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By Paul H. Price, John P. Nolting

The history of the salt industry in West Virginia dates back nearly two hundred years; howTever, the history of salt as an important raw material for the chemical industry is much more recent. The earliest record of West Virginia salt was in 1753, when a raiding party of Shawnee Indians attacked frontier settlements in Virginia taking captive a number of the pioneers. One of these, who later escaped and returned to her friends, described how the Indians camped at a salt spring on the banks of the Kanawha River and evaporated the water to obtain a supply of salt to take back to Ohio with them. Settlement of the Kanawha Valley began in 1774, that same year the Battle of Point Pleasant ended the Indian's power in the Ohio Valley; and settlement of the Kanawha Valley progressed rapidly with a consequent increase in the importance of the Kanawha Licks as a source of salt. In those days the evaporation of the brine was a family matter for which the family wash-kettle was commandeered. In 1797, Elisha Brooks erected the first salt furnace in the Kanawha Valley. It consisted of two dozen small kettles set in a double row, with a flue beneath, a chimney at one end, and a fire bed at the other. He obtained his brine at a depth of 20 to 30 ft by sinking hollow logs, called "gums" into the salt lick and dipping the brine with a bucket. His production was about 150 lb a day and sold for 8 to 10 cents a pound. In 1806, the Ruffner brothers, David and Joseph, prospected for and drilled the first well in America using a spring pole and steel chisel bit. After several failures they succeeded, in 1808, in drilling to a total depth of 59 ft where they secured a good flow of strong brine. Most standard drilling tools, jars, casing, and practically all the basic oil well drilling machinery now in use, were developed in the drilling of salt wells. To evaporate this brine, the brothers built a wood-burning furnace similar to that of Brooks but with a better arrangement and with more and larger kettles. When production was started they reduced the price of salt to 4 cents a pound. By 1817, there were some 30 salt furnaces in the Kanawha area. It was in this year that bituminous coal first was used as an industrial fuel. David Ruffner again pioneered the way by converting his furnace for the consumption of coal. This year also brought about the formation of the first trust which controlled production and set a price of 1 cent a pound for the salt.

Jan 1, 1950

By W. Seymour

Uranium was cold rolled to a reduction in thickness of 90 pct and the preferred orientation of the grains was determined from X-ray intensity data. Complete pole figures for a large number of atom planes were plotted, and the preferred orientation was found to be duplex (102) [0101 + (012) [021]. These preferred orientations are compared with those reported for many of the hexagonal-close-packed metals. THE preferred orientation of a highly reduced cold-rolled uranium strip was determined in order to obtain additional experimental data which would be useful in further understanding the deformation mechanisms of uranium. The preferred orientations reported herein are not in agreement with those theoretically predicted by Calnan and Clews' for cold-rolled uranium sheets, and differ somewhat from those reported from experiments by Fisher, and Burke and Turkalo. Such variations might be accounted for by differences in the fabrication temperature and the reductions. Experimental Procedure The uranium used in this investigation had been hot rolled to 0.060 in. at 575°C from 0.393 in., and from a 0.060 to 0.020 in. thick sheet at 275°C. From this point the sheet was cold reduced 90 pct to 0.002 in. at room temperature. Three specimens were used to obtain complete pole-figure data. The first was a 1/2 in. square section illuminated by the X-ray beam on the rolling surface. The other two were l/2 in. square longitudinal and transverse sections each made as follows: Approximately 200 1/2 in. square sections of the foil were piled one on top of the other, so that the rolling direction for each piece was kept coincident. A 1/2 in. square by 1/8 in. thick steel section was placed on the top and bottom of a pile and the entire assembly was then bolted tightly together through a 1/8 in. diam hole drilled down through the center. Each pile was then surface-ground from the two proper sides to sections 1/2 in. square by 3/16 in. thick. These specimens were then polished flat and electro-polished to remove 0.005 in. of the surfaces to be examined. It can be shown that uranium is so opaque to a Cu Ka X-ray beam that only a small percentage would be transmitted by one micron of uranium. Therefore, a method of measuring the X-ray intensities diffracted from specimen surfaces was used. The specimens were mounted in a modified Schulz reflection holder' which automatically changed the position of the specimen at a constant rate. The holder, in turn, was mounted on a General Electric XRD-3 Spectro-Goniometer and an automatic record made of the diffracted X-ray intensity vs specimen position. While a specimen moved automatically through 10" inclination, at a rate of l° per min, it simultaneously rotated 360" about a normal to the illuminated surface. (The inclination and rotation angles are referred to as F and a, respectively.) The data were then plotted along the resulting spiral path on a stereographic projection, Fig. 1. Because of defocusing effects on the diffracted beam which occur when diffracting surfaces are in-

