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By Alfred H. Hesse, Edwin T. Myskowski

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By N. P. Peterson

The Castle Dome copper deposit is of the porphyry type and occurs in a body of quartz monzonite intruded into the pre-Cambrian formations and possibly into the lower part of Paleozoic limestones. The hypogene sulphide minerals include pyrite, chalcopyrite, and a little molybdenite, sphalerite, and galena. Pyrite and chalcopyrite are disseminated or occur in small closely spaced veins. The hypogene mineralization shows distinct zoning in the distribution of pyrite and chalcopyrite, so that the mineralized area can be subdivided into pyritc and chalcopyrite zones. Supergene enrichment, though not extensive, played an important part in the formation of the ore body, the chalcopyritc zone being the pro-tore. Several thin, gently dipping, diabase sills occur in the mineralized area, and the copper content of the rock in and near these sills is substantially higher than average. The formation of the ore body was caused by the combined effects of three forces: I. Zoning of the hypogene mineralization, 2. Richer copper metallization associated with the diabase sills, and 3. Supergene enrichment. Introduction The Castle Dome copper deposit is about 5 miles west of Miami, Arizona, and about 3 miles west of the Miami-Inspiration ore body. The Castle Dome open-pit mine is on the south flank of Porphyry Mountain, a prominent landmark of the region. In 1941 the deposit was being explored by the Miami Copper Co., but the exploration program was cut short when the decision was made to develop the property as a war project. The Castle Dome Copper Co., Inc., was organized as a wholly owned subsidiary of the Miami Copper Co., and arrangements were made with Defense Plant Corp. for developing and equipping the mine and for construction of a concentrating plant. Construction and development work was begun in January 1942, and milling operations started June so, 1943. Since that date, the mine has been in continuous operation by the Castle Dome Copper Co, under a lease agreement with Defense Plant Corp. producing copper at an average rate of 4,000,000 lb per month. To January I, 1946 the total production amounted to 121,088,000 lb of copper,4,271 oz of gold, and 211,755 oz of silver. A detailed study of the copper deposit and the surrounding area was undertaken by the U. S. Geological Survey in June 1943. Other members of the Survey participating in the work were C. M. Gilbert, G. L. Quick, and J. P. Albers. The results of this work will be published as a comprehensive report by the Geological Survey. General Geology The Globe quadrangle, which includes the Castle Dome area, was studied by F. L. Ransome1 of the Geological Survey in 1901 and 1902. His maps and descriptions were

Jan 1, 1949

By N. P. Peterson

The Castle Dome copper deposit is of the porphyry type and occurs in a body of quartz monzonite intruded into the pre-Cambrian formations and possibly into the lower part of Paleozoic limestones. The hypogene sulphide minerals include pyrite, chalcopyrite, and a little molybdenite, sphalerite, and galena. Pyrite and chalcopyrite are disseminated or occur in small closely spaced veins. The hypogene mineralization shows distinct zoning in the distribution of pyrite and chalcopyrite, so that the mineralized area can be subdivided into pyritc and chalcopyrite zones. Supergene enrichment, though not extensive, played an important part in the formation of the ore body, the chalcopyritc zone being the pro-tore. Several thin, gently dipping, diabase sills occur in the mineralized area, and the copper content of the rock in and near these sills is substantially higher than average. The formation of the ore body was caused by the combined effects of three forces: I. Zoning of the hypogene mineralization, 2. Richer copper metallization associated with the diabase sills, and 3. Supergene enrichment. Introduction The Castle Dome copper deposit is about 5 miles west of Miami, Arizona, and about 3 miles west of the Miami-Inspiration ore body. The Castle Dome open-pit mine is on the south flank of Porphyry Mountain, a prominent landmark of the region. In 1941 the deposit was being explored by the Miami Copper Co., but the exploration program was cut short when the decision was made to develop the property as a war project. The Castle Dome Copper Co., Inc., was organized as a wholly owned subsidiary of the Miami Copper Co., and arrangements were made with Defense Plant Corp. for developing and equipping the mine and for construction of a concentrating plant. Construction and development work was begun in January 1942, and milling operations started June so, 1943. Since that date, the mine has been in continuous operation by the Castle Dome Copper Co, under a lease agreement with Defense Plant Corp. producing copper at an average rate of 4,000,000 lb per month. To January I, 1946 the total production amounted to 121,088,000 lb of copper,4,271 oz of gold, and 211,755 oz of silver. A detailed study of the copper deposit and the surrounding area was undertaken by the U. S. Geological Survey in June 1943. Other members of the Survey participating in the work were C. M. Gilbert, G. L. Quick, and J. P. Albers. The results of this work will be published as a comprehensive report by the Geological Survey. General Geology The Globe quadrangle, which includes the Castle Dome area, was studied by F. L. Ransome1 of the Geological Survey in 1901 and 1902. His maps and descriptions were

