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Jan 1, 1923

By Leendert de Witte, Fred J. Radd

In many areas caring failures can be directly related to electrical currents observed in the casings. It is the thesis of this paper that the observed casing currents are mainly due to electrochemical potentials of the type in evidence on spontaneous potential curves of electrical logs. The general nature of these potentials are discussed and an equivalent circuit is given for current and potential distributions around open holes. The casing forms a short circuit to these potentials and tends to average the effects of local cells. The case of casing corrosion opposite the Dakota water sands in the salt-mud area of Kansas is discussed anil used us a qualitative, illustration of the relation between SP's and casing currents. A method of quantitative derivation of casing current distribution frorn electric log SP curves, using linear transform theory, is described and results are compared with a measured current profile. The effects of hydrogen over-potentials at the cathodic portions of the pipe are considered and some laboratory data are given in support of conclusions regarding the over-1.01tuge.s. INTRODUCTION To date an appreciable amount of work has been done on the measurement of oil well casing currents and on the correlation of the anodic portions of the current profiles with corrosive casing failures. Speculations on the origin of the casing currents have, however, remained rather vague; and although almost every plausible cause has been mentioned, there is to the writers' knowledge no clear-cut expose' on the details of the causes of the corrosive currents in the literature. A study of current surveys and casing failures in the N.W. Burnett field, Ellis County. Kan.. indicated the probability that concentration cell emf's between the Wellington salt section and the relatively fresh waters in the Dakota sands were a major cause of the corrosion currents. A more general concept evolved upon analysis of the severe corrosive conditions in the Pleistocene sands in the Ventura Avenue and San Miguelito fields in California. In this area no major variations in the salt content of the formation waters occur and yet large casing currents are observed. An explanation is found in the fact that the local spontaneous potentials which are set up due to concentration contrast between the drilling fluid and the connate water are short circuited when casing is set. The very conductive path through the casing increases the magnitude of the currents and has the tendency to average local sources over fairly large intervals. Current will flow between the sections that are predominently shaly and the sections that are mostly sandy. At the places where the current leaves the pipe, corrosive attack will occur. This same phenomenon will be present wherever unprotected pipe is set through sections that show large SP kicks on the electric logs over reasonably thick interval~. GENERAL- NATURE OF THE SPONTANEOUS POTENTIALS When a sequence of sedimentary rocks is penetrated by a drill hole filled with a mud which has a different salt concentration from that in the formation waters, various types of electrochemical potentials are established between the formations and different parts of the mud column. Opposite clean sand sections. a simple liquid-liquid junction potential will be observed; while opposite argillaccous formations, a membrane potential, often referred to as shale potential, will be established. The first quantitative analysis of these emf's in terms of liquid junction and membrane potentials is due to Wyllie.1

Jan 1, 1956

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

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

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

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

Jan 1, 1930

By J. R. Long, R. S. Dean, F. S. Wartman, E. T. Hayes

The production of titanium in I5-lb. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,' has provided adequate material for a study of the physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the proper- ties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. Consolidation of the PowdeR The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at 50 tons per

Jan 1, 1946

By J. R. Long, E. T. Hayes, R. S. Dean, F. S. Wartman

The production of titanium in I5-lb. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,' has provided adequate material for a study of the physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the proper- ties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. Consolidation of the PowdeR The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at 50 tons per

Jan 1, 1946

By Robert F. Mehi

The mechanical behavior of metals and alloys is presumably conditioned by two factors; namely, the crystallinc symmetry and the interatomic forces. Considerable attention has been given to the first of these factors through the recent advances in X-ray technique. It is the purpose of the present paper to call attention to the importance of the second of these factors, to point out promising methods of investigation, and to present some pertinent data. Plastic deformation takes place by slip along atomic planes.' This slip may be inhibited in a number of ways: by the interatomic forces of, cohesion which bind the atoms rigidly in a lattice structure, which in pure metals is usually of high symmetry; by latticc distortion caused by solid solution formation or by mechanical strain; by the intercrystalline boundaries whcrc slip is restrained, probably by the non-registration of the atom planes in adjacent crystal1ites;2 and by the presence of small hard particles which serve to "key" the slip along the atom planes.5 In pure metals, and perhaps also in solid solutions, the atom planes of easiest slip are those exhibhing the greatest density of atomic population and the greatest interplanar distance4 and apparently can now be pre-dict,ed from the analysis of the lattices. Concerning the interatomic forccs, which resist this slip by holding the atoms firmly together, little is known. Most textbooks on physical metallurgy, following the work of Bot-tone,5 correlate the hardness of the pure metals with the atomic volume,