Jan 1, 1955

By A. U. Seybolt

A FEW copper-zinc-base alloys meet die-casting requirements reason- ably well, although improvements are desired. Aluminum bronzes, high-tinbronzes and some copper-nickel-zinc alloys can be die-cast, accordingto Herb,1 but seldom are because of such factors as higher melting ranges and greater cost than certain of the brasses. Fox2 has summarized the copper-base die-casting alloys that were in commercial use in 1937 and has given the effects of different alloying constituents. Table 1 gives some of the properties of these alloys as reported by Fox. TABLE 1. Commercial Die-casting Brasses a Constituent Yellow Brass Low-silicon High-siliconb Brass Brass Nickel Silver Composition, Per Cent Cu 57-59 63-65 80 -81.5 42.0 Zn 40-42 33-35 13.5-16.0 41.0 Sn 0.5-1.5 Si 0.75-1.25 3.75-4.25 Pb 1.0 Ni 16.0 Properties Tensile, lb. per sq. in.. 55,000-60,000 65,000-70,000 85,000-95,000 85,000-95,000 Yield, lb. per sq. in.d.. 30,000-35,000 35,000-40,000 65,000-70,000 65,000-72,000 Elong., per cent in 2 in . 15-20 20-30 8-12 10-20 Brinell hardness 120-130 120-130 160-180 160 Specific gravity 8.47 8.50 8.15 8.45 Properties reported by Fox.2 b Trade name of Brastil, Doehler Die Casting Co., similar to Webert Alloy, 3,4 American Brass Co., and Tombasil Alloy,5 Ajax Metal Co. c Trade name Tinicosil, Titan Metal Manufacturing Co. Melting point (liquidus) of the yellow brass is given by Herb' as 1650° F., of the high-silicon Brastil (with 4.5 to 5 per cent Si) as 1600° F., and of the nickel silver as 1675° F. d Criterion not stated.

Jan 1, 1939

By John S. Crandall

Occurrence: small crystals in alluvial sands from the eroding Belt Series mica schists. Flowsheet: dragline, trommel screen, jigs, drier, crusher, screens. Value: ground, $2.50 per cu yd, garnet sand gross $60. per ton. Costs: production and sales $48. per ton. Uses: blasting sand in aircraft plants, monumental works, foundries. Efficiency comparison: superior to silica sand. Future: possibilities only touched upon, research continuing.

Jan 1, 1950

By R. V. Norris, E. W. Parker

Edward W. Parker,* Philadelphia, Pa.—At the New York meeting of the Institute a year ago, Mr. R. V. Norris presented a paper on anthracite mining costs, in which he gave the results of an intensive study of this subject by the Engineers' Committee of the United States Fuel Administration. Within the last 30 days, the Federal Trade Commission has issued an official report on the same subject, which covers a longer period of time and comprises statistics of realization values and margins that were pot comprehended in the paper by Mr. Norris. As, however, the data utilized by Mr. Norris formed also a part of the basis for the report of the Federal Trade Commission, a brief digest of the latter may not be out of place at this meeting. The report of the Federal Trade Commission covers primarily the two calendar years 1917 and 1918, divided into five periods which furnish opportunity for the study of how the influence of certain definite factors affected either the cost of production or the price, or both, during the 24 months. The first period, January to April, 1917, which may be considered the basic period, comprised the 4 months in 1917 during which the wage agreement of May, 1916, without modification, was in effect. During this period, the labor cost on fresh-mined coal is placed by the Commission's report at $1.79 per gross ton, the total cost at $2.66, the average realization at $3.29, and the "margin" (sales realization over total f.o.b. mine cost) at $0.63. The second period covers the four months from May 1 to August 31, during which time the first of the supplemental wage agreements (supplemental to the agreement of 1916) was in effect. It was also the period during which the summer discounts were in effect and when prices were practically fixed by a voluntary agreement between the operators and the Federal Trade Commission. It was, further, the period in which the 75 cents differential on prepared sizes permitted to the individual operators by the Federal Trade Commission began; at that time, also, on account of war conditions an unusually large quantity of steam sizes were marketed at exceptionally good prices. On account of the two latter conditions, not explained in the Commission's report, the "margin"1 on operating