Jan 1, 1949

By Edwin T. Myskowski, Alfred H. Hesse

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,' see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in Cali- fornia, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War 11. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eight-man crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on." Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1953

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,' see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in Cali- fornia, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War 11. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eight-man crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on." Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1953

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon'-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -' and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960

A SPRING meeting is to be held at Cleveland this month under the joint auspices of the Iron and Steel Committee and the Ohio Section with the cooperation of the neighboring sections in Pennsyl-vania, Illinois, and the other States of the Great Lakes region. The discussions will be focused on just one subject, that of manganese, but will cover that thor- oughly as is indicated by the following list of papers. TECHNICAL PROGRAM Some Political Aspects of the World Manganese Situa-tion. By C. K. Leith, Professor of Geology, Uni-versity of Wisconsin, Madison, Wis. Manganese Resources in Relation to Domestic Con-sumption. By J. V. W. Reynders, Consulting En-gineer, New York, N. Y. Manganese Deposits of the' Gold Coast, Africa. By Sir Arthur E. Kitson, Director of the Geological Sur-vey of the Gold Coast, London; with Notes on the Petrology of Certain Associated Manganese Silicate-bearing Rocks. By Maj. N. R. Junner. Reserves of Lake Superior Manganiferous Iron Ores. By Carl Zapffe, Manager, iron ore properties, North-ern Pacific Railway Co., Brainerd, Minn. Iron Manganese Alloys Low in Carbon. By. Sir Robert Hadfield, Hadfields, Ltd., London. Manganese in Non-ferrous Alloys. By M. G. Corson, Consulting Engineer, New York, N. Y. Importance of Manganese in the Steel Industry. By H. M. Boylston, Professor of Metallurgy, Case School of Applied Science, Cleveland, Ohio. Minnesota Manganiferous Iron Ore in Relation to the Iron and Steel Industry. By T. L. Joseph, E. P. Barnett and C. E. Wood of the North Central Min-ing, Experiment Station, U. S. Bureau of Mines, Minneapolis, Minn. Representatives of the leading steel companies, the Army, the Navy, the Geological Survey, Bureau of Mines, and leading technical societies will be present and a lively discussion of the various papers is already assured. Nearly 14 pounds of manganese is needed for every ton of steel made. Estimates indicate that the total reserves of ore in this country suitable for making ferro would hardly supply domestic requirements for ten years, even if it could all be mined in that time. The grade of ore called for by present practice must come from abroad. The present tariff policy of this country is stated to cost industry $8,000,000 in order to force production of manganese ore to the extent of $600,000. What is the wise thing to do? Should a stock be accumulated? If so, how? Is it feasible to change practice and use low-grade ore or to beneficiate the ores of this grade and meet our requirements? What progress is being made in this direction? ,These and similar questions are raised in the various papers that have been submitted and will be open for dis-cussion.

