Search Documents

By Nestor Torres-Acuña, Fathi Habashi

Metallic copper of purity equal to commercial electrolytic copper is deposited during the anodic dissolution of technically available white metal, Cu2S, in m acidic solution of' copper(II) sulfate as electrolyte and copper sheets as cathodes. The process may be applied on commercial scale since it has the advantage of by passing the converting and poling steps, decreasing pollution problems due to SO, and recovering the sulfur of the white metal in the elemental form. The anodic dissolution is believed to take place in three steps: The working conditions that lead to 98 pct cathodic current efficiency are: 30 gpl Cu2+ and 100 gpl H2SO4 in electrolyte, current density 1.0 amp per sq dm, and tetnperature of bath 40°C'. DURING the smelting of copper, nickel, lead, and zinc sulfide ores, large amounts of sulfur dioxide are produced. Because the release of this gas in the atmosphere causes pollution problems, many attempts were made in the past for its recovery either in liquified form or processed to sulfuric acid. Although these two forms of sulfur are the usual forms that are consumed by the chemical and metallurgical industries, their storage and transport usually raise economic problems. It was realized, long ago, that a process by which sulfur can be recovered directly in the elemental form would be most attractive. Elemental sulfur is easily stored and transported, and is readily converted to SO2, H2S, or H2SO4 when needed. Processes aimed to recover the metals from their sulfide ores, and at the same time by-product sulfur in the elemental form, were recently reviewed.' As early as 1882, Marchese2 patented a process in which a matte having the composition: Cu 15, Pb 14, Fe 41, and S 25 pct was electrolyzed. According to cohen3 the process was applied on a pilot scale by the Aktiengesellschaft fur Bergbau-, Blei-, und Zinkhiitten-betriebe at Stolberg, Rheinland, Germany. The process was unsuccessful, however, owing to the contamination of the electrolyte during electrolysis. Studies in this field were reported by Bernfeld4 and Egli.5 Borchers et a1.6-8 developed the process further by using white metal (Cu 78.2 pct, S 19.6 pct) instead of the matte, and a pilot plant was operated by the Mansfeldschen Kupferschiefer Co. at Eisleben, German~.~ It appears, however, that the process never went into commercial operation. Further studies in this direction were carried out by Russian workers.10-23 The International Nickel Co. of Canada erected a pilot plant at Port Colborne in 1951 to apply the process to nickel matte which is essentially pure nickel sulfide."'- 26 Full-scale plant went into operation at the Thompson Refinery in Manitoba in 1964.27 In this method nickel sulfide matte is melted and cast into anodes analyzing 76 pct Ni and 20 pct S with small amounts of copper, cobalt, and iron. These anodes are then electrolyzed in an aqueous solution of NiS04 at pH 4. Further work on this method was reported in the literature.28-31 In this paper, experiments on the anodic dissolution of white metal in aqueous copper sulfate solution are reported. EXPERIMENTAL White metal, Table I, obtained from The Anaconda Co., was cast in form of anodes 10 by 7.5 by 1 cm, Fig. 1. The anodes are mechanically strong and do not break easily; when polished they gave a shiny gray metallic appearance. From the chemical composition shown in Table I, it can be seen that the atomic ratio Cu:S corresponds approximately to the formula CU2.06S. The copper in excess to the formula Cu2S is most probably present as a separate phase since metallic copper could be seen under the microscope, Fig. 2. Fig. 3 shows the X-ray diffraction pattern of white metal which matches fairly well with that of reagent-grade Cu2S.

Jan 1, 1969

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By J. L. Brimhall, R. A. Huggins, M. J. Klein