Jan 1, 1920

By V. I. Purcell, S. C. Sun. R. E. Snow

A study including effects of 7) pH value, 2) fatty acid collector, 3) fuel oil, 4) interfering ion, 5) particle size, and 6) operational variables. Test results indicate feasibility of fatty acid flotation under certain restrictive conditions. FATTY acids have been used as standard collectors for floating the matrix1-8 but not the leached zone phosphate ores. After a series of investigations, Davenport9 and Tarbutton10 concluded that the Florida leached zone ores tested were unamenable to fatty acid flotation and must be upgraded by floating the siliceous gangue with Armac-T as collector. The cationic flotation was estimated11 to cost almost ten times as much as a fatty acid process that would ideally give the same flotation grades and recoveries of phosphates. Mineralization: Extensive deposits of leached zone aluminiferous phosphate occur in Florida."= The ore sample used for this work was obtained from the Virginia-Carolina Chemical Corp., Clear Springs area, Florida. The ore is a potential source of uranium and aluminum as well as phosphorus. Since the uranium and the recoverable aluminum are contained in some of the phosphate minerals, an upgrading of phosphate results in a corresponding enrichment of both uranium and aluminum. The phosphate minerals in the ore are primarily pseudo-wavellite, millisite, and carbonate fluorapatite, with a minor amount of wavellite. Quartz and clay are the common gangue minerals, quartz being predominant. Others present in small amounts are ilmenite, hydrated iron oxides, staurolite, monazite, and zircon. Experimental Procedures: After being dried to less than 1 pct surface moisture the material was dry-ground in a Hardinge conical ball mill to —6 mesh. The ground product was classified into 6/20, 20/200, and —200 mesh size fractions. On the basis of Table I, the coarse and fine size fractions were considered as phosphate concentrates, because of their high phosphorus contents. In contrast, the 20/200 mesh fraction, which was low in phosphorus, was used as the flotation feed. All the flotation tests, unless otherwise stated, were performed in a laboratory Fagergren machine under the following conditions: 1) 400 g of solid feed for each test, 2) 2000 rpm impeller speed, 3) 8.9 pH and 4-min conditioning, and 4) 3-min flotation. The procedure used for the quantitative bubble pick-up tests has been described previously.18

Jan 1, 1958

By R. E. McNulty, R. D. Heidenreich, C. H. Gerould

TIIE electron microscope techniques and their application to magnesium alloys that are to be discussed in this paper are the result of research at The Dow Chemical Co. over the past three years. The view- point underlying the work is not wholly metallurgical, but has evolved through a variety of problems related to the physics and chemistry of surfaces. It can be said that the interest and stimulus were closely associated with a desire to employ effectively the electron microscope in research concerning the properties of solids as related to their physical structure. Only a portion of this work will be described here, and, consequently, many points of interest and debate are of necessity either only briefly recognized or are completely omitted. As has been pointed out by Desch,1 a great deal of the knowledge of the structure of metals has been obtained through microscopic studies of the surfaces of metallic specimens prepared in a particular manner. This information, when added to that obtained by means of thermal, electrical, X-ray, dilatometric and other methods, has been of great value both from a theoretical and a practical view- point. With the introduction of new instruments such as the electron diffraction camera and the electron microscope, it would be expected that still more information could be obtained. These two instruments have in many instances been very effective when directed toward the investigation of metallic surfaces, provided the proper methods of surface preparation were employed. Experience shows that the problems of surface preparation greatly limit the general application of these instruments to metallographic studies. It was found necessary to discard the standard metallographic procedures in applying the electron microscope to magnesium alloys and to work out new methods, which were required to satisfy certain conditions. These methods are unique to magnesium only in the specific chemical reactions occurring during etching. The presentation of the methods and results will be ordered as follows: I. Electron Microscopy of Surfaces. 2. Surface Preparation of Magnesium Alloys. 3. Discussion of Microstructures. a. Pure Magnesium and Single-crystal Studies. b. Types of Precipitation. c. Some Common Structures. d. Special Micrographs and Techniques. e. Structure of Mg-A1 Solid Solutions. 4. Correlation of "Fine Structure" with Corrosion Behavior of Magnesium Alloys.