Jan 3, 1927

By Robert W. Elayer

In August 1973, Fluor Utah, Inc. was awarded a contract by the Office of Coal Research (now part of the Energy Research and Development Administration), Department of the Interior, for the examination of the unique problems of large-scale surface coal mining to supply coal conversion complexes. The project consists of two phases: (I) data base development and organization and the formulation of a mathematical computer modeling system for surface mining; and (II) computer manipulation of the data base in accordance with the model to formulate several typical preliminary mine and preparation plant designs. Phase I is scheduled for completion by the end of July 1975 and Phase II is scheduled to be complete by the end of January 1977. This paper briefly discusses the effort for only one aspect of this project-the foundation for geologic modeling developed in Phase I. The Phase I task of geologic modeling can be broken down into two subtasks: (1) identify areas containing sufficient resources of surface-minable coal to support at least one large-scale mining complex, and (2) characterize the coal deposits in these areas for computer storage and retrieval. Identification of Resource Regions The basic production design criteria for large-scale surface mining, as stated in the contract, is the production of 75,000 tpd, or more, of bituminous coal. Based on a constant total Btu delivered to the preparation plant, daily production requirements for the different coals are as follows: Bituminous Coal 75,000 tons Subbituminous Coal 99,500 tons Lignite 143,500 tons Although surface mining on this scale is presently non-existent, it is deemed that future operations, in order to meet the increased energy demands, will have to look forward to much larger scale mining complexes. These tonnage requirements are meant to be used only for the delineation of general areas suitable for large-scale surface mining, termed "Strippable Coal Resource Regions." They were determined largely from the latest complete detailed coal resource estimates of the U.S. Bureau of Mines. Nine strippable coal resource regions, containing over 100 billion tons of strippable coal resources, were identified [(see Fig. 1)]. The delineation of these regions was based entirely upon estimates of surface-minable coal resources and the production design criteria for large-scale surface mining. If surface-mined coal was combined with underground production, or if smaller production rates were specified, then other areas which were omitted here would be included in the regions. Changing the outline of the regions, however, would not add any new mining situations to be studied in Phase II. Characterization of Coal Deposits The second subtask involved the general characterization of the coal deposits contained in the strippable coal resource regions. The geological information gathered

Jan 1, 1976

By D. K. Deardorff, Haruo Kato

D. K. Deardorff and Haruo Kato (U. S. Bureau of Mines)—We wish to refute the 1875" 20°C value that Giessen, et al., report as the transformation temperature of hafnium. Although these authors state that their work along this line will be reported later, we can't leave their value undiscussed, for we believe it to be 125°C too high. Our value of 1750° 20°C, which the authors mention, has been substantiated in our laboratories by the use of three other methods. The first method of substantiation was by heating and cooling curves using a hafnium/tungsten thermocouple, the couple having first been calibrated against a t/Pt-10 pct Rh couple. The second method was by quenching and metallography of dilute Hf-Ta alloys. The third cussion, it may be pointed out that the observations of Rogers referred to large unidirectional strains where the internal cracks or voids appeared only after a strain of 32 pct or more. On the contrary the internal fissures observed, as a result of fatigue cycling, occurred for a total extension of some 5 pct and furthermore followed the directions of the slip zones. Finally, it is not our contention, as implied in Dr. Alden's last paragraph, that the tensile stress is an important factor in crack propagation. Indeed, in connection with the reference to the companion report, special note is made of the fact that "Deformation was apparently concentrated in grains which have a slip plane nearly perpendicular to the specimen axis and thus near the plane of maximum applied shear." This dependence of the growth of fissures on the orientation of the slip planes with respect to the direction of maximum applied shear is clearly shown in work on the torsional cycling of single crystals which has been submitted for publication. method was by heating and cooling curves with W/W-26 pct Re thermocouple. Counting the original resistometric method, four different methods have yielded 1750" 20°C as the transformation temperature of hafnium. All our work on determination of the hafnium transformation temperature has shown that the specimen under test must be quickly heated to and through the transformation temperature if the lowest possible transformation value is to be determined; otherwise a higher value not representative of pure hafnium will result. Speed was emphasized in all methods. In our resistometric work the corresponding voltage, amperage, and temperature readings were taken quickly and the transformation temperature was usually reached within 5 min total heating time. In the thermal analysis work involving Hf/W or W/W-26 pct Re thermocouples the transformation temperature was attained within three minutes total heating time, this time being less because the two variables were

