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APPLICATIONS for loan contracts for the exploration, development and mining of strategic and critical metals and minerals are now being accepted by the Department of the Interior. The RFC is authorized and directed by Executive Order 10161 to make such loans but the Secretary of the Interior must pass on the necessity for the loan. Applications should be addressed to James Boyd, acting deputy administrator, Defense Minerals Administration, Department of the Interior, Washington, D.C. rather than to the Field Offices of the Bureau of Mines as was first planned. Application forms are not yet available but it has been learned that data accompanying the application should include the known quantity and grade of reserves, the anticipated rate of production, the equipment, supplies, and man power required for the additional production, etc.

Jan 12, 1950

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult's law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and' oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1'2 The PbO-SiO2 melts are ionic conductors.' During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By P. W. Bridgman

FLOW and fracture are admittedly complicated phenomena of which we are yet only partially masters. There is not even universal agreement as to the details of the language best adapted merely to describe the phenomena, to say nothing of any theory. Certain points of view, however, are widely held, and there are certain general expectations as to what sort of procedures will prove permissible. A complete description of any situation involving fracture would demand a complete history of all the variables in the control of the experimenter. The experimenter endeavors so to choose his independent variables that they are adequate to determine completely the situation in the sense that when an experiment is repeated on the same initial material and with the independent variables running through the same sequence, all the other measurable properties of the system will also run through the same course. It is, I think, the universal conviction that when we are dealing with phenomena of flow and fracture, the most important of the necessary variables are the external forces acting on the various parts of the body; when the force history repeats, with certain obvious restrictions such as that temperature must be constant and non- mechanical forces, such as magnetic field, must be small enough to be ineffective, then the history of all measurable properties will repeat; in particular the alteration of geometrical shape due to flow will run through the same course, and when fracture comes, the character of the fracture will be reproduced. Complete mastery of merely the descriptive aspects of flow and fracture would demand the ability to predict the entire course of flow and complete characterization of the final fracture for every possible combination of forces, varying in time in all possible ways, when applied to bodies of all possible shapes. This full situation is obviously of prohibitive complexity. The first stage in reduction to manage- able simplicity is to resolve the total situation into the sum of contributions made by small elements. Our thesis is that if each of the elements is adequately characterized, the behavior of the whole system is fixed. The element is usually taken of a simple geometrical shape, suggested by the mathematics best adapted to the particular situation. The forces acting across the faces of the elements are ultimately determined by the forces acting across the free faces of the whole system. The detailed process of finding the precise forces on the faces of all the elements in terms of the external forces involves the use of a special mathematical invention, the stress, a constructional quantity consisting of six components. The stress at any point in the body is determined by both the external force system and by the physical properties of the body at all points; quite different stresses prevail at the interior of bodies of the same shape under the same external forces in the elastic and plastic ranges. The forces on the faces of any element are, however, uniquely determined by the stress system at the element. Our fundamental thesis

