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By F. Michael Wahl

With the exception of reports on commercial deposits of kaolin, fuller's earth, and other specialty type clays, there is little published information on the extent, properties, and potential uses of the clay resources of Florida. Recent studies by the Florida Bureau of Geology in cooperation with the University of Florida and the U.S. Bureau of Mines have proven the existence of two extensive Miocene clay deposits, one in peninsular Pinellas County and the other in southeastern Charlotte County. Drilling and subsequent testing of the clays from these deposits indicate their potential for economic development. Both deposits consist of montmorillonite type clays, have an average thickness of 25 to 35 feet, and are overlain by unconsolidated Pleistocene sediments. Preliminary firing tests indicate that the clays from Pinellas County are a potential raw material for lightweight aggregate production. The clay has good bloating characteristics across an acceptable temperature range with a resultant aggregate density of less than 1.00 specific gravity. The clays from Charlotte County have poorer natural bloating characteristics but might well be used after treatment or with additives. The economic potential and locations of both deposits emphasize the need for locating similar clay resources in the state that might have economic potential so that land use planning and subsequent urbanization will not prohibit their development.

Jan 1, 1972

By E. T. C. Spooner, Ioannou S. E.

"Abstract- The Dixie Zone Au-Ag deposit is a low sulfidation (adularia-sericite) epithermal system located 1.4 km from the producing Ken Snyder mine (7.0 M oz Au equivalent reserve/resource), Midas Mining District, north-central Nevada. This WNW striking, steep south dipping, fault system is hosted by mid-Miocene (17 Ma to 14 Ma) felsic volcanic rocks that were erupted from a vent(s) to the northeast. The system was mineralized by approximately 250 ± 20°C (n = 86), near-neutral pH, ascending fluids of predominantly meteoric origin [volatile corrected salinity = 0.52 ± 0.35 eq.wt% NaCl (n = 86)]. Bulk analytical fluid inclusion gas chromatography identified a mineralizing fluid volatile composition of 99.68 ± 0.18 mole % H2O, 0.16 ± 0.09 mole % CO2, 0.11 ± 0.05 mole percent N2, 0.05 ± 0.04 mole % CH4, and 0.01 ± 0.01 mole % CnHn+i (n = 7). Sulfur species were not analyzed due to absorption within the chromatography system; however, a H2S concentration of 16 ppm to 160 ppm molar is estimated. The volatile content contributes approximately 50% of the microthermometrically measured freezing point depression. Cl- concentrations up to approximately 9000 ppm suggest an additional, probably magmatic, fluid component.Ascending fluids were channelled along approximately NW striking faults related to the same primary extension (17 Ma to 14 Ma) responsible for Nevada basin and range physiography. Boiling induced by CO2 effervescence led to precipitation of Au and Ag over a 150 m vertical interval. At the time, this interval was about 460 m below the water table (approximately 38 bars), but because of erosion, it is now within 90 m of the surface. A Ag:Au ratio of 25:1 has been calculated for the Dixie Zone."

Jan 1, 2000

Mirador - Overview ? Located in Andean foothills of SE Ecuador ? Copper-gold porphyry hosted by calc-alkaline Late Jurassic granitic and porphyritic rocks ? 438 MT of 0.61% Cu and 0.19 g/t Au measured and indicated resources (at 0.4% Cu cut-off) ? Additional inferred resources of 235 MT of 0.52% Cu and 0.17 g/t Au ? Initial 25,000 tonnes/day production, expanding to 50,000 in year 6 320 MT of 0.62% Cu, 0.2 g/t Au ore mined at an average 1.4:1 strip ratio over a 21 year mine-life

May 1, 2006

By Z. Q. Yue

Many large rock avalanches and/or landslides have occurred in mountainous regions around the world. Their occurrences are normally rapid and unexpected, which can cause disasters. They have been investigated extensively by many researchers and engineers since the 1903 Frank Slide on Turtle Mountain, Alberta, Canada. They are one of the most peculiar phenomena because the rock debris of more than one million m3 can move over the horizontal distances exceeding those expected from conventional friction physics. This paper presents a gas cause hypothesis responsible for the large rock avalanches. It is the migration and expansion of a certain amount of highly pressurized and dense natural gas mass from deep geological grounds into the mountainous rock mass slopes. The natural gas with high pressure and density can escape from the deep geological ground and flow through faults, weak zones and/or porous channels into the rock mass forming a mountainous slope. The rock mass forming the slope has the high tensile and compressive strength and can resist the initial loading of the gas mass migrated into and stored in their voids, pores, holes, gaps, openings, apertures and cavities. With time, more and more gas mass from deep ground can migrate into and stored in the slope rock mass. Eventually, the peak equilibrium of forces and deformation reaches. The expanding power of the gas in the slope rock mass would instantly and rapidly break, erupt and/or explode them. The compressed and dense gas mass would mix, flow and expand together with the broken rock debris mass and continue offering their remaining expanding powers to the moving and sliding debris mass. As a result, the rock debris of large volume can reach the runout distances exceeding those expected from the conventional friction physics. The gas would escape into the sky and the solid rock debris would remain on the ground spreading over large ground area. The 1903 Frank Slide is examined to show this gas cause and mechanism in mountainous regions.