Jan 1, 1963

By Joseph E. Worthington

Many thousands of years ago when our earliest ancestor first swung out of a tree, picked up a rock, and threw it at what he hoped might be his lunch, the minerals industry, in a manner of speaking, was born. It was then a very long step indeed to the primitive metal industry of our early civilizations, for we know that precious metals were accumulated and some metal objects were produced several thousand years ago. Prospecting, or "exploration" to use the modern euphemism, consisted of little more than outcrop examination and the use of a gold pan, and it probably did not change much from our earliest civilizations until relatively recent times. In a general sense, all the early explorers of North America were also prospectors, for mineral wealth was certainly one of the goals of the first pioneers and settlers. The earliest pioneers didn't do too badly either, for they discovered copper and iron in various places in the Appalachians and Michigan, gold in the Southeast Piedmont and many mineralized areas in the Southwest. In most places these were outcropping ores or gossans, and the prospecting was incidental to the arduous task of ekeing out a living in a new land. It was the explosive discovery of rich placer gold deposits at Sutter's Mill in California that caught the public fancy and precipitated the establishment of prospecting as a full-time occupation. After the end of the Civil War in 1865, full-time prospecting became an important occupation and continued as such for almost three generations. Prospectors equipped with picks, shovels, gold pans and four-footed transportation swarmed all over what are now our Western States, discovering thousands upon thousands of mineral showings-and certainly most of today's large mining districts. Our vigorous western mining industry is a tribute to the courage and persistence of these men. The techniques of these picturesque prospectors, however, were essentially the same as those of their predecessors-examination of every outcrop and assiduous use of the gold pan. The great increase in discovery at this time was therefore due to increased activity rather than to different techniques. An important result of this in- creased prospecting was the growth of interest in geology. It was during this period that the U.S. Geological Survey began to grow. Many of the major mining districts were mapped, and geological studies and projections began to have an impact on further ore discovery. Ore search and development gradually became more geologically oriented and the geologist became a fixture in most mining camps by the 20th century. The development of mass-mining techniques in the early part of the century also changed exploration concepts.

Jan 1, 1971

By C. P. Kempter, H. L. Brown

Recently Chang determined heat content values of tantalum monocarbide and tungsten monocarbide from 325" to985°Kand 326" to 912"K, respectively, and, using other published data, made certain solid-state calculations for these two compounds. Chang expressed his Cp values in units of cal per "g-atom alloy" OK. We consider this poor usage since l) tantalum monocarbide and tungsten monocarbide are not alloys, and 2) an atom of an alloy does not exist. However, one may convert his values to units of cal per mole OK by merely doubling them. For TaC he calculated a Nernst-Lindemann parameter of 9.07 x lo-' "g-atom per cal". We have refined the calculation of this parameter and have arrived at a much lower value. Rather than approximating the true coefficient of volume expansion, a,, as three times the true coefficient of linear expansion, a, we calculated u, from the TaCo.99, lattice expansion data of Fries and Wahman.38 At 25°C a, = 14.3 x 10s per OC. The molar volume was calculated to be 13.32 cu cm per mole at 25°C. From the lattice compression data of Champion and Drickamer~' for "TaC,.,," we determined the room-temperature compressibility to be 3.5 x 10-l3 sq cm per dyne by plotting l/Vo (aV/ap) vs applied pressure. (Since the lowest pressure at which Champion and Drickamer reported a relative volume was 20 kbars, one may calculate an approximate compressibility only. Chang calculated a compressibility of 3.175 x 10-l3 sq cm per dyne from the same data.) We also used twice Chang's value of Cp = 4.38 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated a Nernst-Lindemann parameter of 5.8 x 10-l4 mole per erg or 2.4 x lo- ' mole per cal, and a Cdil value of 2.3 x 10' ergs per mole OK. In the case of tungsten monocarbide no isothermal compressibility has been reported; however, one may calculate an approximate Nernst-Lindemann parameter by using the adiabatic compressibility reported by Brown, Armstrong, and Kempter." Using the WC lattice expansion data of Mauer and Bolz~l we calculated a, to be 12., x l0-' per OC. The molar volume was calculated to be 12.5 cu cm per mole. We used twice Chang's value of Cp = 4.18 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated an approximate Nernst-Lindemann parameter of 2 x lo-' mole per cal, which is much