By K. Hodgson, N. C. Joughin

The detailed mechanism of rockbursts and other forms of damage due to rock failure in underground mining is as yet unknown. Studies of the energy changes which necessarily occur when an excavation is made underground seem to provide the best understanding of the phenomena leading to rock failure and damage (see Cook 1). It is common knowledge that the damage and rockburst hazard increases with depth and is greatest at remnants and in regions mined in an irregular manner. The rate at which energy is released as an excavation is enlarged provides an objective parameter to describe mining geometry in terms which are significant to studies of rock failure. In this paper, it is shown empirically that the rate of energy release per unit area increase in the size of an excavation is closely related to seismicity and incidence of damage in the mine. Consequently, it is suggested that the energy release rate is an important parameter in the design of underground mine layouts. Observations were made at two mines: the East Rand Proprietary Mines, Ltd. (E.R.P.M.), at a depth of about 9000 ft, and at Harmony Gold Mining Co., Ltd., at a depth of about 5000 ft. At both of these mines continuous recording seismic networks were in operation. (See Cook and Joughin.3) DESCRIPTION At E.R.P.M. the gold-bearing reef dips at approximately 35 degrees and is presently being mined at depths from 8000 ft to 11,000 ft below surface. The rock surrounding the excavation consists of a very homogeneous quartzite extending far into the hangingwall and footwall. The stoping width is approximately 40 in.

Jan 1, 1967

A HIGHLY successful joint conference on coal-mine transportation was held at Pittsburgh on Oct. 20 by the Pittsburgh Section of the American Insti-tute of Mining and Metallurgical Engineers and Mining Section of the Engineers' Society of Western Pennsyl-vania. C. E. Lesher, executive vice-president of the Pittsburgh Coal Co., presided over 215 members and others in the morning and Graham Bright, sales en-gineer with the Mine Safety Appliances Co., presided over about 180 in the afternoon. There were four prepared papers and much discussion, as well as a good luncheon between the sessions. Mechanical loading in the Pittsburgh district was discussed by L. E. Young, production vice-president of the Pittsburgh Coal Co. More companies in this district are using loading machines, more types of machines are being tried, and more coal is being mined by them than heretofore. The draw-slate above the Pittsburgh seam is the main problem; but devices for supporting and moving draw-slate are being tested. Except in two mines, the slate is being taken down. The fundamentals of the machines are similar, but the electrical drive and other parts have been improved. The problem is to recover or move as much coal as possible without hand labor. Methods of cleaning coal must be improved to meet the new methods of loading. The Pittsburgh Coal Co. has ten Joy machines and others are under order, a Myers-Whaley machine, Jeffrey conveyors, and Eichoff conveyors. The last mentioned are used in entries and other conveyors in rooms. At Montour No. 10 mine, one Joy machine is worked in rooms and one in entries.

Jan 12, 1927

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"' the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,' and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,' or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By D. A. J. Swinkels

The problem of determining oxygen levels in liquid steel to aid in deoxidation control has received general attention for a number of years. Work in this direction started at the B.H.P. Central Research Laboratories early in 1967 with an evaluation of sampling techniques followed by vacuum fusion analysis to determine the oxygen content of the samples (1). It was found that these techniques had a number of drawbacks if they were to be used for deoxidation control. The method of analysis was rather too slow to allow effective control and measured total oxygen level rather than dissolved oxygen. Furthermore, the results were found to be very variable due to slag entrainment in the samples. Attention therefore turned to the galvanic cell method using a solid oxygen ion conductive electrolyte such as cubic stabilised zirconia. The ionic conductivity properties of electrolytes such as (ZrO2) 85 (CaO).15 had been studied by a number of investigators and had already been applied to the measurement of oxygen activity in gases, in lower melting metals such as copper, lead, tin, silver, alkali metals and indeed the first studies in steel had been made (2,3). Since then the results of a number of studies in the development of an expendable oxygen probe for steel have been reported (4-9).