Jan 1, 1946

By Kichizo Niwa

A LTHOUGH studies on the roasting of ferrous A sulfide have been carried out by several investigators, some disagreements still remain among those results. Schwab and Philinis1 have measured the rate of oxidation by a precise thermobalance and have concluded that the rate is controlled by diffu-

Jan 1, 1958

By George S. Barnett

The Equis and El Roble projects are located in the Cordillera Occidental of Colombia. The Equis vein deposits have sulfide ore reserves of 95,955 mt (105,770 st) grading 8.51 g/mt (0.248 oz/st) gold and 12.4 g/mt (0.36 oz/st) silver with 0.94 % copper, 1.10 % lead and 11.06 % zinc. Ore reserves at El Roble are estimated as 1.1 Mmt (1.21 million st) grading 4.89 % copper and 3.39 g/mt (0.099 oz/st) gold. Geologically possible reserves at Equis may total 1.6 Mmt (1.76 million st). El Roble has the potential to contain several tens of millions of metric tons. Exploration included diamond drilling, trenching, channel sampling, rock and soil geochemistry, geophysics and tunneling. Erratic high grade samples affect the weighting of channel and drill core samples. Secondary reconcentration of gold is also a factor. Sample maps and graphs show the distribution of values to be highly variable. Geostatistical treatment of some of these data gave important guidelines for parameters such as sampling densities, drill hole spacing and confidence limits.

Jan 1, 1985

By Michael Tenebaum, C. C. Brown

In recent years, the importance of slag control in basic open-hearth operations has been universally recognized. To effect such control during the working period of the heat, methods have been developed to measure or estimate slag oxidation and slag basicity. While satisfactory rapid chemical methods have been developed to determine slag oxidation, no completely adequate method of evaluating basicity has yet been provided. The most generally accepted control methods of measuring slag basicity are based on visual cstimates. While considerable benefit may be derived from such estimates, the need for some measurable indication of slag basicity has become increasingly apparent. In a recent paper, Philbrook and Jolly suggested a promising technique for making the basicity determination. Their method consists of measuring the pH of a mixture of powdered open-hearth slag and distilled water. It was found that a relation could be established between the slag basicity and the alkalinity of the water mixture as measured by the hydrogen-ion concentration. The general procedure followed in making the measurements and the considerations involved in constructing the original curves are given in the paper of Philbrook and Jolly and need not be repeated. It is the purpose of this paper to discuss some of the factors considered in applying the pH measurements to actual slag control and to present some of the results of its apphcation. Factors Involved in Measuring pH of Water-slag Mixtures To facilitate the application of the pH control system, it was desirable that no alteration be made in the routine methods of sampling and crushing the furnace slag. Some of the factors considered before establishing a curve to relate slag basicity with the pH reading arc reviewed individually in the following paragraphs. Effect of Cooling Rate Under actual operating conditions there can be considerable variation in the temperature of the piece of slag crushed for the pH determination. To determine whether variations in crushing temperature or in cooling rate would affect the pH reading, a series of four samples was prepared from each of two separate slags. These samples represented conditions far more extreme than would actually be encountered. To obtain these samples, a thick pancake of slag was poured. One piece of this pancake was crushed immediately after it had solidified. Another piece was water-quenched and then crushed. A third piece was allowed to air-cool to room temperature before crushing. The fourth sample was prepared from a chilled slag. This sample was poured onto a heavy inclined steel plate at the

