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By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.' Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts' Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg's method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By Keith R. Bock, Norman Parlee, Albert M. Barloga

Coils of pure iron and iron-carbon alloy wire (0.05 to 0.80 pct C) and sufficient sulfur to saturate the solid phase were equilibrated in evacuated or argon filled tubes. After rapid cooling, and removal of the outside nonmetallic layer, the wires were analyzed for carbon and sulfur and the data used to construct an Fe-S binary and isotherms of the Fe-C-S ternary in the range 1149° to 1427°C. THE solid solubility of sulfur in steel is of interest in connection with such phenomena as hot shortness, burning, and so forth. "Burning," the more or less permanent damage that some steels suffer when heated for forging or rolling, has been shown to be related closely to the behavior of sulfur and less closely to carbon and oxygen.' Attempts to interpret burning phenomena in steels fail because of lack of data on the Fe-C-S and the more complex systems in this family. Rosenqvist and Dunicz 2 and Turkdogan, Ignatowicz, and pearson3 have largely elucidated the Fe-S diagram in the region of interest but no information on the Fe-C-S diagram in this region appears to be available in the literature. This paper deals with the elucidation of the Fe-C-S diagram in these interesting ranges. The method employed is different from those used by previous workers2'3 on the Fe-S system. EXPERIMENTAL METHOD Pure iron wires (Ferrovac E) or iron carbon alloy wires of 1 mm in diam were cleaned with acid and acetone, coiled, and placed in silica tubes (7 mm OD and 5 mm ID) previously closed at one end. Enough sulfur was added to assure saturation of the solid iron phase. The filled tubes were either simply evacuated and sealed, or filled with argon at a reduced pressure and sealed. The argon was required at the higher temperatures to prevent collapse of the tubes. The filled and sealed tubes were placed in the middle uniform temperature zone of a Globar tube furnace and equilibrated at temperatures ranging from 2100°F (1149°C) to 2720°F (1493°C). After equilibration the tubes were removed from the furnace and quenched in air or water, the form of quenching being found to have no effect on the results. The tubes were broken open and the coils were placed in a 1 : 1 HC1 solution to remove the sulfide-rich layer. The coils were then cut into small pieces and analyzed for sulfur and carbon. In the early stages of the investigation different equilibration times ranging up to 17 hr were tried and the cores of the wires were analyzed to test for saturation. One hour appeared to be sufficient to reach maximum sulfur content at 1454°C and 2 hr sufficient at 1149°C. The practice adopted was to use at least 3 hr at the higher temperatures and at least 5 hr at the lower temperatures. The iron-carbon alloy wires used were made by carburizing pure iron wire with carbon monoxide gas in a one inch diameter ceramic tube at about 1204°C. Differing carbon contents were obtained by allowing fairly large coils to react with the gas for varying lengths of time at a flow rate of 800 cc per min. The reacting times ranged from 15 min to 4 hr depending upon the amount of carbon desired. The furnaces used were controlled by means of Leeds and Northrup Speedomax Type H instruments with D.A.T. Control attachment. Thermocouples were calibrated against the melting points of gold and copper. The temperatures recorded appear to be accurate within i2.7OC. Starting with run No. 85 and continuing with the