IN a recent paper1 it was shown that small additions of magnesium, copper, and oxygen decrease the stacking fault probability in plastically deformed silver. Correlation of :X-ray data with measurements of the twinning frequency and metallographic observation of slip lines indicated that this effect may be due to an increase in the relative stacking fault energy. It is the purpose of the present note to report experiments on these alloys of known stacking fault probability that relate to the stacking fault contribution to electron scattering in silver. There has been a considerable amount of disagreement in the literature concerning the contribution of dislocations to electrical resistivity in metals. Calculations relating to the scattering of conduction electrons by the dislocation core, its strain fields, and related effects have been made by several authors.2-5 In addition, experimental work on Cu,3,6-10 Ni,11 and Ni-Co alloys1:! has shown that dislocations in those materials exert an anomalously large effect on resistivity, this effect being related to the presence of extended dislocations. The problem of the scattering due to the stacking fault region between partial dislocations has been treated theoretically using several different procedures.13-'0 The results of these calculations show a wide range of predicted values, from rather large to completely negligible, due to the models and the approximations involved. Almost all of this work has been applied to the specific problem of scattering in copper. The more complete theoretical treatments depend rather critically. on the shape of the Fermi surfaces and the effective mass parameters. The scattering from stacking faults might therefore be expected to vary significantly from one metal to another. Unfortunately, sufficiently accurate information is not available .which would allow one to have any confidence in a theoretical prediction of the scattering in the case of silver. Resistivity measurements were made on small wire specimens of vacuum melted high purity silver and several dilute alloys. These measurements were made at approximately 20°C, with great care being given to temperature measurement and corrections. At such temperatures phonon scattering is significantly greater than imperfection scattering. However, the experimental technique was such that measurements on similarly treated samples were reproducible to better than 2.4 X 10-9 ohm-cm, which was satisfactory for this work. Values of the stacking fault probability and the increase in resistivity after severe plastic deformation are given in Table I. The increases in resistivity resulting from plastic deformation agree quite well with previous work on silver.14,21-26 In addition, it has been previously found that interetitials and vacancies in silver anneal out well below room temperature, so that the residual imperfection scattering in these experiments could be expected to be primarily associated with dislocations;. It is seen from the data in Table I that large changes in stacking fault probability are accompanied by differences in resistivity due to imperfection scattering of only a few percent. If the scattering of conduction electrons by extended dislocations is primarily due to the area of the stacking fault region independent of the stacking fault energy, and not the core and strain fields associated with partial dislocations, the resistivity increase should be proportional to the product of the dislocation density and the stacking fault width, as is the stacking fault probability. Therefore, the imperfection scattering caused by plastic deformation of the alloys should be considerably smaller than that found in the pure silver. Since this was not observed, these results sugegest the possibility that stacking faults do not themselves contribute appreciably to the electrical resistivity of silver deformed at room temperature. An alternative explanation of these observations is that the scattering by the stacking fault is roughly proportional to the stacking fault energy, rather than being determined by the total area of such faults. Sufficient evidence is not yet available to separate these two possibilities. This work was supported by the Office of Naval Research.

Jan 1, 1962

By AIME AIME

AN unusually interesting meeting devoted to the discussion of the ways and means of improving coal mining practice, through the larger use of machinery underground, was held in the Auditorium of the Engineering Societies Building on March 11. The meeting was organized by the Materials Handling Division of the A. S. M. E. and held under the auspices of the Metropolitan Section of that Society and the National Coal Association. The New York Section of the A. I. M. E., which had been invited to participate, found itself unable to do so formally because of a conflicting date for its March meeting but informally did its part to aasure the success of the meeting. As a result of the discussion at and preceding the meeting, the National Coal Association, through Walter Barnum, chairman of its research committee, has asked the A. S. M. E. and A. I. M. E. to join the Association in a study of the present problems of the bituminous coal industry. Messrs. Harry L. Gandy, Calvin W. Rice and H. Foster Bain have been selected to act as a committee which shall develop plans for a joint program.

Jan 1, 1926

By J. T. Lapsley, I. I. Cornet, A. E. Flanigan, R. Hultgren, J. E. Dorn

With the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that procedures of heat treating common magnesium casting alloys be investigated systematically. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. Research on the solution heat treatment and aging of magnesium alloy AZg2, (formerly ASTM No. 17; also known as Dowmetal C or AM26o) which was done under "Restricted" Project NRC-2I, in 1942-1943, and reported in detail in a final report to the OSRD on September 3, 1943, is the basis of this paper, which has been released for publication by the OSRD. American experience with magnesium alloys prior to World War II was limited, although some of these alloys had been in commercial use since 1909. Requirements of the aircraft industry for light alloys made it imperative to understand and utilize the advantageous strength-weight properties of magnesium castings. Magnesium casting alloys are commonly solution heat- treated to increase their ultimate tensile strength and ductility; this treatment may be followed by an age hardening at elevated temperatures, which raises the tensile yield strength but diminishes the ductility. In the present investigation, AZp was studied to determine the effects on properties of various solution heat treatment and aging schedules. The principles of heat treatment of magnesium alloys are the same as for other non-ferrous alloys. The alloy studied, AZp, has a nominal composition of 9 pct aluminum, 2 pct zinc, and minor constituents. Fig I shows, by the projection of isothermal sections on the concentration plane, the solubility surface1 of the ternary magnesium-rich solid solutions as determined by X ray 'analysis. From this figure it may be seen that above approximately 375°C (707OF), AZp alloy is a single phase alloy at equilibrium; below this temperature the equilibrium condition is a two phase alloy. The beta constituent which precipitates from the solid solution exerts a hardening effect. Because the zinc concentration is only 2 pct, ancl because of its solubility relations, AZqz resembles a binary alloy of magnesium with aluminum. The solubility curve1 of Fig 2 shows how rapidly the solubility of the beta phase decreases with decreasing temperatures. Unlike many aluminum alloys, magnesium alloys do not age harden at room temperatures; precipitation hardening of AZ² alloy is performed at about 177°C (350°F). At this temperature about 3 pct aluminum