Jan 1, 1945

Geological and Natural History Survey of Wisconsin, The University of Wisconsin, Madison, Wis - E. F Bean, State Geologist. A complete list of publications of this Survey will be sent upon request Only a portion of the Bulletins and Maps fall within the scope of this directory, and most of them are available They are: Bulletin 4, Building and ornamental stones of Wisconsin (1898), $2 50, 6, Preliminary report on the copper-bearing rocks of Douglas County, and parts of Washburn and Bayfield counties (1901), 50 cents, 7, The clays and clay industries of Wisconsin (pt 1) (1901), 50 cents; 14, Report on lead and zinc deposits of Wisconsin (the report is out of print but the 18 maps which accompanied it can still be had) (1906), 20 cents (a series of six maps, supplementary to these (1909), may be had for 6 cents), 15, The clays of Wisconsin and their uses (1906), 50 cents; 16, The geology of north-central Wisconsin (1907), $2, 17, The abandoned shore lines of eastern Wisconsin (1907), 50 cents, 19, Zinc and lead deposits of the Upper Mississippi Valley (1907), 25 cents; 34, The limestone road materials of Wisconsin (1914), 50 cents, 35, Underground and surface water supplies of Wisconsin (1915), $150, 36, The physiography of Wisconsin (new edition now in press) (1916), $125, 41, A study of methods of mine assessments and valuation (1914), 50 cents; 44, Mineral land classification in parts of northwestern Wisconsin (1915), $5, 45, The peat resources of Wisconsin (1915), 50 cents, 46, Mineral

Jan 1, 1933

By Walter W. Fisher, Samuel Rudy

Secondary treated sewage effluent was substituted for normal process water in laboratory tests simulating froth flotation recovery of copper and molybdenum sulfides. Sewage effluent caused significant detrimental response in the flotation process. First, a voluminous, uncontrollable froth was generated, even in the absence of a frothing agent, that has little mineral carrying ability. Second, sewage effluent caused a small loss in copper recovery and a large loss in molybdenum recovery. The detrimental effects of sewage effluent on flotation were partially overcome by tertiary treatment of the effluent by activated carbon adsorption and anion exchange. The frothing problem was significantly reduced after treating the sewage effluent by foam fractionation. Dilution of the effluent with normal process water resulted in a significant improvement in metal recovery. In addition, the large loss in molybdenum recovery was overcome by using a secondary collector in a combination reagent schedule. However, the secondary collector caused an appreciable loss in copper recovery.

Jan 1, 1979

By Booker Morey, Ashok Gupta

Amid controversy, the resource recovery industry is rapidly approaching its first commercial operations. Some of the problems are reviewed along with some of the important systems that are being developed for resource recovery. Market specifications for the inorganic fraction recovered from municipal solid waste are reviewed along with the details of the unit operations that have been tested.

Jan 1, 1976

By L. E. Young

The progress of mineral industry education will be limited to the period prior to World War II and will be considered as primarily a division of engineering education. Its relation to progress in the mineral industry and to the activities of the American Institute of Mining and Metallurgical Engineers will be emphasized. The history of mineral industry education has been recorded most completely and authoritatively by Dr. T. T. Read in his recent volume in the Seeley W. Mudd Series of American Institute of Mining and Metallurgical Engineers publications, entitled, The Development of Mineral Industry Education in the United States. Therefore, most of the historical details will be omitted from the discussion and an effort will be made to point out significant developments and to analyze trends. Introductory Statement and Significant Points in Progress Among the significant points in the development of mineral industry education in the United States since 1871, the following deserve particular mention: 1. The number of institutions offering undergraduate instruction has increased, particularly during the years 1890 to 1925; the number of students enrolled in undergraduate study has increased greatly, largely on account of the development of courses in petroleum engineering and increasing interest in metallurgy. 2. The selection of students to be admitted to undergraduate courses has been improved through the advisement, counseling, and guidance programs sponsored by the Engineers' Council for Professional Development. 3. Improved instruction methods all the training of the teaching staff have been promoted by the educational institutions themselves, but with the most effective stimulus and guidance of the American Society for Engineering Education and the Engineers' Council for Professional Development. 4. The accrediting of undergraduate curricula through the Engineers' Council for Professional Development, consitlering both qualitative and quantitative criteria, has done much to improve standards of instruction in engineering education for thc mineral industry. 5. Undergraduate curricula and courses are revised currently to meet the needs of the American mineral industry. New curricula are developed currently to permit specialization in technical fields, particularly in the fourth year of undergraduate work. 6. There has been a strengthening of the fundamental courses in mathematics, physics, mechanics, and chemistry, and at the same time these courses are being adapted to the most recent developments in the industry, including metallurgy, geophysics. petroleum engineering, petroleum technology, ceramics and SO forth. 7' There has been continuing improvement in plant and laboratory facilities of the educational institutions.