Jan 1, 1962

By Martin Rubenstein

CdS crystals have been grown from a number of metallic solvents such as bismuth, tin, lead, and cadmium. Etching studies have shown that plastic deformation occurs if the crystals are not removed from the solvent prior to the solidification of the solvent, on cooling. The deformed crystals show a umique exciton fluorescence as a function of edge dislocation density. If one grows the CdS in the eutectic alloy of the above four metals (commonly called Wood's metal) the crystals can be removed from the solvent with hot water and no plastic deformation occurs. In this paper, the liquidus solubility measurements of CdS, as a function of temperature, are presented. The data were obtained using a high -temperature filtration technique. CADMIUM-SULFIDE crystals have been grown from a number of metallic solvents1 such as cadmium, bismuth, tin, and lead. Liquidus solubilities of CdS in cadmium,2 bismuth,3 and tin4 have already been measured. Crystals of CdS, in all four metals, have been grown by solution growth: 1) by cooling a saturated solution and 2) by a solution transport method.1'"1 CdS crystals grown in these four solvents have a few characteristics in common: 1) 1.8°K photolumines-cent emission consisted mainly of the radiative recombination of the bound exciton commonly known as I,, 2) slip lines which could easily be seen by the naked eye, and 3) edge dislocation densities in the order of l05 per cu cm.1 It was decided that these slip lines and the high edge dislocation densities were caused by a plastic deformation of the CdS crystals. It was felt that this plastic deformation did not occur during the growth of the crystals nor during the cooling of the solution, but did occur when the solvent which was in contact with the crystals froze. If these assumptions were valid, the slip lines and the high number of dislocations could be reduced or eliminated by removing the crystals from the solvent before the solvent froze. Since crystals of CdS had already been grown separately in such solvents as bismuth, lead, tin, and cadmium, it was felt that crystals could be grown in a eutectic mixture of these four metals. In this work a eutectic (or near eutectic) mixture of bismuth, lead, tin and cadmium in the proportion 50, 26.5, 13.5, and 10 wt pct, respectively, was used to grow CdS crystals. Such a mixture has a melting point of about 70°C and is close in composition to the alloy commonly known as Wood's metals. If the crystals could be grown from this mixture of solvents, and if hot water (>75°C) could be used to separate the crystals of CdS from the metallic solvent, it was hoped that CdS crystals could be grown with little or no plastic deformation which had been ob- served when crystals were grown from these solvents uncombined. CdS crystals were grown from this low melting eutectic mixture of bismuth, lead, tin, and cadmium using the solvent transport method. CdS powder and the appropriate amount of metals were sealed in a quartz tube under a pressure of about 5 X 10-6 torr. This ampule was then placed in a vertical position in a furnace. The temperature was raised to about 900°C. The furnace was designed so that the top of the liquid column within the ampule was between 10° to 40°C higher than the bottom of the liquid column. These temperatures were measured on the outside of the quartz ampule. The ampule was maintained at temperature for 7 to 14 days (depending on the temperature at which transport was taking place) and then the furnace temperature was lowered until the temperature was about 125°C. The ampule was then removed from the furnace, placed in water maintained at about 90°C, and opened in this 90°C environment. The crystals could then be removed from this two-phase liquid (Wood's metal and water) by mechanically picking them out. Alternatively, the crystals could be quantitatively removed by adding an excess of mercury to the mixture of metals, crystals, and hot water. The hot solution of metals and the hot water could be evacuated using a small diameter tube connected to a vacuum. Small amounts of mercury and water could be removed by heating the crystals in vacuum. Crystals prepared using this technique showed no evidence of slip. However, some of these crystals did show edge dislocation densities as high as l04 per cu cm. Some few selected crystals showed no dislocations. Single crystals of CdS were grown as large as 5 by 5 by 0.5 mm. The ampules for the growth of these crystals were 13 mm O.D., 11 mm I.D., 150 mm! LIQUIDUS SOLUBILITY MEASUREMENTS The CdS starting materials was G.E. 118-8-2 powder which was fired in H2S at 1000°C, and then a vapor transport technique5 was applied to produce a "sound" mass of CdS. The Wood's metal was prepared by weighing out bismuth, lead, tin, and cadmium in the proportions of 50, 26.5, 13.5, and 10 wt pct, respectively. The bismuth, cadmium, and lead were from the American Smelting and Refining Co. (ASARCO) and all had purities of 99.999+ pct. The tin was 99.9999 pct spectroscopic grade from the Vulcan Materials Co. The appropriate mixture was placed in a quartz tube, evacuated to a pressure of 5 X 10-6 torr, melted to a liquid, cooled to room temperature under this same vacuum. This ingot was then placed in another quartz tube, evacuated to 5 x l0-6 torr, and sealed off under vacuum. The ampule was then horizontally placed in a furnace. The temperature was raised to 600°C, and over a period of several hours the ampule was vigorously shaken several times. The ampule was then removed from the furnace, and the metallic liquid was