Jan 1, 1949

By Earl E. Hunner

At the end of the year 1914, the main North Star incline shaft had reached the 6300-ft. level, and encountered a vein dipping southwest, or exactly opposite to the North Star. Subsequent development failed to find the North Star vein continuing beyond this intersection, so the 6300-ft. level proved to be the bottom level of the North Star vein, and very little ore was found below the 5300-ft. level. The new vein was called No. 1 vein. Development work carried on for the next 10 years discovered a third vein, called No. 2, branching off about 1200-ft. to the east, with a north-south strike and a west dip. No. 1 vein had about 900 ft. of backs above the 6300-ft. level before reaching the boundary line of the property, and No. 2 vein died out about 800 ft. above. During these 10 years, the money spent on development was increased from $54,000 in 1914 to $184,000 in 1924; the ore reserves steadily diminished until it was evident that the mine must close down unless by some means a large tonnage of ore could be developed quickly. Problems and Plans In order to understand what follows, the general layout and equipment of the mine as it was at this time must be briefly described. Fig. 6 indicates the relative positions of the shafts. The North Star (incline) shaft extends from the surface to the 6300-ft. level following the vein, with an average pitch of 26", between limits of 11" to 38. There is at present no hoisting equipment in this shaft between the 2700 and 4000-ft. levels. The Central (vertical) shaft connects with the North Star shaft at the 4000-ft. level, at a vertical depth of 1600 ft. In two compartments of this shaft 4-ton skips made a vertical turn of 15 ft. radius at the 4000-ft. level and ran down the incline to the 6300-ft. level. A cage operated in the third compartment to the 4000-ft. level. Men and supplies were transferred to a truck running on a third track down the incline shaft to the 6300, operated by an electric hoist on the 4000-ft. station. When the shifts changed double-deck cages were substituted for the skips in the vertical shaft, but they stopped at the 4000-ft. station. The truck to 6300 carried 22 men, and it required 8 min. to make a trip down and back. This arrangement was satisfactory as long as a fairly large proportion of the work was

Jan 1, 1930

By Arthur T. Allen

THE Kingsport formation, a part of the Knox dolomite of Ordovician age, is composed of 538 ft of dolomitc and limestone. Numerous bands, layers and nodules of chert, arenaceous and shale zones are present. The characteristics displayed by these features have been useful in mapping, prospecting and mining. Perhaps a better understanding of the origin of these zones will increase their usefulness. Introduction The presence of numerous bands, nodules, and irregular bodies of chert within the Kingsport formation in the Mascot locality has long been recognized. Oder and Miller1 mention the general characteristics, but do not deal with the chert occurrences in detail. When the occurrence of chert is studied in fresh exposures underground, a variety of characteristics is noted which has been useful in correlation and in detailing the sub-surface stratigraphy. Although the writer has no desire to enter into a controversy over the origin of chert, many observations have been made of its local characterigtics. A detailed stratigraphic section is included which shows the position of the individual horizons discussed in the following paragraphs. The term "chertification" has been adopted from Fowler and Lyden2 for use here. It refers to the replacement of lime- stone by introduced silicic acid. The writer uses it to refer to the occurrencc of introduced or original chert in limestone and dolomite. In this writing "syngenetic chert" refers to chert which has been deposited contemporaneously with the enclosing limestone or dolomite. Also, it is considered to include interstitial silica shown by chemical analysis and insoluble residues. The term "epigenetic" is applied to all chert which has been introduced after consolidation of the rocks in which it occurs, regardless of the nature of the depositing solutions. Syngenetic Chert It is the belief of the author that a large percentage of the chert found in the Kingsport formation is syngenetic. The widespread occurrence of similar nodules and bands of chert in the same horizon far from one another and far from areas of deformation or alteration of the enclosing rocks is difficult to explain by infiltration of the silica after compaction of the enclosing rocks. When chert of this type does occur near zones of movement it is likely to be involved in faulting and brecciation which indicates that it was deposited prior to deformation. Older Epigenetic Chert There are several occurrences of nodules in the Kingsport which seem to be epigenetic as pointed out in the following examples: A cherty zone occurs 26 ft above the o bed (Fig =). This is not always present but is found in the greater part of mine work-