Jan 1, 1949

By R. W. Guard, W. R. Hibbard

As part of a program to determine the deformation characteristics of pure metals, the tensile creep properties of high purity aluminum (99.994 pct Al) have been determined using a constant stress loading. The effects of prior annealing temperature, stress, and temperature were studied. These data have been examined on the basis of present-day theories. None of the methods was found to give an accurate representation of the data over all conditions studied. The structures of several specimens after creep were examined by optical and X-ray metallography. Marked changes in the grain size were found and it was substantiated that the magnitude of these changes was greatly influenced by the applied stress (or creep strain). The changes in fiber texture which occur on creep deformation are shown to be consistent with those observed on deformation at lower temperatures. UNDERSTANDING the properties of new mate-*-J rials under different experimental conditions must be based on considerable knowledge of the mechanisms involved in plastic flow and how to control them. Tension and creep tests have been carried out on a number of pure metals in order to document their deformation characteristics. It is hoped that a comparison of these data with theory will indicate those areas where work on mechanisms and their relation to metallurgical variables may be most fruitful. Since aluminum has often been used for studying the qualitative aspects of creep behavior, it was chosen for detailed study. The effects of annealing temperature, stress, and test temperature on the constant stress creep behavior were studied. Although most of the tests were made above one half the absolute melting temperature, a few tests were made at lower temperatures to give qualitative comparisons. Some specimens were examined metallo-graphically and by X-ray diffraction techniques after creep. Since only a limited number of specimens could be made from the available material, no effort was made to study detailed changes in sub-grain structure or other metallographic features. Servi and Grant3 nd Dushman et al.' have previously published studies of high temperature creep of high purity aluminum. In both cases, a great deal of emphasis was placed on the minimum creep rate.

Jan 1, 1957

By B. F. Decker, J. H. Keeler, W. R. Hibbard

Textures of hot-rolled, of cold-rolled, and of cold-rolled and annealed zirconium sheets were determined by use of an X-ray spectrogoniometer. All textures showed a tilt of the basal planes 240" from the rolling plane about the rolling direction. Deformation textures showed the [1010] direction to be approximately in the rolling direction. After recrystalliza-tion, the 111201 direction was approximately in the rolling direction. This texture was sharpened by annealing above the allotropic transformation. Textures of sheet produced by alternately cold rolling and then annealing were less strongly oriented than sheets that underwent severe deformation without intermediate anneals. THIS study of the deformation and annealing textures of high purity zirconium was carried out to supplement an investigation of zirconium and zirconium-base alloys. The spectrogoniometer method of pole figure determination was used and yielded more detailed and precise information than the photographic techniques used by previous investigators. Earlier investigations of the rolling textures of hexagonal metals titanium,1,2 beryllium," and zirconiumL having a c/a ratio slightly less than 1.6 disclosed a rotation of the basal planes from the rolling plane about the rolling direction so that the basal poles were inclined toward the transverse direction, and with one exception,& the [1010] direction was found parallel to the rolling direction. Similarly, hot rolling produced a spread of the basal poles in the transverse direction,2,3,5 With the [1010] direction parallel to the rolling direction. The textures of these metals after recrystallization differ somewhat from each other although still exhibiting the transverse rotation of the basal poles about the rolling direction. Zirconium" was found to have the [1120] direction in the rolling direction, beryllium" continued to have the [1010] direction in the rolling direction, and titanium' was shown to have the [1010] direction in the rolling direction (the cold-rolling texture) when annealed at 1000°F, changing to the [1120] direction in the rolling direction when annealed at 1500°F. It was suggested2 that the titanium retains the deformation texture after re-crystallization, and preferred grain growth at higher temperatures produces the second texture. Annealing above the allotropic transformation temperature did not appreciably change the high temperature recrystallization texture for titanium.' Coarsegrained zirconium showed more spread" in the transformation texture than in the recrystallization texture. The material used in this investigation was crystal-bar zirconium prepared by the iodide process. The major impurity was hafnium which was less than 0.3 pct. The composition obtained by spectro-graphic analysis is given in Table I. The hot-rolled specimen was prepared from a 50-g button of zirconium arc-melted in a water-cooled crucible under an argon atmosphere. This button was enclosed in a welded sheath of soft iron and the ensemble was rolled at 825°C. After each pass the sheath was put back into the furnace to allow it to return to the desired temperature. The zirconium ingot was reduced in this manner to a thickness of about 0.035 in., a reduction of approximately 90 pct. The sheet after removal from the sheath was alternately polished and etched to a thickness of 0.001 in. Cold-rolled specimens were prepared from crystal bar by a series of reductions of approximately 0.010 in. until the sheet reached a thickness of 0.010 in. after which it was cold-rolled to 0.001 in. thickness between sheets of alloy steel. The total cold reduction amounted to about 99.8 pct. Specimens were annealed in an evacuated Vycor or quartz tube. The transmission pole figures were obtained by the quantitative method of Decker, Asp, and Harker6 modified by Geisler7 using an X-ray spectrogoniometer with Cu Ka radiation. Unless otherwise specified all four quadrants were examined with 5" increments along the radius of the pole figure. Absorption corrections were made for changes in length of the X-ray path through the sample as inclination of the