Jan 1, 1969

By J. K. Stanley

It has been known for many years that the magnetic properties of a ferromagnetic material are very sensitive to internal strain. Any structure-sensitive property such as ferromagnetism, which is a function of the regularity of the atomic arrangement, and discontinuities such as grain boundaries must show deviations from an equilibrium state when the regularity of the lattice is disturbed. Experience has shown that such distortions have a marked effect on the magnetic properties of a ferromagnetic material. The purpose of this paper is to show the feasibility of using magnetic methods in detecting internal strains. More specifically, it will be shown how such properties as permeability, rema-nence, and coercive force change on cold-working of aluminum iron and how these magnetic properties change during the annealing below the recrystallization temperatures. This work was conducted for two reasons. One was the desire to see in what manner strains are relieved in aluminum iron at low temperatures—a subject of practical importance in soft magnetic materials—and the other was the feeling that a study of cold-working and strain relief might shed some light onour understandingof what takes place in the deformation of metals. Definition of Terms It is necessary to define the terminology used in this Paper because magnetic nomenclature is usually unfamiliar to the metallurgist, and certain other terms, such as recovery, have been used ambiguously by metallurgists and others. Magnetic terms are best explained by reference to the common hysteresis loop of ferromagnetic materials (Fig. I). In Fig. 1 the coordinates are magnetic induction, B, (ordinate) and magnetizing force, H. (abscissa). The c.g.s. unit for the magnetic induction is the gauss, the number of flux lines per square centimeter, and the unit for the magnetizing force is the oersted, the number of lines of force per centimeter in air or vacuum. If one starts with a completely demagnetized specimen and magnetizes it, a typical virgin magnetization curve beginning at the origin is obtained. This curve is also the locus of tips of a family of smaller hysteresis loops. From this curve it is to be noted that the induction is not proportional to the magnetizing force, and that it appears to approach a limiting induction called the saturation value, and does so for values of H of 1000 oersteds. The ratio of the magnetic induction (gauss) to the magnetizing force (oersteds) is called permeability, . Thus u= B/H and if the magnetizing force H (oersteds) is specified as ro or 100 oersteds, the permeability is written as or l00 This is the accepted notation, and will be used in this paper. The values of permeability for H = 10 or I00 are chosen as indices for 106

Jan 1, 1945

By S. Froes

Official daily output of the Reconcavo (Bahia) oil fields, which amounted to 300 bbl., increased by the end of 1944 to 500 bbl. The new productive wells are in the district of Candeias. This figure is expected to further increase during 1945. The Itatig Company, which had drilled five wildcats in the state of Sergipe, stopped in 1944, but intends to resume work during the current year, or as soon as the war is over, in order to try the Cretaceous areas around its salt deposits. Several concessions applied for in the states of Sao Paulo, Parana arid Santa Catarina were favorably considered by the Conselho Nacional de Yetroleo, which is interested in fostering prospecting activities in the country. Several national groups are interested in exploring the federal gas field of Aratu (Bahia), a proposal having been made to use the gas in the manufacture of Portland cement. Undoubtedly the most important fact in the 1944 activities was the visit by two outstanding petroleum geologists, who had the opportunity to examine some of the principal areas and reported their opinions to the Brazilian Government. By special courtesy of the U. S. Government, Mr. E. DeGolyer spent a few weeks inspecting the gas and oil fields of the so-called "Reconcavo" of Bahia (a large tract surrounding All Saints Bay, on whose shore lies the city of Salvador) Later he exchanged ideas with Colonel Joao Carlos Barreto, President of the Conselho Nacional de Petrolco, as to the most adequate measures to develop production. Considering the oil problem in the southern part of Brazil, in the sedimentary belt including formations from the Devonian to the Triajsic, Mr. DeGolyer suggested a visit there by Mr. Lemis MacNaughton. The latter traveled during the months of June, July and August, accompanied by Brazilian geologists Avelino de Oliveira, Vice-president of the Conselho Nacionial de Pctroleo, Pedro Moura, Annibal Bastos, Burdot Dutra and J. Felicissimo, and verified the actual possibilities of the region, thus confirming the opinion of Pedro Moura, Avelino de Oliveira and Froes Abreu as to the advisability of thoroughly prospecting the south of Brazil. It is to be hoped that on the recommendation of these proficient American experts the Brazilian Government will take the necessary measurcs to carry out a complete search 01 such areas, which hitherto have been unsuccessfully drilled because knowledge of the structure was not adequate. The old Government policy of monopolistic essence has now given way to the more enlightened tendency of reconciling official action with private enterprise, which should in no way be curbed but rather encouraged. Such trend is heartily welcomed by financiers and technicians alike, who realize how indispensable is the cooperation of private capital, both national and foreign, in