Jan 1, 1949

By Arthur T. Allen

THE Kingsport formation, a part of the Knox dolomite of Ordovician age, is composed of 538 ft of dolomitc and limestone. Numerous bands, layers and nodules of chert, arenaceous and shale zones are present. The characteristics displayed by these features have been useful in mapping, prospecting and mining. Perhaps a better understanding of the origin of these zones will increase their usefulness. Introduction The presence of numerous bands, nodules, and irregular bodies of chert within the Kingsport formation in the Mascot locality has long been recognized. Oder and Miller1 mention the general characteristics, but do not deal with the chert occurrences in detail. When the occurrence of chert is studied in fresh exposures underground, a variety of characteristics is noted which has been useful in correlation and in detailing the sub-surface stratigraphy. Although the writer has no desire to enter into a controversy over the origin of chert, many observations have been made of its local characterigtics. A detailed stratigraphic section is included which shows the position of the individual horizons discussed in the following paragraphs. The term "chertification" has been adopted from Fowler and Lyden2 for use here. It refers to the replacement of lime- stone by introduced silicic acid. The writer uses it to refer to the occurrencc of introduced or original chert in limestone and dolomite. In this writing "syngenetic chert" refers to chert which has been deposited contemporaneously with the enclosing limestone or dolomite. Also, it is considered to include interstitial silica shown by chemical analysis and insoluble residues. The term "epigenetic" is applied to all chert which has been introduced after consolidation of the rocks in which it occurs, regardless of the nature of the depositing solutions. Syngenetic Chert It is the belief of the author that a large percentage of the chert found in the Kingsport formation is syngenetic. The widespread occurrence of similar nodules and bands of chert in the same horizon far from one another and far from areas of deformation or alteration of the enclosing rocks is difficult to explain by infiltration of the silica after compaction of the enclosing rocks. When chert of this type does occur near zones of movement it is likely to be involved in faulting and brecciation which indicates that it was deposited prior to deformation. Older Epigenetic Chert There are several occurrences of nodules in the Kingsport which seem to be epigenetic as pointed out in the following examples: A cherty zone occurs 26 ft above the o bed (Fig =). This is not always present but is found in the greater part of mine work-

Jan 1, 1949

By McHenry Mosier

MeRcuRy is one of the strategic metals of which the supply has been raised from critical uncertainty to more than enough for essential demands. Work by the Bureau of Mines has contributed substantially to increased production of mercury in the United States and to consequent accumulation of Government stocks. Other contributing factors have been higher prices for mercury and Government loans to operators. The Bureau has undertaken 13 exploration projects, 10 of which have been completed. This work has comprised 28,376 ft. of several types of drilling and 23,798 lin. ft. of surface trenching, and has indicated commercial ore containing 34,800 flasks of mercury and marginal ore containing 26,200 flasks, a total of 61,000 flasks; equivalent, respectively, to domestic production for 8 months, 6 months, and 14 months. As Government stocks are now adequate, domestic production (currently at the rate of 50,000 flasks per year) is gradually being curtailed through Government control of labor and operating supplies. Introduction Mercury was one of the seven metals designated as strategic by the Army and Navy Munitions Board in 1939, when Congress appropriated funds for the investigation of domestic sources of supply of war minerals. The Bureau of Mines immediately started a limited search for strategic minerals, but the first mercury project was not begun until December 1940. The U. S. Geological Survey assisted in the search for cinnabar by contributing information on domestic mercury deposits, preparing maps, and making geological studies of exploration projects. The present high rate of production of mercury in the United States was encouraged by the increase in price to $196 per flask at New York (Fig. I) and Government loans to operators for mine development and plant construction. The Bureau of Mines has issued, for restricted distribution subject to wartime controls, 13 War Minerals Reports on individual mercury deposits (listed in appendix A). In March 1942 it also published a Progress Report of the Metallurgical Division, R. I. 3627, Cinnabar-reduction Plants of the Southwestern Arkansas Quicksilver District. Uses of Mercury Mercury and its compounds have more than 3000 uses. Its principal use is as a catalyst in the manufacture of gases for chemical warfare; the next largest is in pharmaceuticals. Mercury is essential also for: (I) certain electrical apparatus, (2) industrial control instruments at many war plants, (3) munitions, including blasting caps, (4) insecticides in agriculture, (5) antifouling paint for ship bottoms, (6) dental preparations, (7) general laboratory use, and (8) amalgamation of free-milling gold ores.