Jan 1, 1970

By Albert C. Harding

FOR several years barite (BaSO4) production has topped such better known minerals as feldspar and fluorspar in annual tonnage and is now well established among our foremost nonmetallic industries. DESCRIPTION Of widespread occurrence in the United States, barite is relatively soft (hardness, 2.5 to 3.5), inert, heavy (specific gravity, 4.5), and is also called "barytes" (sometimes pronounced "bear-i-tease"), "heavy spar" and "tiff." It occurs with granular and earthy structure but usually has coarse, orthorhombic crystallization. It is commonly white, and although occurring in various shades of red, yellow, and gray, barite always gives a white streak and can be scratched by the ordinary prospecting pick. Its softness and weight are usually sufficient to establish field identification. Another aid is the "rotten egg" odor of H2S which sometimes emanates from freshly fractured surfaces. Barite can be readily distinguished from two other minerals which have somewhat similar occurrences and characteristics. The relatively rare celestite, strontium sulphate, has a specific gravity slightly less than 4.00 and gives a distinctively crimson color in a flame test. The very rare witherite, barium carbonate, has a specific gravity of 4.3 but readily effervesces with dilute hydrochloric acid. OCCURRENCE All known commercially important barite deposits in the United States occur as re placements or cavity fillings in schists, shales, limestones, dolomites, and quartzites, or as residual deposits from such formations. In Georgia, Tennessee, North Carolina, and Missouri, high-grade barite is recovered as fragments from residual clays covering quartzites and dolomites. In Arkansas, Nevada, and California, barite, usually of lower grade, is mined from replacement deposits. These seven states contributed the entire production reported by the U. S. Bureau of Mines for 1945 as given in Table I. [TABLE 1-Crude Barite Sold or Used by Producers in 1945 STATE SHORT TONS Arkansas260,660 Missouri225,467 Georgia110,393 Tennessee32,812 Nevada28,919 Other States37,811 Total 696,062] "Other States" included only California and North Carolina. Such a large part of this undistributed production came from California that that state probably outranked both Nevada and Tennessee. For the second consecutive year Arkansas was the leading producing state, particularly worthy of note because there was no commercial production of barite there prior to 1941 and because the entire production of Arkansas has come from one large deposit which is being operated by two companies. CONSUMPTION [The 1945 consumption as reported by the Bureau of Mines was: 482,442 tons as ground barite 139,288 tons in making lithopone 99,173 tons in producing barium -- chemicals Total 720,903 tons]

Jan 1, 1947

By A. A. Berk

LAGGING technology and the slow spread of information have been the chief obstacles to widespread participation in minimizing the industrial pollution load. These obstacles can be conquered by fact finding and applied research. There are three aspects to the problem of water-borne mineral waste: to minimize the amount being thrown away, to select a predisposal treatment, and to use the products or dispose of them. It is often possible to minimize the waste by making very minor changes in the process that produces it. For example, a manufacturer of automobile bumpers greatly reduced the dragout 'from a plating bath by modifying the design and position of two boltholes.' A plater of automobile hubcaps installed a drainage bar and decreased the loss of chrome-plating solution to the rinse water by about 80 pct.' The mill at a western mine found it possible to discard 60 to 70 pct of an ore with minimum treatment," so that the processing effort could be concentrated on a high-graded slime, with significant reduction in costs and improvement in recovery. The possibilities for waste reduction through process changes are limited only by the imagination. A recent patent points out the advantages of using No. 1 fuel oil instead of water in wet-process cement making;& the fuel oil presumably has better properties than water for this purpose and is said to be almost com'pletely recovered or utilized, so that there is no waterborne waste. Recycling to reduce wastes and improve process economy is very well illustrated in vanadium and uranium recoveries from relatively low grade ore. Ores containing 6 pct calcium carbonate were found to give poor vanadium recovery by the salt-roasting process because the vanadium was converted to water-insoluble calcium vanadate. Following the salt-roasting process, sulfuric acid was used to leach the uranium. Enough calcium sulfate was formed