Jan 1, 1945

By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly i00 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi¬tion is accompanied by a change in volume of as much as S per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potters have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to g0 per cent Mn. is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to ½ in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,1 see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in California, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War II. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eightman crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on.2 Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1952

By W. R. Seyfried

THE -problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations, An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper, The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reaent for re-use. THE PROCESS AS PLANNED In April 1941, a group of chemists and engineers of the Chemical Construction Corp, became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the Company, first drafted a process in July of that year-five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant, By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or low-grade bauxite would be roasted at 700 to 800°C (1292° to 1492°F). (b) The roasted ore would then be leached .with hot aqueous ammonium bisulphate to form a slurry. In this way the

Jan 1, 1948

By Frederick W. DeVries

Since we first agreed to present this talk we have learned that some of you may have been covering ground we intend to discuss: Bob Schechter, Daryl Tweeton, Don Seidel, Herb Burgman; however, the ideas were original when we began, "novel" as in the title of the talk, and whether our results are news or merely corroborative, we feel they point a direction that could be valuable to all. We worked with many of you in the past on using hydrogen peroxide in in-situ uranium leaching. Our talk today is not directly related to peroxide; it is, I hope, illustrative of Du Pont&apos;s interest in providing service to this industry in any way we can. The scouting work we are presenting was stimulated by field inputs: First, ammonium carbonate leaches cause restoration problems, primarily because ammonium ions exchange on clays with calcium. Second, sodium carbonate solutions, especially in South Texas deposits, can cause intolerable swelling of clays. From discussions with Dr. van Olphen, who wrote the book on clay chemistry, we inferred by comparison of the radii of the hydrated ions of the elements in these clay systems, that since potassium had about the same radius as ammonium, and sodium was much larger, potassium occupied a unique position to solve both problems. We have shown: FIGURE 1 Potassium bicarbonate systems leach uranium without loss of permeability found with sodium Potassium salts are very effective in restoring ammonia-leached sites Before reviewing the details of our work, which was performed by Hazen Research, Inc., I should like to stress its scouting nature. We are trying to assist the in-situ industry by pointing out new, potentially important directions. But, as with our previous work on sodium silicate to restore permeability, we feel the development phases can generally best be carried out in cooperative programs with companies directly involved with operations. DISCUSSION Test Parameters Now for the details: Our leaching tests were designed to note pressure-drop changes across the ore sample as the uranium was leached. Figure 2 shows the apparatus. The [ ] packed length was 20.5 inches (52 cm) with fifteen hundred grams of ore in the two-inch (5 cm)-diameter bed. Pressure drop was measured by manometer and feed rates were maintained constant with a tubing pump. The samples, from a South Texas leach site, were sealed in "Zip Loc" bags, frozen with "dry ice", crushed (still frozen) through six mesh, and blended before placement into the columns. The ores analyzed as shown here: FIGURE 3 Ore Analyses [Sample A Sample B U308 015% 0122% Mo 0004% 0086% Se0012% <0001% Fe3,078%076% Fee- 098% 044%]