Jan 1, 1949

By McHenry Mosier

MeRcuRy is one of the strategic metals of which the supply has been raised from critical uncertainty to more than enough for essential demands. Work by the Bureau of Mines has contributed substantially to increased production of mercury in the United States and to consequent accumulation of Government stocks. Other contributing factors have been higher prices for mercury and Government loans to operators. The Bureau has undertaken 13 exploration projects, 10 of which have been completed. This work has comprised 28,376 ft. of several types of drilling and 23,798 lin. ft. of surface trenching, and has indicated commercial ore containing 34,800 flasks of mercury and marginal ore containing 26,200 flasks, a total of 61,000 flasks; equivalent, respectively, to domestic production for 8 months, 6 months, and 14 months. As Government stocks are now adequate, domestic production (currently at the rate of 50,000 flasks per year) is gradually being curtailed through Government control of labor and operating supplies. Introduction Mercury was one of the seven metals designated as strategic by the Army and Navy Munitions Board in 1939, when Congress appropriated funds for the investigation of domestic sources of supply of war minerals. The Bureau of Mines immediately started a limited search for strategic minerals, but the first mercury project was not begun until December 1940. The U. S. Geological Survey assisted in the search for cinnabar by contributing information on domestic mercury deposits, preparing maps, and making geological studies of exploration projects. The present high rate of production of mercury in the United States was encouraged by the increase in price to $196 per flask at New York (Fig. I) and Government loans to operators for mine development and plant construction. The Bureau of Mines has issued, for restricted distribution subject to wartime controls, 13 War Minerals Reports on individual mercury deposits (listed in appendix A). In March 1942 it also published a Progress Report of the Metallurgical Division, R. I. 3627, Cinnabar-reduction Plants of the Southwestern Arkansas Quicksilver District. Uses of Mercury Mercury and its compounds have more than 3000 uses. Its principal use is as a catalyst in the manufacture of gases for chemical warfare; the next largest is in pharmaceuticals. Mercury is essential also for: (I) certain electrical apparatus, (2) industrial control instruments at many war plants, (3) munitions, including blasting caps, (4) insecticides in agriculture, (5) antifouling paint for ship bottoms, (6) dental preparations, (7) general laboratory use, and (8) amalgamation of free-milling gold ores.

Jan 1, 1949

By M. E. Hassan, J. C. Calhoun, R. F. Nielson

An apparatus was constructed for the measurement of inter-facial tensions over a range of temperatures and pressures. This apparatus utilized the pendent drop method, and resembles in construction similar apparatus recently described in the literature and in use in some petroleum research laboratories. The interfacial tensions of benzene, propane, n-pentane, n-hexane. n-octane. and iso-octane against water were measured at temperatures ranging from 26" to 82" C and at pressures ranging from 1 to 204 atm. Values of interfacial tensions for the henzene-water system and their variations with temperature and pressure are generally in good agreement with value? of previous investigations. The data in all cases showed a slight decrease of interfacial tension with pressure at constant temperature in the range studied. The effect of pressure became less as the pressure was increased, with an indication of a reversal of the effect at higher pressures. There was a decrease of interfacial tension with temperature at constant pressure in all cases, as would normally be expected. This rate of decrease became greater the higher the temperature. A general equation is presented for the interfacial tensions as a function of presPurp and temperature over the range studied, and the constants calculated for each system. A definite trend was found in the effect of molecular weight on the interfacial tension at a given temperature and pressure, for the homologous series from propane to n-octane. Data for n-decane from the literature fitted well into this trend. INTRODUCTION It has been recognized for many years that surface forces play an active part in the production history of an oil reservoir as well as in determining the amount of unrecoverable oil. The magnitudes of these forces are governed by the values of the interfacial tensions. These vary greatly with composition, pressure, and temperature. The effect of composition is greater than that of pressure and temperature over the ranges normally encountered. In fact, because of the variety of compounds present in a crude, no attempt has yet been made to correlate crude composition with its surface tension or with its interfacial tension against water. The amount of dissolved methane greatly affects the surface properties of an oil, and there are "surface-active" compounds in crudes which have a much greater effect on boundary tensions than do equal amounts of hydrocarbons. The purpose of the present work was partly to contribute data that would eventually be used in correlations applicable