Jan 1, 1972

NEW MEMBERS The following list comprises the names of those persons who became members during the period Aug. 10 to Sept. 10, 1914: Members ALLEY, HARRY MCCAMMON, Mill Foreman .... Churchill Mining Co., Wonder,2 Nev. AMBLER, J. OWEN, Met..; ... Calumet and Arizona Mining Co., Douglas, Ariz. ANDERSON, JAMES WILLOUGHBY, Duell, Warfield and Duell, 2 Rector St., New York, N. Y. ANTISELL, FRANK L., Asst. Supt Raritan Copper Works, Perth Amboy, N. J. CARRINGTON, FRANK GAMBLE, Sec'y and Asst. Mgr., Standard Foundry Co., Anniston, Ala. CONKEY, CHARLES ROLLAND, Structural Draftsman, Barnett McQueen Co., Ft. William, Ont., Canada. COOK, PAUL RICHARDSON, Mill Shift Boss, Buckhorn Mill and Cyanide Plant, Buckhorn. Nev.

Jan 10, 1914

By J. L. Bruce, N. B. Braly, F. A. Linforth, Wm. B. Daly, Paul A. Gow, C. L. Berrien, R. H. Sales, P. F. Beaudin, John Gillie, G. W. Roddewig

Butte mining district is situated in Silver Bow County, in the southwestern part of Montana. Butte originated as a placer mining camp, gold having been discovered in 1864, on Silver Bow Creek, near the southerly end of what is now Main Street. The Butte placer gold was heavily alloyed with silver, and only commanded $13 an ounce. Placer mining was vigorously prosecuted along Silver Bow Creek and its tributary gulches for about 5 years, at the end of which time, in 1870, the Butte camp was practically deserted. In the meantime, the quartz veins prominently traceable over the hillsides were located, the first location, July 12, 1864, being made by the Missoula Mining Co. and called the Missoula Lode Claim, and later relocated by G. 0. Humphreys. Reasoning from the presence of the gold placers, free milling gold and silver ores were eagerly looked for by the early prospectors. Claims covering the great Rainbow and other silver lodes were located in the 60's. The presence of valuable silver ores in these veins caused the staking of many claims, believed to be valuable only for silver, but which later, at depth, proved to be enormous copper producers.

Jan 1, 1925

T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—Mr. Killian is to be commended for his inquiry as to why a decrease of 15.3 pct in coke consumption was accompanied by a decrease of only 1.9 pct in the CO/CO, ratio of the top gas. Although I encouraged him in his efforts to find a more significant and meaningful carbon-gas ratio, the method, calculations, and conclusions originated entirely with the author. Whether we agree entirely with the assumptions underlying his corrected ratio, I think we can all agree that a better ratio is needed, and that he deserves credit for recognizing the need and for doing something about it. To be most useful, the CO/CO, ratio for the top gas should reflect the way in which the carbon is gasified in the furnace, particularly the degree of oxidation and the extent of heat release. The effect of CO, from the decomposition of the limestone and the effect of the reaction of CO and water vapor in the upper part of the furnace on the quality of top gas should be isolated from the effect of more basic reactions such as ore reduction and solution loss. The reduction of sufficient iron oxide to produce a ton of pig iron and the accompanying changes in the proportions of the carbon gases can be expressed on a mol basis as follows: 16.5FeA + 16.5CO - 33FeO + 16.5CO, [1] 33FeO + 33.0CO = 33Fe + 33CO. [2] The CO, from eq 1 normally escapes from the furnace because it does not react with coke at the temperature of its release. However, as much as 50 pct of the CO, from eq 2 may react with coke because it is released at temperatures above 1000°C: 16.5CO. + 16.5CO2 = 33CO [3] Thus we see that the gasification of 16.5 mols or about 200 lb of C in solution loss will regenerate as much CO as is required for the last stage of reduction. The pronounced effect of reaction 3 on the final proportions of CO and CO, in the gas stream is obvious. It also follows that reaction 3 materially alters the heat release but it cannot be entirely eliminated in Lake ore practice. A previous study indicates that 100 lb of solution loss may be necessary to maintain the reducing power of the gas. A reduction of 100 lb from the normal level of 200 lb would mean that over 1,-000,000 additional Btu are released in the process. The 100 lb of additional carbon which will be burned at the tuyeres will release 437,000 Btu and the absorption of 583,000 Btu by eq 3 would be prevented. One of the chief objectives of sized ore burdens and more uniform distribution of the gas stream is to minimize solution loss by completing reduction higher in the furnace and in turn to release the maximum amount of heat from the carbon charged. It was odd, indeed, to find that the use of sized ore and sinter in the careful tests reported by Dobscha had changed the CO/CO2 ratio very little. The author has stressed the close correlation between his corrected CO/CO, ratio and production. A correlation of fuel consumption and the CO/CO, might be more logical. Fuel consumption on the prepared ore burden decreased 15.3 pct whereas the corrected CO/CO2 ratio decreased 19.0 pct. Although this agreement between the reduction in fuel and the reduction in corrected CO/CO2 ratio is not as close as the correlation with tonnage, it indicates the corrected ratio is superior to the normal ratio which decreased less than 4 pct. Some adjustment should be made for the reaction: CO + H2O = CO2 + H2 —700Btu [41 because there is evidence to indicate that about one half of the hydrogen is formed in the upper 21 ft of