Jan 1, 1944

By W. L. Zeigler

During the middle 1880's, shortly after the discovery of silver-lead ores in the Coeur d'Alene district of northern Idaho, it became apparent that concentration of the ores would be necessary to obtain a profitable product. Too much siliceous material was present for direct smelting, and the majority of the ores found at depth were too low in metallic content for economic smelting processes at the time. As the ores occurred in quartzite shear zones with siderite and quartz gangue, a large quantity of waste material was present in all the mines. As the galena was not finely disseminated, this made possible relatively good extraction of the argentiferous galena by coarse concentration. The first concentrators consisted mainly of coarse crushing, screening and jigging, principally by Harz jigs, the slimes being treated on buddles. Later Wilfley tables took the place of sand jigs and vanners superseded the buddles. Because of the marketing conditions, no attempt was made until 1900 to effect a recovery on the zinc minerals present, which were found associated in varying amounts with the galena. All through this period, the greater part of the production was obtained from mines containing ore assaying high in lead and low in zinc. Parts of some ore bodies would be reversed in this respect, so that ores high in zinc were left intact. During the decade after 1910, several important mines, The Success and The Interstate Callahan, containing ores high in zinc, were put into operation and were a material aid in the needed zinc production during World War I. Gravity concentration by jigs and tables was used during this period, with bulk flotation increasing in popularity for the treatment of the fine material that had already been treated by ordinary slime concentrating machinery. No extra fine grinding for flotation concentration was thought profitable at the time. Tailings Discharged into Streams From the start of mining and milling operations in this district until 1904, no attempt was made by the various mills in the upper district to impound or stack their tailings. They discharged them directly into the adjacent creeks or streams, to be carried away by high water. The Bunker Hill and Sullivan and the Last Chance mines, both in the relatively flat valley of the district, stacked huge piles of the coarse jig tailings on the near-by river bottom. Rain and snowfall are heavy in the Coeur d'Alene district, as it is on the heavily timbered Pacific slope of the Bitter Root Mountains. A heavy runoff occurs every spring and there is an occasional flood of disastrous proportions when warm "Chinook" winds accompanied by rain

Jan 1, 1949

By H. L. Brunjes, G. B. Gould

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By G. B. Gould, H. L. Brunjes

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

The opening session of the Institute was held at the rooms of the American Society of Civil Engineers, No. 4 East 23d Street, VicePresident R. W. Raymond in the chair. After a short introductory address by the chairman, the following names were presented by the Council for election as members and associates of the Institute. They were unanimously elected : MEMBERS. Abbott, James W.,.....Lake City, Col. Abbott, J. J., Jr.,...... Lake City, Col. Bartlett, J. C.,.....Cambridge, Mass. Billings, G. H.,.....Boston, Mass. Blake, Frank C.,.....Lafayette College, Easton, Pa. Dewey, Fred. P.,.....Lafayette College, Easton, Pa. Douglass, Samuel T.,. .. . Ann Arbor, Mich. Emmons, 9. F.,.....New York City. Engle, George U.,.....Philadelphia. Harrington, Dr. Bernard J.,. .. Montreal, Canada. Hayden, Wm. B.,.....Columbus, O. Hill, Leslie C.,.....Capelton, Quebec, Canada. Land, W. J.,......Atlanta, Ga. May, Wm. A.,.....Scranton, Pa. Mills, James E.,.....St. Louis, Mo. Moore, Charles W.,.... Montezuma, Ind. Page, William Byrd,.... Lexington, Ky. Putnam, Douglas, Jr.,.... Ashland, Ky. Richards, Henry,.....Dover, N. J. Boberts, Percival, Jr.,. .. . Philadelphia. Sackett, S. G.,......Brooklyn, N. Y. Schley, Wm. S.,.....Atlanta, Ga. Setz, Gustav,......Mine La Motte, Mo. Talhutt, John H.,.....Lexington, Ky. Torrey, Herbert G.,.... U. S. Assay Office, New York City. Wernlitz, Fred. W.,..., Cartersville, Bartow Co., Ga. Wiestling, Geo. B.,.....Mont Alto, Franklin Go., Pa.