Jan 1, 1953

Granduc lies near the Alaskan border in British Columbia, about 600 miles (960 km) north of Vancouver. Prospecting in the area must take place in the short summer months of fog and rain because the winter is bitter cold, with snowfall up to 960 inches (24.4 m) accompanied by avalanches. Despite these difficulties, the mineral ized area was discovered in the 1920's. By 1956, Newmont Mining Corporation had developed mineable ore reserves estimated at 32,500,000 tons of 1.93% copper. Newmont and ASARCO, in a joint venture, then began development of the ore body, which was partially covered by glaciers. It was apparent a concentrator could not be built at the mine site where overland access was impossible due to the weather conditions and the terrain. Years of engineering studies of all possible access routes finally dictated the driving of an 11 mi long (17.6 km) tunnel passing under three glaciers and three mountain ranges to the nearest feasible concentrator site at Tide Lake. Even then, a mountain road subject to an average snowfall of 800 in. (20. 3 m) had to be built 32 mi (51 krn) from the concentrator through Alaska to Stewart, British Columbia, the nearest port. At Stewart, which is located at the head of a fjord 120 mi (192 krn) from the Pacific Odean, a fully equipped marine terminal was built. The tunnel, the lifeline between mine and mill, was to be driven from both ends; however, in 1965, an avalanche occurred at the Leduc portal, killing 26 crew members and wrecking much of the camp. The tunnel was then driven from one heading adjacent to the concentrator site at Tide Lake, a distance of 53,744 ft (16,381 m) to a point under the ore body. The remote location, type of terrain, and bad weather made supply of crews, equipment, and construction materials difficult; but in spite of these extremely adverse conditions, the tunnel crews set many world records. Mineralization throughout the ore zone is generally uniform in grade and composition and is primarily chalcopyrite and pyrrhotite associated with pyrite. Mining is mainly by sublevel caving. After blasting, rubber-tired load-and-haul equipment moves from level to level by means of an internal connecting ramp system on a 15% slope. At the gathering haulage level, 15-ton bottom-dump cars deliver the ore to a 600-ton pocket equipped with a Hudson "Rock-Flo" dump. The bottom of the ore pocket forms the feed chute to the primary

Jan 1, 1978

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By Harold Margolin, W. R. Hibbard, R. W. Fenn, H. P. Moore

Deformation lines, also called etch markings or strain markings, are non-effaceable lines developed in individual grains by etching a metal specimen which has been cold worked sufficiently to cause atomic non-conformity or slight orientation differences within the grains. Etching occurs more rapidly at these lines of high chemical reactivity to produce a result similar to that revealing grain boundaries. Wider etching effects forming bands have been found. They are believed to be bands of deformation lines which form areas of measurably different orientation from the crystal matrix. The crystallite rotations causing these bands have been shown by Barrett2 to contribute to deformation textures. Although deformation lines have been observed in many metals, the amount of deformation requireti for their appearance has been established only in general terms. Mathewson and Phillips3 observed the first appearance of deformation lines in cold-rolled alpha brass at about 20 pct reduction in thickness using the standard ammonium hydroxide hydrogen peroxide etchant. Price and Davidson4 noted defor- mation lines in common high brass after 26.5 pct reduction by cold rolling using the same etchant. Johnson6 observed dark thick forklike lines in 99.99 pct pure copper reduced 31.8 pct. Adcock6 observed deformation lines in 80-20 copper-nickel alloy rolled 50 pct. Samans7 found no deformation lines in alpha brass single crystals cold rolled 9.5 pct but they did appear after 25 pct reduction using ammonium hydroxide and hydrogen peroxide etchant. Barrett and Levenson8 observed deformation bands in drawn polycrystalline iron at very small reductions in area and noted that their initial appearance perhaps depends on grain size and other conditions. They reported deformation bands in a single crystal of iron reduced 6 pct by drawing. Brickg noted that deformation lines in 70-30 brass apparently associated with I I I I ) planes appeared after reductions of from 20-50 pct by cold rolling. Brick and Williamson10 noted that in single crystals of 70-30 alpha brass "as in polycrystalline brass, no deformation markings appeared until reductions exceeded 20 pct." Cook and Richards" reported that in Copper cold rolled less than about 50 Pet few strain markings were apparent but for higher reductions many strain markings appeared transverse to the rolled direction. In a review article Brick and Phillips12 noted that previous studies had not shown deformation lines in cold rolled alpha brass below 20 pet reduction and added that 4