Jan 1, 1953

(The following list contains the names of those members of the Institute of whose connection with military service. we have only recently become acquainted; it also includes the names of a few who have recently been promoted or transferred. A complete list was published in the Year Book, issued as a supplement of the Bulletin for March, 1918.) ADAMS, HENRY, Major, Assistant to Department Engineer, North-eastern Dept. ALINE, P. A., Co. C, 316th Supply Trains. * Low-cost cottage construction in America; a study based on the housing collection in the Harvard Social Museum, by Winthrop A. Hamlin. Cambridge, Mass., Harvard University, 1917. (Publications of the Department of Social Ethics, No. 7.) 30 pp., 4 charts. Illus.

Jan 5, 1918

R. L. Fleischer (Department of Metallurgy, Massachusetts Institute of Technology)— The authors have presented valuable observations of oehavior of aluminum at intermediate and high temperatures. I should like to consider their interpretation of the appearance of cross slip plane traces in sample B-3 as partly due to "bending of the crystal due to grip constraint." Because bending moments might be set

Jan 1, 1960

By James D. McClung, H. J. Gluskoter, M. R. Geer

INTRODUCTION The purpose of coal preparation is to improve the quality of coal to make it suitable for a specific purpose by (1 ) cleaning to remove inorganic impurities; (2) sizing-crushing or screening, or both; or (3) special treatment, such as dedusting. The properties and quantities of impurities in coal are of major importance in the design and operation of steam generating equipment. Al- though boilers are often designed and equipped to use a wide range of coals, no boiler will perform equally well with all types of coals. All coals have certain properties that place limitations on their most advantageous use. These limitations are especially stringent for many of the older installations. Because of a general lowering of quality of raw coal in recent years, the need for coal cleaning has significantly increased. Among the factors contributing to the need for increased coal preparation are (1) increased demand for quality brought on by market and environmental requirements; (2) increased extraneous dilution caused by mine, health, and safety laws; and (3) depletion of the higher-quality coal seams.

