, and personnel have been properly instructed in their use. In addition, since the tin shortage, a number of solders containing less than 10 per cent Sn, and some with no tin, are being used in special applications; however, a solder of this type has yet to be developed that is satisfactory for general use. Table i.—Composition Ranges Prescribed for a Commercial Substitute Solder Element Per Cent Tin............................ 18.0-20.0 Bismuth (maximum)a............ 0. 80 Silver.......................... O. 10-1. 25 Bismuth plus silver (minimum).... 0. 85 Antimony (maximum)............ o. 50 copper (maximum),,,,,,,,..,,,, 0. I3 Other elements, each (maximum)6 0.03 Lead........................... balance a When silver is present in excess of I per cent, the Bi content shall be 0.50 per cent or over. b Total not to exceed 0.10 per cent. The Purpose of this investigation was to develop an alloy containing a maximum of 15 per cent tin, with no cadmium or bismuth, having solder properties equivalent to or better than those of substitute solders now specified containing 18 to 20 per cent tin (Table I), or even approaching the properties of the standard 40 to 60 tin-lead solder. The wartime restriction of bismuth and cadmium, elements that have beneficial effects on fluidity, solidification range and strength, makes it increasingly difficult to develop a general-purpose solder containing a maximum of 15 per cent tin. In the course of this investigation, 11 elements were used in various combinations with the basic I5-85 tin-lead alloy. These elements were antimony, silver, copper, indium, thallium, lithium, calcium, barium, potassium, sodium and arsenic. In all, 116 low-tin solders were investigated, with the idea of developing a solder that will give satisfactory working properties, specifically in regard to "wetting" of copper, brass and iron, solidification range, capillarity and shear strength of a soldered joint. The relative importance of these various properties plays an important role in the search for substitute solders, since it is almost impossible to retain all of the desired qualities of a high-tin solder and still make drastic changes in the alloy composition. Because of the expected uses of a general-purpose solder, it is necessary that it have properties, especially in regard to wet-tability, that will enable it to be used on the metals in common use. Basic Considerations The maximum liquidus temperature of a solder is determined by the particular application involved and the temperature that can be obtained by the source of heat. If a soldering iron is used, it must not only

Jan 1, 1945

By G. K. Manning, A. R. Elsea, A. B. Westerman

A considerable number of high-tem-perature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. .4t the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in vitalliurn after various heat treatments. Howcver, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chro-mium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja and Guertler2 indicated that cobalt and chro-mium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to 85 pct chromium undergo a transformation at [zoo to 12 50 c More recently, Wever and Haschimoto,3 Wever andLange,4and Matsunaga5 carried Out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallogra~hic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Mat-SUnaRa. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these excep-tions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data arid the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitalhum by deter-mining the diagram for the cobalt-chro-mi~m system- Experimental Work For the convenience Of the reader, the diagram as determined by the present investigation is presented in Fig 3. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the melting point for pure chromium is the

Jan 1, 1949

By Robert I. Jaffee, Bruce W. Gonser, Eugene M. Smith

There has been little investigation of the gold-germanium binary alloys. Haughtonl does not mention any work on the system. In a review article commemorating the fiftieth anniversary of the discovery of germanium, E. Einecke2 mentioned a gold-germanium eutectic at 24 atomic per cent Ge (10.4 weight per cent) melting at 359°C., but did not give the source of his information. From measurements of electrical conductivity, J. 0. Linde3 estimated that at least 0.6 weight per cent germanium is soluble in gold. The recent availability of germanium in this country in commercial quantities has led to interest in its properties and its alloys. This study is part of a program of investigation on germanium alloys; work on ternary alloys involving germanium and gold will be reported later. In this investigation, the composition and melting point of the Au-Ge eutectic reported by Einecke has been found to be substantially correct. Eutectic composition has been placed at I2.0 per cent germanium, however. An alloy of 10.4 per cent Ge, Einecke's value, was found to have a few gold dendrites in it. The cutectic temperature has been determined as 356.0 6 ± 0.5°C., slightly less than the temperature of 359°C. reported by Einecke. The liquidus curves and the solid solubility of ger- manium in gold have been determined, and are shown in Fig. I. Materials and Alloying The germanium used in this investigation was prepared by the Eagle-Picher Lead Co. from pure germanium oxide, by reduction in clay crucibles with sodium cyanide. The regulus is quite pure, assaying over 99.9 per cent Ge. High-purity gold obtained from Handy and Harmon was used. Alloying was carried out in graphite crucibles in an atmosphere of purified hydrogen. The temperature was brought up to 1050" to iioo°C., and the metal was allowed to freeze in the crucible. Prepared in this way, the gold dendrites in hypoeutectic alloys were somewhat segregated at the bottom and sides of the ingot, and on the hyper-eutectic side the lighter primary germanium tended to gather at the top. Most of the alloys were made from virgin metal. Low-germanium heats were made by alloying pure gold with the eutectic. Melting losses were consistently a few milligrams or less, and the composition could safely be taken from the intended analysis. The 30 per cent and 50 per cent germanium heats for thermal analysis were made in part from remelted higher germanium heats, and they may be OR composition as much as one per cent. Because of the high cost of materials, the weight of heats for thermal analysis were 15 to 20 grams and heats for metallo-graphic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