Jan 1, 1949

By H. P. Moore, R. W. Fenn, Harold Margolin, W. R. Hibbard

Deformation lines, also called etch markings or strain markings, are non-effaceable lines developed in individual grains by etching a metal specimen which has been cold worked sufficiently to cause atomic non-conformity or slight orientation differences within the grains. Etching occurs more rapidly at these lines of high chemical reactivity to produce a result similar to that revealing grain boundaries. Wider etching effects forming bands have been found. They are believed to be bands of deformation lines which form areas of measurably different orientation from the crystal matrix. The crystallite rotations causing these bands have been shown by Barrett2 to contribute to deformation textures. Although deformation lines have been observed in many metals, the amount of deformation requireti for their appearance has been established only in general terms. Mathewson and Phillips3 observed the first appearance of deformation lines in cold-rolled alpha brass at about 20 pct reduction in thickness using the standard ammonium hydroxide hydrogen peroxide etchant. Price and Davidson4 noted defor- mation lines in common high brass after 26.5 pct reduction by cold rolling using the same etchant. Johnson6 observed dark thick forklike lines in 99.99 pct pure copper reduced 31.8 pct. Adcock6 observed deformation lines in 80-20 copper-nickel alloy rolled 50 pct. Samans7 found no deformation lines in alpha brass single crystals cold rolled 9.5 pct but they did appear after 25 pct reduction using ammonium hydroxide and hydrogen peroxide etchant. Barrett and Levenson8 observed deformation bands in drawn polycrystalline iron at very small reductions in area and noted that their initial appearance perhaps depends on grain size and other conditions. They reported deformation bands in a single crystal of iron reduced 6 pct by drawing. Brickg noted that deformation lines in 70-30 brass apparently associated with I I I I ) planes appeared after reductions of from 20-50 pct by cold rolling. Brick and Williamson10 noted that in single crystals of 70-30 alpha brass "as in polycrystalline brass, no deformation markings appeared until reductions exceeded 20 pct." Cook and Richards" reported that in Copper cold rolled less than about 50 Pet few strain markings were apparent but for higher reductions many strain markings appeared transverse to the rolled direction. In a review article Brick and Phillips12 noted that previous studies had not shown deformation lines in cold rolled alpha brass below 20 pet reduction and added that 4

Jan 1, 1949

By Raymond Ward

IN the past few years several papers have appeared dealing with different aspects of the oxidation of dilute alloys, especially with respect to the formation of internal oxides or subscales. Subscale has been defined1 as that layer or zone of oxide particles precipitated in a matrix of metallic metal in which the oxide particles are dispersed uniformly and occur by diffusion of the oxygen inward from the metal surface. Alloys composed of a solvent metal more noble than the alloying elements are subject to subscaling or internal oxidation. In these alloys the solute must be present in such quantities that if the alloy is exposed to an oxidizing atmosphere at elevated temperatures, the rate of diffusion of the oxygen into the metal will be greater than the rate of diffusion of the solute outward. There is a composition range of the iron-silicon system that falls into this classification. Knowledge of the nature and rates of oxidation of iron-silicon alloys is of great commercial importance, but very little information of this nature is available. Darken2 recently has made calculations to show the limits of concentration of silicon for which subscales are produced in iron-silicon alloys; however, the main thesis of his paper was to analyze and to explain the already existing data. The purpose of this paper is to present the effect of com position, temperature, time, and atmosphere on the type of scale-metal layer obtained and to give some qualitative indication of the effect of these variables on the rates of oxidation. Since this paper is a study of silicon steels that are available commercially, extremely low-silicon and high-silicon alloys are not included. EXPERIMENTAL PROCEDURE The alloys used in the experiment were taken from heats of silicon steel that ranged in analysis from 0.70 to 5.8 per cent silicon. This composition range takes in most of the commercial silicon steels. In Table I are listed the compositions of alloys used. Other than iron and silicon, the alloys normally contained approximately the following impurities: carbon, 0.03 per cent; manganese, 0.07; phosphorus, 0.008; sulphur, 0.02; copper, 0.07; tin, 0.01, and from nil to a trace of chromium, nickel and copper. All of the alloys used were melted in open-hearth furnaces, except where otherwise noted, and were hot-rolled to 0.100-in. plate. Samples approximately 1/2 in. square were then cut from these materials. So that the surface conditions of the samples used for oxidation would be standardized, each sample was ground through 000 emery paper immediately before oxidation. Two different techniques were employed in carrying out the oxidizing treatments. One consisted simply of heating the samples with free access to air. In this treatment the samples were set on edge on a refrac-