Jan 1, 1979

By H. Le Chatelier

An evident connection exists between chemical and calorific phenomena: the most important, of our sources of heat, the combustion of coal, is nothing else than a chemical reaction. Not satisfied with this indefinite statement, investigators have attempted to establish a more precise correlation between these two orders of phenomena, and have questioned whether there be not a necessary connection between the possibility of a chemical reaction and the algebraic sign of the quantity of heat which it would call into play (i.e., liberate or absorb). This question possesses the highest interest for metallurgical chemists. But the study of it by experimental methods only could not completely elucidate it. To arrive at a definite solution, it was necessary to appeal to a science much more general than chemistry,—namely, that of energetics, which embraces all the physical sciences. We can place absolute confidence in its conclusions, because they rest upon a proposition which can scarcely be denied, namely, the impossibility of The main facts in the history of the development o‡ this field of Triassic coals have been already set before the Institute in the papers of Mr. Oswald J. Heinrich, a former member of the Institute and the superintendent of the mines at Midlothian. † From these and other references to the field, it appears that coal was known to exist here as early as 1701; for on the 10th of May that year Colonel Byrd reported to the Colonial Council of Virginia the discovery of coal. Coal was mined from 1770 to 1780; but the amount shipped is unknown. It was much used in Richmond at this early date for gratefires. In 1789 shipments were made to northern ports. During the first half of the century just passed, mining operations attained in this field their greatest development, the number and extent of the collieries and the tonnage of coal raised per annum being greater for that period than for any similar period since. The maximum annual output exceeded 100,000 tons, while in two years only since the Civil War has the amount of coal raised exceeded 50,000 tons. This field covers about 150 sq. in. Its outline and the position of the strata in which the coal-outcrops occur are shown on the accompanying map, reproduced from the latest survey by the U. S. Geological Survey. Mining has been carried on along the margins of the area, often in the primitive manner in vogue at the beginning of operations, by means of shafts and slopes, usually too small in cross-section to permit the proper working of the beds. Most of the output has been won from

Jan 1, 1902

By P. D. Hunt, I. Johnson, M. G. Chasanov, H. M. Feder

The solubilities of the transition metals from scundium to nickel, inclusive, in liquid cadmium were determined by sampling saturated solutions. At 400°C these solubilities (ppm) are:Sc, Co, 22; Ni, 12000. Relative partial molal enthalpies and excess partial molal entropies at infinite dilution for the solutes Cr, Mn, Fe, and Co are compared zoitlz similar data for the post-transition metals. Three new intermetallic phases, ScCd,, TiCd, and Ti,Cd, encozaztered in the course of this work, are reported. Measurements of the solubility of the 3-d transition metals in liquid cadmium have been reported&apos; only for iron. The present measurements for the entire series were made as an aid to the study of the systematics of alloy formation. EXPERIMENTAL The apparatus and sampling techniques used for the solubility determinations were similar to those described by Martin etal.&apos; Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple sheathed in recrystallized alumina and immersed in the solution. The thermocouple was recalibrated periodically during the course of the investigation. Thermocouple voltages were measured to the neares 0.01 mv with a Rubicon model 2732 potentiometer. A scaled-down version of the apparratus, in which the total metal charge was about 90 g, was employed to measure the solubility of scandium. Two-mm ID Vycor filter pipets were used to sample the scandium-cadmiurn solutions; the samples weighed about 2g- Cadmium with a minimum purity of 99.95 pct was used; the only impurities detected spectrochem-ically were C&apos;u and Mg, both less than 10 ppm. The purities of the other metals were: scandium, 99.9 pct; titanium. 99.92 pct; vanadium, 99.9 pct; chromium, 99).99 pct; manganese, 99.9+ pct; iron, 99.90 pct; cobalt, 99.95 pct; and nickel, 99.96 pct. Solidified melts were routinely analyzed spectro-graphically. No significant contamination by the crucible, sampling pipets, or other materials of construction was observed. The entire specimen obtained by sampling was dissolved to preclude analytical errors due to segregation on cooling. Colorimetric methods3 were used for the analyses of cobalt (2-nitroso-l-naphthol), manganese (permanganate), nickel (dimethylglyoxime), titanium (peroxide), and vanadium (thiocyanate).4 Chromium, iron, and scandium were neutron-irradiated to produce The dissolved samples were gamma-counted to determine solute concentration.For the separation of intermediate phases from cadmium-rich alloys selective leaching by saturated ammonium nitrate solutions was employed. The concentration of cadmium in the successive leaches was followed polarographically and the process was terminated when the rate of cadmium dissolution decreased markedly. For the further investigation of intermediate phases 1/4- in. diam powder compacts were pressed at 80,000 psi and annealed in argon at 315" to 330°C for 10 days. Larger quantities of alloys were prepared in sealed tantalum capsules heated in a rocking furnace.

Jan 1, 1962