Jan 1, 1979

By A. P. Anderson, J. H. Jensen, W. E. Breckoff

Bromine is the intermediate member of the halogen family of elements between iodine, a solid, and chlorine, a gas. The name is derived from the Greek "bromos," meaning stench. Bromine is the only nonmetallic element that is liquid at room temperatures with a melting point of -7.2° C and a boiling point of 58.78º C. Reddish brown in color, it dissolves easily in water to yield a red solution. Bromine volatilizes at ordinary temperatures to a red vapor that is very irritating to the eyes, nose, and throat. Density of the liquid is 3.12 and gas weighs 7.59 gpl at standard conditions. As the element is highly active, it exists in nature only as bromide compounds. Bromine was discovered by Antoine Jerome Balard in seawater bitterns in 1826 and first prepared in quantity in 1860. Distribution Bromine is widely distributed in nature and compounds occur in solution in natural brines, in seawater, saline lakes, oil and gas well brines, and in evaporite chloride minerals. The concentration of bromine salts ranges from 60-65 ppm in seawater to several thousand ppm in oil well brines and saline lakes. The distribution of bromine in marine evaporite minerals and in the solutions from which they crystallized was determined many years ago by H. E. Boeke (1908). Theoretical aspects regarding the geochemistry of bromine have been published in numerous papers (Raup and Mite, 1969). Bromine occurs in solid solution in carnallite and sylvite associated in potash deposits; in halite in salt beds; salt in oil shales; and in trona deposits. Its presence is useful as a guide in geochemical exploration. The analysis of small amounts of bromides in the presence of large amounts of chlorides is discussed by W. Schwerdtner (1963). Manganese, iron, and iodine may interfere with the determination. Other analytical methods are discussed at length in the literature (Stenger and Atchison, 1964). Sources and Reserves The sources and reserves of bromine, given in Table 1, appear ample to meet present and foreseeable requirements in all producing countries. With the occurrence of bromine salts in seawater and other brines, the potential for bromine production is worldwide. It has been estimated that 99% of all commercially recoverable bromine is in the ocean. However, actual subterranean brines having a higher bromine content than seawater will continue to be the preferred sources of bromine for the foreseeable future. [ ]

Jan 1, 1983

By S. Senderoff, D. E. Couch

A PROCESS for the electrolytic preparation of molybdenum from molten salts has been described previously. This previous work centered on electrowinning and electroplating characteristics of the process. In this paper the properties of the process as a refining medium are discussed. In producing metals from ores, it frequently has proven most economical to obtain a comparatively impure metal by smelting, and to purify the product by electro refining. Direct electrowinning from molten salts is rather difficult when a porous diaphragm is required in the process, as in the case of molybdenum, since satisfactory refractory materials for such a diaphragm in molten salts have not yet been developed. In electrorefining, however, a soluble anode is used. By suitable control of anode and cathode current densities, the lower-valent molybdenum compound used in the electrolyte is not oxidized, and a diaphragm is not needed, thus avoiding difficulties which are encountered with other electrowinning processes. Electrorefining may result from two different processes in the cell: Dissolution of the molybdenum and the less noble impurities with a separation of the more noble impurities as an anode sludge; the electrodeposition of molybdenum and the more noble metals at the cathode, leaving the less noble metals in the electrolyte. The amount of separation which occurs in each process is determined by the potential of the operating electrode and the relative concentration of the various species at (or in) that electrode. Since molybdenum has a comparatively noble position in the EMF series in molten alkali halides,2 most refining would be expected to occur at the cathode. In this work only the cathodic process was studied. The objective was to determine to what extent various metallic ions, if they dissolve from the anode or are otherwise introduced, were concentrated in the electrolyte. The necessary conditions for the separation of each and the limiting concentration which may be tolerated in the electrolyte for effective refining were studied. The deposits were chipped from the cathode and analyzed spectrochemically for metallic impurities. Besides determining the major contaminant, a general qualitative analysis was obtained to be sure that other metallic ions were kept at a very low level during each series of runs and to be sure that the baths were not being contaminated accidentally. Samples of the bath, for analysis, were taken at the temperature of operation so there was no chance of selective crystallization during cooling. In this way the ratio of molybdenum in the bath to the other metal could be determined readily. These data permitted a check on the anode efficiency and any volatilization that took place during the electrolysis. Experimental Apparatus—The apparatus as shown in Fig. 1 was used to determine the effect of the various foreign ions upon electrodeposited molybdenum. The entry chamber A allowed the cathodes to be removed without cooling the bath and without allowing oxygen or moisture to enter." The cathodes were made Prom 0.25-in. tungsten rods and were rotated during the electrolysis. The balloon in the lower arm B was inflated with helium after the cathode was drawn up into the upper section for removal. A new cathode was then placed into the entrance chamber A after which the chamber was flushed

Jan 1, 1959