Jan 1, 2015

By Peter F. Pullen

The need to apply the latest available technology to develop better tools and methods to meet problems in the mining industry was recognized by six of Canada's leading mining companies. As a result, MIROC (Mining Industry Research Organization of Canada) was chartered to identify problem areas in Canadian mining and to have research carried out to develop the tools and equipment to meet these perceived needs. The initial activity of MIROC has been in the environmental field, with improved clothing and protective devices being developed by contractors. Work clothing for miners is now being field tested. Respiratory protection and a new personal light source combined in a new "space-age" helmet are about to be issued for testing. Further developmental work is being carried on to offer these units and probably other personal protective devices on an individual basis as well as in a combined package.

Jan 1, 1979

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

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

Jan 1, 1936

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

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

Jan 1, 1936

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

Jan 1, 1979

US 4,181,588 - Direct extraction of lead from lead sulflde ore. Ore is leached with a solution of ferric chloride and sodium chloride. The leach liquor is filtered to remove sulfur and gangue, then cooled in a crystallizer to precipitate lead chloride The slurry from the crystallizer is subjected to electrolysis to deposit lead chloride on the cathode plate. Solution from the electrolysis cell is used in the leaching step. M.M. Wong and F.P. Haver, assigned to US Secretary of the Interior Jan 1, 1980. 6 pp. (204-115). Filed: 1-4-79 (1,026).

Jan 1, 1982

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

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

Jan 1, 1951

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

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

Jan 1, 1951

By J. E. Harris

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

Jan 1, 1935

C. R. CORNING, Chairman. ADOLPHE E. BORIE, First- Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. Vice-Chairmen. JOHN H. ALLEN, GEORGE M. COLVOCORESSES, RICHARD M. ATWATER, JR., -ROBERT PEELE, GEORGE D. BARRON, CHARLES P. PERIN, A. CHESTER BEATTY, JOSEPH A. VAN MATER, J. PARKE CHANNING, ARTHUR L. WALKER. D. C. Bard, Howard Eckfeldt, Milton H. McLean, W. de L. Benedict, R. C.Gemmell, ' Philip N. Moore, John C. Branner, F. Louis Grammer, T. H. O'Brien, Palmer Carter, Ernest A. Hersam, James J. Ormsbee, Allan J. Clark, Edwin C. Holden, Edward W. Parker, F. Crabtree, William L. Honnold, John B. Porter, George G. Crawford, Reginald E.. Hore, R. M. Raymond, O. C. Davidson, C. Colcock Jones; Robert B. Richard's, E. V. D'Invilliers, Eugene P. Kennedy, LeRoy Salsich, James S. Douglas, Chester F. Lee, Henry L. Smyth, Walter Douglas, Richard S. McCaffery, F. W. Traphagen, Howard N. Eavenson, James F. McClelland, Elton W. Walker. Meetings of this committee were held at the Institute headquarters on April 18, May, 3 and 15, and June 19.. At the meeting of June 19, the Secretary reported that letters of invitation to apply for membership in the Institute had been sent to all the alumni of the School of Mines of Columbia University and also to all State Mine Inspectors and their deputies. He also reported the securing of lists of the alumni of the Harvard Engineering Schools, and of the Mining Schools at Houghton, Mich. ; Butte, Mont. ; State College, Pa. ; Seattle, Wash. ; Fayetteville, Ark.; Laramie, Wyo.; Montreal, Canada, and Wor-cester and Rensselaer Polytechnic Institutes. Arrangements were made to invite all these to join the Institute. It was suggested that a. member' of the Institute resident in Australia be appointed to this Committee, also one from Japan. Attention of the members of the Committee was drawn to the fact that letters requesting, others to join the Institute will be written in the offices of the Institute if desired. The applications for membership received recently have been as follows March, 30; April, 02; May, 70; June, 54. The next meeting will be held July 17. THOMAS T. READ, Secretary.