By W. C. Ellis, E. S. Greiner

Metallic titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arke12 and Fast prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kr0ll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725 C," it may be classed as a light metal since the specific gravity is 4.5 g per cc-I. The crystal structure is close-packed hexagonal from room temperature to 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat,8 electric resistanceg and theimoelec-tric force10 at temperatures near 890°C. It is reportedll that annealed titanium has a tensile strength of 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between — zoo and I000 C have been determined. Materials For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was made from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at I000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was made from a rod of titanium, 0.19 in. in diam, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table 1. Oxygen and nitrogen which Were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1949

The cut-and-fill mining methods in use in the mines of The International Nickel Company of Canada Limited, at Falconbridge Nickel Mines Limited, in the Sudbury District, and at McIntyre Porcupine Mines Limited in the Porcupine District, are typical of the general cut-and-fill practice in both the base-metal mines and the gold mines in the Province of Ontario. The following pages describe the methods in use. HORIZONTAL CUT-AND-FILL STOPING Horizontal cut-and-fill stoping, as practiced in the mines of The International Nickel Company of Canada Limited, falls into two main classifications: (I) transverse cut-and-fill stoping, where ground conditions or wide ore bodies make it necessary to establish narrow stopes and pillars across the width of the ore body; (2) longitudinal cut-and-fill stoping where ore body widths and ground conditions allow safe mining of the full width of the ore body. Transverse Cut-and-fill StopiNg General Stoping Layouts Stope and Pillar Widhs.—For transverse stoping, experience has indicated that narrow stopes and pillars, 27 ft. 6 in and 22 ft., respectively, are most satisfactory. These width are multiples of 5 ft. 6 in., which is the center to center dimension of a standard square set. Thus any stope, or block of stopes, can be readily converted from cut-and-fill to square set-and-fill if ground conditions should warrant such a change. Formerly, pillars were established 16 ft. 6 in. wide, the equivalent of the width of three square sets, with the intention of extracting the pillars by mining an overhand slice one set wide and an underhand slice two sets wide. However, subsequent experience proved that a two-set overhand slice is so much more efficiently mined than a one-set slice, and 22-ft. pillars have been made standard. Chutes.—The stope chutes are established on the longitudinal center line of the stopes and are spaced at 22-ft. centers from footwall to hanging wall. The footwall chute is usually from 5 to 10 ft. from the footwall of the stope. It is offset where necessary at an angle of 52° and vertical chutes are carried from the offset at 22-ft. centers. In sections of the ore body where a flat hanging wall would cut off hanging-wall chutes within a few cuts of the sill, it has proved to be more economical to use temporary chutes or slushers, or both, for these first few cuts, rather than to el permanent chutes at the hanging wall.

Jan 1, 1946

By A. F. Brock

The cut-and-fill mining methods in use in the mines of The International Nickel Company of Canada Limited, at Falconbridge Nickel Mines Limited, in the Sudbury District, and at McIntyre Porcupine Mines Limited in the Porcupine District, are typical of the general cut-and-fill practice in both the base-metal mines and the gold mines in the Province of Ontario. The following pages describe the methods in use. HORIZONTAL CUT-AND-FILL STOPING Horizontal cut-and-fill stoping, as practiced in the mines of The International Nickel Company of Canada Limited, falls into two main classifications: (I) transverse cut-and-fill stoping, where ground conditions or wide ore bodies make it necessary to establish narrow stopes and pillars across the width of the ore body; (2) longitudinal cut-and-fill stoping where ore body widths and ground conditions allow safe mining of the full width of the ore body. Transverse Cut-and-fill StopiNg General Stoping Layouts Stope and Pillar Widths.—For transverse stoping, experience has indicated that narrow stopes and pillars, 27 ft. 6 in and 22 ft., respectively, are most satisfactory. These width are multiples of 5 ft. 6 in., which is the center to center dimension of a standard square set. Thus any stope, or block of stopes, can be readily converted from cut-and-fill to square set-and-fill if ground conditions should warrant such a change. Formerly, pillars were established 16 ft. 6 in. wide, the equivalent of the width of three square sets, with the intention of extracting the pillars by mining an overhand slice one set wide and an underhand slice two sets wide. However, subsequent experience proved that a two-set overhand slice is so much more efficiently mined than a one-set slice, and 22-ft. pillars have been made standard. Chutes.—The stope chutes are established on the longitudinal center line of the stopes and are spaced at 22-ft. centers from footwall to hanging wall. The footwall chute is usually from 5 to 10 it. from the footwall of the stope. It is offset where necessary at an angle of 52° and vertical chutes are carried from the offset at 22-ft. centers. In sections of the ore body where a flat hanging wall would cut off hanging-wall chutes within a few cuts of the sill, it has proved to be more economical to use temporary chutes or slushers, or both, for these first few cuts, rather than to el permanent chutes at the hanging wall.

Jan 1, 1946