THE opening session of the Institute was held at the rooms of the American Society of Civil Engineers, No. 4 East 23d Street, Vice-President R. W. Raymond in the chair. After a short introductory address by the chairman, the following names were presented by the Council for election as members and associates of the Institute. They were unanimously elected : MEMBERS. Abbott, James W., - Lake City, Col. Abbott, J. J., Jr., - Lake City, Col. Bartlett, J. C., - Cambridge, Mass. Billings, G. H., - Boston, Mass. Blake, Frank C., - Lafayette College, Easton, Pa. Dewey, Fred. P., - Lafayette College, Easton, Pa. Douglass, Samuel T., - Ann Arbor, Mich. Emmons, S. F., - New York City. Engle, George U., - Philadelphia. Harrington, Dr. Bernard J., - Montreal, Canada. Hayden, Wm. B., - Columbus, O. Hill, Leslie C., - Capelton, Quebec, Canada. Land, W. J., - Atlanta, Ga. May, Wm. A., - Scranton, Pa. Mills, James E., - St. Louis, Mo. Moore, Charles W., - Montezuma, Ind. Page, William Byrd, - Lexington, Ky. Putnam, Douglas, Jr., - Ashland, Ky. Richards, Henry, - Dover, N. J. Roberts, Percival, Jr., - Philadelphia. Sackett, S. G., - Brooklyn, N. Y. Schley, Wm. S., - Atlanta, Ga. Setz, Gustav, - Mine La Motte, Mo. Talbutt, John H., - Lexington, Ky. Torrey, Herbert G., - U. S. Assay Office, New York City. Wernlitz, Fred. W., - Cartersville, Bartow Co., Ga. Wiestling, Geo. B., - Mont Alto, Franklin Co., Pa.

Jan 1, 1877

By Frank Van Horn

INTRODUCTION IN June, 1911, the writer spent a few days in studying the economic geology of the vicinity of Park City. During this rather hurried visit a number of specimens of ore were collected, which have since been examined. The results of these investigations show that bournonite (PbCuSbS3) is present in the ores in greater or less quantity. This fact has never before been reported, as far as can be learned. The failure to recognize this mineral is due to its similarity to tetrahedrite, with which it has probably been confused during a long period of years. Jamesonite (Pb2Sb2S5) has been reported from the region in a rather doubtful manner, but the writer has seen it in notable amounts from several mines, and can offer the first analysis of this mineral from the district. Calamine (H2Zn2SiO6) was found at one mine and has never been recognized and reported from the district.

Jan 8, 1914

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By L. H. Robinson

Triaxial compression tests on Indiana limestone indicate that chemical additives in the pore fluids can increase or decrease the strength in plastic failure but not in brittle failure. Tests using a series of the sodium salts of dicarboxylic acids show that odd-number carbon-atom chains decrease the yield strength as much as 3.0 x 10 3 psi, and even-number carbon-atom chains increase the yield strength as much as 9.0 x 102 psi. ,The most effective chemical (sodium citrate) decreased the yield strength of Indiana limestone from 16.0 x 103 to 12.0 x 103 psi. The chemical additives investigated have no influence on microbit drilling rate when drilling with zero differential pressure. However, when drilling at a 2.0 x 103-psi pressure differeniial and using an odd-number carbon chain compound as the circulating fluid, the roller bit drilling rates were slower than with water whereas the drag bit drilling rates were faster. One even-number carbon chain compound added to the circulating fluid produces the opposite effect: the roller bit drilling rate is slightly faster than with water and the drag bit slower than with water. INTRODUCTION A Russian book by Rehbinderl published in 1944 generated much interest in the possibility of aiding and accelerating the destruction of solids by the action of a liquid in which the solids are deformed. This book describes a process in which microcracks are generated during elastic deformation. To describe this process, the rock is divided into three zones: (1) the zone in which the destruction takes place, (2) the predestruc-tion zone (an affected area immediately below the destroyed zone) and (3) the undisturbed specimen. Consider a load applied normally to a surface of an infinite slab of rock. Immediately below the point of application of the load, the rock is destroyed by compression or shear forces. Below this area of destruction, because of a great number of discontinuities ranging from defects to weak points in crystals of discontinuities in crystal latices, very small cracks are created in or between the crystals (often referred to as microcracks). Upon removing the load, the broken rock in the destroyed zone could be removed. In the lower predestruction zone, however, the microcracks in and between the crystals could disappear by the process of rehealing, i.e., the molecular attraction from one side of the crack to the other side being sufficient to completely eliminate the crack. Thus, a large number of these microcracks possibly exist only for a relatively short period of time. The concept of small cracks being generated within the crystals of a rock is not unreasonable. If the rock matrix is deformed below the yield point, some of the defects present within the crystalline structure could start small cracks through the interior of the grains. Upon removal of the load, these microcracks reheal (or the newly generated surfaces come back together) so that all evidence of cracks completely disappears. Under various types of loading, and in various types of fluids, the rehealing of these cracks would be time dependent. If a liquid adhered to the surface of a rock, it could penetrate into the microcracks and thus delay or prevent the rehealing process. This suggests that the prevention of healing of the microcracks may be dependent upon the wetting characteristics of the solid. Thus, rocks which are water-wet should be more easily destroyed in water than in nonpolar hydrocarbon liquid. Adsorption of a liquid could also reduce the free surface energy which could explain the decrease in strengths of materials under nonrepetitive-type loading. Rehbinder's work prompted Boozer, Hiller and Serdengecti 2 to examine the effects of pore fluids on the deformation of rocks subjected to triaxial compression over a range of confining pressures, temperatures and strain rates. Fluids which strongly adsorbed on the rock grain surfaces decreased the strength of sandstone and limestone, which deformed plastically. For certain strain