Jan 1, 1954

By M. T. Martinson, I. W. Nicholson, C. J. Chindgren, F. P. Williams, L. C. Bauerle, S. F. Ravitz

THE vanadiferous shales of southeastern Idaho and southwestern Wyoming constitute the largest known reserve of vanadium in the United States.1 These deposits have never been exploited except for the relatively small amounts of vanadium recovered by the Anaconda Copper Mining Co. in the treatment of phosphate rock from southeastern Idaho. The major domestic source of vanadium has been the sandstone ores of southeastern Utah and southwestern Colorado. Early in World War II, it appeared that these ores could not meet the greatly increased demand for vanadium, so the investigation described in this report was undertaken to develop processes for the recovery of vanadium from the Idaho-Wyoming deposits. The utilization of these deposits became unnecessary, however, because of greatly expanded production from the Utah-Colorado sandstone ores and the continued availability of vanadium from other sources, chiefly Peru. The major use of vanadium is as an alloying agent in the manufacture of high-quality steels. Vanadium constructional steels usually contain 0.05 to 0.20 pct vanadium, which refines the grain and increases the strength, elastic limit, and resistance to shock and fatigue. Vanadium tool steels not used in high-speed work contain 0.10 to 0.60 pct whereas high-speed tool steels contain 1.0 to 4.0 pct. Vanadium compounds are used as catalysts (principally for the oxidation of SO2 to sulphuric acid and of naphthalene to phthalic acid) and in the paint, chemical, ceramic, dye, and printing industries. The selection of the particular ore deposit to be exploited would involve consideration of many factors besides the metallurgical results that might be obtained. Chief among these would be the reserves of ore available, the grade of the ore, and the mining costs. As very little was known about any of these factors, it was necessary to investigate methods of treatment of all the ores under consideration, working with samples obtained in the course of the exploration work, even though they were not positively representative of the whole deposit from which they were taken. Because of wartime conditions prevailing when this investigation was started, first consideration was given to processes that could be put into operation most quickly and would involve minimum use of strategic materials, even though these processes might not be the most economical.

Jan 1, 1947

By M. T. Martinson, I. W. Nicholson, C. J. Chindgren, F. P. Williams, L. C. Bauerle, S. F. Ravitz

The vanadiferous shales of southeastern Idaho and southwestern Wyoming constitute the largest known reserve of vanadium in the United States.' These deposits have never been exploited except for the relatively small amounts of vanadium recovered by the Anaconda Copper Mining Co. in the treatment of phosphate rock from southeastern Idaho. The maior domestic source of vanadium has been the sandstone ores of southeastern Utah and southwestern Colorado. Early in World War 11, it appeared that these ores could not meet the greatly increased demand for vanadium, so the investigation described in this report was undertaken to develop processes for the recovery of vanadium from the Idaho-Wyoming deposits. The utilization of these deposits became unnecessary, however, because of greatly expanded production from the Utah-Colorado sandstone ores and the continued availability of vanadium from other sources, chiefly Peru. The major use of vanadium is as an alloying agent in the manufacture of high-quality steels. Vanadium constructional steels usually contain 0.05 to 0.20 pct vanadium, which refines the grain and increases the strength, elastic limit, and resistance to shock and fatigue. Vanadium tool steels not used in high-speed work contain 0.10 to 0.60 pct whereas high-speed tool steels contain 1.0 to 4.0 pct. Vanadium compounds are used as catalysts (principally for the oxidation of SO2 to sulphuric acid and of naphthalene to phthalic acid) and in the paint, chemical, ceramic, dye, and printing industries. The selection of the particular ore deposit to be exploited would involve consideration of many factors besides the metallurgical results that might be obtained. Chief among these would be the reserves of ore available, the grade of the ore, and the mining costs. As very little was known about any of these factors, it was necessary to investigate methods of treatment of all the ores under consideration, working with samples obtained in the course of the exploration work, even though they were not positively representative of the whole deposit from which they were taken. Because of wartime conditions prevailing when this investigation was started, first consideration was given to processes that could be put into operation most quickly and would involve minimum use of strategic materials, even though these processes might not be the most economical.