Jan 7, 1913

INTERNATIONAL GEOLOGICAL CONGRESS. (For further particulars apply to the Secretary, 12th International Geological Congress, Victoria Memorial Museum, Ottawa, Canada ; cable address, Geocong, Ottawa.) The Coal Resources of the World.-Three quarto volumes of about 400 pages each, 8 1/4 by 10 3/4 in., and an atlas of about 70 maps in colors, 13 1/3 by 19 1/2 in., bound in heavy paper cover. Edition limited to 3,000 copies, One thousand copies will be reserved for members of the International Geological Congress, and the remainder of the edition will be distributed in the order in which applications are received. Price, $35 per set. Ready in July, 1913. This book is an inquiry made upon the initiative of the Executive Committee of the Twelfth International Geological Congress, with the assistance of geological surveys and mining geologists of different countries, published by: Morang & Co., Ltd., Toronto, Canada. Headquarters During Session at Toronto. The headquarters will be a t the University of Toronto, where there will be a branch post-office open at all hours and at which registered mail may be received or despatched, money orders sent or cashed, etc. A hank will be established at which money may be exchanged. A typewriting service will be maintained, also a telephone service and messenger service. Railway and steamship agents will also be in attendance. A restaurant service providing luncheon in the middle of the day will be arranged.

Jan 8, 1913

COMMITTEE ON INCREASE OF. MEMBERSHIP. C. R. CORNING, Chairman. ADOLPHE E. BORIS, First Vice-Chairman. THOMAS T. READ, .Secretary, Woolworth Bldg., New York, N. Y. Vice-Chairmen. JOHN H. ALLEN, GEORGE M. COLVOCORESSES, RICHARD AL ATWATER, JR., ROBERT PEELS, GEORGE D. BARRON, CHARLES P. PERIN, A. CHESTER BEATTY, JOSEPH A. VAN MATER, J. PARKE CHANNING, ARTHUR L. WALKER. D. C. Bard, Howard Eckfeldt, Philip N, Moore, W. de L. Benedict, R. C. Gemmell, T. H. O'Brien, John C. Branner, F. Louis Grammer, James J. Ormsbee, Palmer Carter, Ernest A. Hersam, Edward W. Parker, Allen J. Clark, Edwin C. Holden, John B. Porter, F. Crabtree, William L. Honnold, R. M. Raymond, George G. Crawford, Reginald E. Hore, Robert H. Richards, O. C. Davidson, C. Colcock Jones, LeRoy Salsich, E. V. D' Invilliers, Eugene P. Kennedy, Frederick H. Sexton, James S. Douglas, Chester F. Lee, Henry L. Smyth, Walter Douglas, - Richard S. McCaffery, F. W. Traphagen, Howard N. Eavenson, James F. McClelland, Elton W. Walker. Milton H. McLean, Meetings of this committee were held at the Institute headquarters on April 18, and May 2 and 15. It was resolved that meetings shall be held monthly on the third Friday of each month.

Jan 6, 1913

S. F. EMMONS RESEARCH FELLOWSHIP. The movement was started by a number of the friends and admirers of the late S. F. Emmons, Economic Geologist of the United States Geological Survey, to perpetuate his name through a fellowship to be known as the ?S. F. Emmons Research Fellowship," and they have succeeded in raising some $13,000 for the purpose of carrying on research work in economic geology. The Committee in charge of this Memorial Fund has succeeded in obtaining the co-operation of Professors Kemp, of Columbia, Irving, of Yale, and Lindgren, of Massachusetts Institute of Technology, in the administration of this fellowship. These three gentlemen are respectively geologists of the institutions mentioned and are exceptionally qualified to determine in what direction the fund can be best administered. It is hoped that additional contributions will be forthcoming from many who have heard of this movement. Subscriptions are invited and may be sent to any one of these gentlemen, or to Benjamin B. Lawrence, Treasurer, No. 60 Wall Street, New York City.

Jan 10, 1913

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

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

Jan 1, 1949

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

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

Jan 1, 1949

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

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

Jan 1, 1945

By J. W. Hickman

Most of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.' In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,~ nickel,= chromium,= copper,z tungsten,s molybdenum,3 beryllium,' uranium,' thorium,' titanium6 and zirconium6 while investigations are in progress on tantalum and columbium. The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally. Examples of solid solutions which may present difficulties are MOO* and WOp, Fe304 and FeO.CrnOa since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of loglo Kg for the several temperatures. AF"B = -RT In KR AF°R and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the the given in I 1 to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium oxide to form

Jan 1, 1949