By Joseph Cervik

INTRODUCTION Common methods of controlling gob gas in U.S. mines are by means of ventilation of gob areas and gas drainage through surface boreholes. Costs of drilling surface gob holes increase as deeper coal- beds are mined. Where gob holes cannot be drilled because of topography, ventilation is the only means of control. Even then, sufficient air may not be available to dilute methane in the bleeder entries to acceptable levels. Thus, new methods of gob gas control need to be developed that are independent of surface topography, and of the mine ventilation system, and less costly than present systems. Except for slight variations in procedures and equipment, Great Britain, West Germany, France, Belguim, Poland, and Czechoslovakia use a common methane control method that is different from the system generally used in the United States. This Bureau of Mines paper reviews European mining methods, mining conditions, and methane control technology and discusses their applicability to U.S. mines.

Jan 1, 1981

By B. T., Colley

AS always when metallurgical operations are conducted within or close to agricultural and stock-raising regions, the question of damage due to fume and smoke presented itself when the Cerro de Pasco Copper Corporation's new smelter commenced to operate in La Oroya in 1922, For more than twenty years the Corporation had operated its old plant close to Cerro de Pasco without encountering difficulties from smoke claims, owing to the fact that it was in an open plain where more or less constant air currents carried and dissipated the smoke over large areas, affording ample dilution. But Oroya is in a deep canyon formed by four contributing valleys up and down which the smoke travels for long distances in a more or less concentrated form. Though the altitude of Oroya is more than 12,000 ft., and the surrounding country rises to much greater elevations, nevertheless there exists there a large and important stock-raising industry and also a considerable development in agriculture, consisting of the cultivation of potatoes, barley, etc.

Jan 1, 1945

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

The nickel suppliers are hard at work across the entire spectrum of the industry-from exploration and mining on the one hand to the development of new applications of this unique metal on the other. The reason-a surging demand for nickel by the free world. Evidence of interest and activity in nickel abounds. Companies such as Anaconda, American Metal Climax, Kaiser Aluminum & Chemical, Patino, Newmont-firms that have not been in the nickel industry before-are now involved in various exploration and development ventures around the world. International Nickel, Falconbridge, Le Nickel and Sherritt Gordon-the big names in the industry -have committed vast sums of money and talent in a variety of new developments designed to ensure their status as leading producers of this commodity. As a result, the world is now seeing a rapid build- up in nickel capacity, and in this issue of [ ], the editors have prepared a summary of these fast- moving major developments.