Jan 1, 1949

By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By N. K. Chen, R. Maddin

THE textures of straight-rolled and of cross-rolled molybdenum were first determined with the aid of pole figures by Custers and Riemersma.' These authors have shown that for straight-rolling, the main texture was (100) [0111 with a considerable spread about the rolling direction. After cross-rolling a second texture was obtained in which there was a [111] axis perpendicular to the rolling plane, possessing a rotary symmetry. Recently Semchy-shen and Timmons2 in their study of preferred orientation of arc-cast molybdenum sheet obtained similar pole figures. In these two investigations, polycrystalline materials were used. In the main, the textures of molybdenum in these cases are qualitatively consistent with rolling textures of other body-centered cubic metals, such as iron and Fe-Si alloys." In the present investigation, single crystals of molybdenum were deformed by rolling with respect to specific crystallographic planes and directions. Since the deformation textures of polycrystalline aggregates have been related intimately to the behavior of individual grains,4 a study of possible correlations of final textures with respect to the initial orientations of the single crystals might conceivably lead to a better understanding of the textures. Annealing treatments were carried out after deformation in order to study the recrystallization characteristics as well as the recrystallization texture. Rolling of Single Crystals Single crystals of molybdenum (about 1/8 in. in diarn x 1-in. long), grown by the method previously described,5 were cold-rolled without intermediate anneals. Except for specimens MR-1 and MR-2, which were rolled at random in the preliminary test in order to find a proper rate of reduction, all other specimens were carefully documented as to their respective orientation before deformation by means of X-ray Laue back-reflection methods. A stereo-graphic projection was constructed from which it was possible to determine a particular plane and direction to be considered for rolling. Parallel flat surfaces were then polished metallographically with respect to a reference scratch on the specimen which was mounted in sealing wax. These flat surfaces contained the plane chosen for rolling. After etching, a Laue back-reflection photogram was again made of one of the flat surfaces to determine the exact plane of rolling. The initial orientations of all the specimens (specified by two elements for each crystal, direction of rolling and the pole of the rolling plane) are summarized in Fig. 1. The specimens were mounted in plasticene between two hardened Si-Fe plates. The sandwich was then rolled down, keeping the direction constant in the case of straight-rolling. In cross-rolling (MR-10, MR-11, and MR-12) the sandwich was rotated 90" after each pass so that every first and third pass contained the same rolling direction. Specimens MR-14, MR-15, and MR-16 were compression-rolled following the manner of Barrett." In these cases the direction of the sandwich through the rolls was changed by 3" to 5" for each pass until the specimens were rolled to the desired reduction in thickness. It was found that if extreme care was exercised in rolling, i. e., the amount of deformation per pass was extremely small, the specimens could be rolled to a large reduction in thickness. The rate of reduction used, with a single exception of MR-1. was generally 0.001 in. per 10 passes. Thus, it took about 800 passes to reduce a specimen to a final reduction in thickness of 87 to 98 pct. The results of rolling are shown in Table I. Cold-Rolling Textures The final orientations were determined by the conventional Laue transmission method," using molybdenum radiation, with or without a zirconium filter. Pole figures were plotted from (1101 and (200) reflections in which three degrees of intensity— heavy, medium, and light—were determined visually. Three main types of textures have been observed from the deformed single crystals. These are: 1—a

Jan 1, 1954