Jan 1, 1945

By L. B. Herring, Harold Decker

The South Texas area, discussed herein, represents districts 2 and 4 of the Texas Railroad Cominission and extends from Jackson, Lavaca, and Gonzales Counties on the northeast to the Rio Grande River, comprising a total of 26 counties.$ The present boundaries of this district do not coincide with those of earlier reports published in the annual volumes of Petroleum Development and Technology. The war, in its various ramifications, determined and controlled all the phases of the oil and gas industry. Priorities for material and governmental subsidies determined all new operations. New Pools In our opinion, the combine' quantity of crude and distillate reserves added in '943 approached Or possibly exceeded the amount produced. Thirty-five new pools were added to the area' Of these, five have significant reserves and ten offer possibilities of containing consequential reserves. The largest proven reserve discovered during the year was the Slick pool, on the DeWitt-Goliad County line. This is also the most important Wilcox discovery to date in the area. The most significant extension was at Willimar, Willacy County. Other important extensions were developed at Agua Dulce, Seeligson, and Odem. Except for the Porter field, in Karnes County, the Laredo trend, which produces lrom the Jackson and Yegua, proved very disappointing, and this pool is o:C secondary importance. The Scott and Hopper pool, Brooks County, has only orie well, but offers excellent possibilities of becoming an important discovery. It represents at this time the major Frio discovery of the year. The Hobson pool, Karnes County, is not a major reserve, but can be classed as important in that it produces at a shallow depth from the Wilcox. This proves that the potential area of production for this zone occupies a broad trend. Gas and Condensate During the year construction was begun on only one recycling plant, this being in the Sejita field, Duval County. Several others were colltemplated, but no actual operations were begun. The most important development in recycling was the rebuilding of old plants to allow for the fractiona-tion of isopentane, n-butane, isobutane, and propane. Heretofore all pentanes plus have been marketed as cLdistillate,n only a minor portion of the butanes being isolated and sold for fuel purposes. All these new the except propane, are considered vital to the war effort and propane is being marketed as fuel gas. In other instances propane is being isolated and then pumped back into the gas reservoirs for storage. It is anticipated that the demands for this product will increase in the future. Drilling in the Wilcox trend during the year showed the existence of valuable gas

Jan 1, 1944

By L. B. Herring, Harold Decker

The South Texas area, discussed herein, represents districts 2 and 4 of the Texas Railroad Cominission and extends from Jackson, Lavaca, and Gonzales Counties on the northeast to the Rio Grande River, comprising a total of 26 counties.$ The present boundaries of this district do not coincide with those of earlier reports published in the annual volumes of Petroleum Development and Technology. The war, in its various ramifications, determined and controlled all the phases of the oil and gas industry. Priorities for material and governmental subsidies determined all new operations. New Pools In our opinion, the combine' quantity of crude and distillate reserves added in '943 approached Or possibly exceeded the amount produced. Thirty-five new pools were added to the area' Of these, five have significant reserves and ten offer possibilities of containing consequential reserves. The largest proven reserve discovered during the year was the Slick pool, on the DeWitt-Goliad County line. This is also the most important Wilcox discovery to date in the area. The most significant extension was at Willimar, Willacy County. Other important extensions were developed at Agua Dulce, Seeligson, and Odem. Except for the Porter field, in Karnes County, the Laredo trend, which produces lrom the Jackson and Yegua, proved very disappointing, and this pool is o:C secondary importance. The Scott and Hopper pool, Brooks County, has only orie well, but offers excellent possibilities of becoming an important discovery. It represents at this time the major Frio discovery of the year. The Hobson pool, Karnes County, is not a major reserve, but can be classed as important in that it produces at a shallow depth from the Wilcox. This proves that the potential area of production for this zone occupies a broad trend. Gas and Condensate During the year construction was begun on only one recycling plant, this being in the Sejita field, Duval County. Several others were colltemplated, but no actual operations were begun. The most important development in recycling was the rebuilding of old plants to allow for the fractiona-tion of isopentane, n-butane, isobutane, and propane. Heretofore all pentanes plus have been marketed as cLdistillate,n only a minor portion of the butanes being isolated and sold for fuel purposes. All these new the except propane, are considered vital to the war effort and propane is being marketed as fuel gas. In other instances propane is being isolated and then pumped back into the gas reservoirs for storage. It is anticipated that the demands for this product will increase in the future. Drilling in the Wilcox trend during the year showed the existence of valuable gas

Jan 1, 1944