Jan 10, 1968

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

(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, indicated by a *. A complete list was published in the Year Book, issued as a supplement of the Bulletin for March, 1918.) ANDERSON, AMIL A., Co. A, 309th Regiment Engineers, 84th Div., American E. F., Care Postmaster, New York. ARMSTRONG, HAROLD K., Pilot, Naval Aviation, U. S. Naval Air Station, Miami, Fla. BASSETT, ARTHUR F., Co. 6, -E. 0. T. S., Camp Humphreys, Va. BEDDALL, THOMAS H., Adjutant, 1st Battalion, 1st Gas Regiment, American E. F. BERNARD, CLINTON P., Candidate, 12th Observation Battery, F. A. C. 0. T. S., Camp Taylor, Ky. BROOKE, LIONEL, 50th Co., 13th Battalion, 5th Replacement Engineers, Camp Gordon, Ga. BROWNING, EDWARD, Corp., 1st Regiment Engineers, Co. D, American E. F. BUGBEE, EDWARD E., S. A. T. C. Headquarters, Raleigh N. C. BUTTERFIELD, G. BRUCE, CO. C, 605th Engineers, American E. F. CADOT, J. J., 1st Lieut., U. S. Air Service, American E. F., Care Post- master, New York. CARLOCK, J. B., Major, 2d Battalion, 1st Gas Regiment, American E. F., France.

Jan 12, 1918

By H. H. Stout

In the early fall of 1925, the writer was conducting, in the Ledoux and Co. laboratory, New York, experiments directed toward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various different gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500º to 1600ºF. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode particles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500ºF." Smoot's reaction, after a few moments considera- tion, was, "It looks perfectly all right to me.'' The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after conferring as to ways and means, decided to go ahead with preliminary laboratory experiments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: 1. Since brittle cathodes were often unintentionally produced, it seemed probable that the laws controlling this type of deposition could be ascertained. 2. We had already proved the gas-cleaning feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia University for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrouilded and heated by a resistance coil 01 Nichrome wire. Broken tough cathodes were used. Experimental Procedure The first run took place March 18, 1926. The resistance wire gave out when temperature of 1000ºF. was obtained. Pressure was immediately applied: perceptible ram movement stopped when 39,000 lb. per sq. in. on the copper was reached, with a maxi-

Jan 1, 1941

By Harold V. Pearce

(Chattanooga Meeting, October, 1908.) THE fire which occurred in the fall of 1906, at the works of the Boston & Colorado Smelting Co., Argo, Colo., destroyed entirely the gold- and silver-refinery of the plant; and in view of the development of modern practice in the refining of copper-mattes, etc., the management decided that it would be inadvisable to rebuild that part of the works for the continued use of the process which had been conducted therein for so many years as a metallurgical secret. This decision probably removes altogether from the sphere of practice the " Pearce " method for the separation of gold. At all events, it removes the business reasons which have prevented hitherto the publication of the principles involved. At the suggestion of Dr. Raymond, Secretary of the Institute, my father, Richard Pearce, the former manager of these works, has requested me to prepare a brief description of this process for the benefit of our members. Since I severed my connection with the Boston & Colorado Smelting Co. some time ago, I am indebted for some practical details to the present superintendent, Charles Rees, whose friendly assistance I would gratefully acknowledge. With regard to the history of the inception and development of this process by its inventor, Richard Pearce, I cannot do better than quote freely from his own notes and papers. HISTORY OF THE PEARCE PROCESS.' "In 1874 my entire time was directed to the improvements and additions to the plant at Black Hawk. The changes which I had made in the construction of the furnaces at Black Hawk proved so beneficial that I was requested to introduce the improvements at the branch works at Alma. These changes were carried out as speedily as possible, and proved of great advantage as compared with the old system. "The separation and refining of the gold from the matte now engaged my attention, and since previous experience in the treatment of gold-bearing matte and

Feb 1, 1909

The General Electric Co., in cooperation with the Montana School of Mines and under a research grant from the Anaconda Co., is presently experimenting on a new non-explosive method of breaking rock with radio-frequency electrical power. The method is known as electrothermal forcing. It must be understood that present equipment has not been designed to perform primary blasting functions. Its conceived use will be restricted to small pieces of rock too large to pass through a chute or grizzly. However, even this use is still far in the future. Experiments to date have been limited mostly to rock smaller than 18 in.

Jan 11, 1961