Jan 1, 1958

By Cyrus Garnsey

NECESSITY FOR PRICE FIXING DURING the latter part of 1916 and the early months of 1917, clue to war activities, there was a threatened shortage of coal which resulted in panic among consumers and a rush to obtain coal at once at any price. As a result of this insistent demand for immediate delivery, prices were bid up by the consumers to unprecedented heights; spot coal which had previously been selling at from $1.50 to 82 per ton was bid up to $5, $6, and, in exceptional cases, as high as $7.50 or more per ton. Then when the April, 1917, contract period arrived, contracts could be made only at prices ranging from $3 up to $5 and $6 per ton for the year's delivery. This condition caused such a demoralization of the business, and so much complaint, that some action to regulate prices was considered essential by the National Administration. LANE-PEABODY AGREEMENT In May, 1917, a committee under the chairmanship of F. S. Peabody, of Chicago, was appointed by the Council of National Defense, through Mr. Lane, to consider the whole question of bituminous coal. This committee, with the Secretary of the Interior, Mr. Lane, after numerous meetings and long negotiations with the operators throughout the country, announced on June 29 an agreement between the Committee and the producers, fixing a tentative maximum price for bituminous coal throughout the country at $3 per net ton f.o.b. mines, to which was added 25 c. for selling commission to wholesalers. This plan was based on the idea of fixing a maximum price, high enough to greatly-stimulate production, with the expectation that the laws of supply and demand would, with ample production, operate to maintain fair and just prices for coal throughout the country.

Jan 9, 1918

By Jack A. Kanz, Samuel R. Shortes, E. C. Wurst

Zinc diffusion into GaAs from the vapor phase through reactively sputtered SiO, films Izas been inrestigated for various zinc pressures at 1000"C. Diffusions were carried out in evacuated quartz ampules with elemental zinc and with various Zn-Ga alloys. Sputtered films have proved effective in lowering surface concentrations and preventing surface deterioration during diffusion. Approxin.ate complenzentary error-function impurity distributions were found when surface concentrations were reduced to approximately 3 -—4 x 10" atoms cm'3 or less with dilute zinc sources or by diffusion through SiO, films. Zinc difhsions in GaAs tlzrough SiO, films produced more planar diffusion fronts than were observed with uncoated zuafers under identical conditions. A) Surface Deterioration During Diffusion. Device technolorn-- in compound semiconductors has been hampered by several difficult problems not normally encountered with silicon and germanium. 111-V and 11-VI compound semiconductors generally have volatile constituents at temperatures used for diffusion. To achieve specific junction depths in reasonable lengths of time, or to obtain particular impurity distributions and doping levels, it is often necessary to use temperatures which cause surface deterioration and erosion of the wafer. The resultant surfaces are generally unsuitable for devices. The type and extent of surface damage depends to varying degrees on the particular environment of diffusion and on the particular impurity in question. The most common type of deterioration results from simple dissociation of the gallium and the arsenic during diffusin.' The deterioration process is significantly enhanced by thermal gradients in the diffusion zone, usually resulting in vapor transport and condensation at the cooler portion of the system. The resulting damage sometimes appears as a general haziness over the surface or an array of pyramidal etch pits characteristic of the particular orientation. Occasionally, erosion of the surface occurs uniformly over the wafer so that surface loss is not readily apparent. Workers in GaAs usually resort to the sealed-ampule type of diffusion system3"5 rather than the more conventional open system used for silicon and germanium. Another type of deterioration results from direct interaction of the impurity with the surface. The form of deterioration may vary from surface alloying, as in the case of zinc, to direct chemical attack and vapor transport of the reaction products, as in the case of sulfur. Surface alloying with zinc occurs at higher temperatures and source vapor pressures.4 The process is largely controlled by the amount of free gallium on the surface of the wafer in equilibrium with the arsenic lost to the system. The group-VI elements, sulfur, selenium, and tellurium, are commonly used donor impurities for gallium arsenide. These elements are characterized by high vapor pressures and high chemical

Jan 1, 1964

The University of Chicago Press, 5750 Ellis Ave , Chicago, Ill This Press publishes books on a wide variety of subjects of scientific interest, as well as several journals Only a few books on geology have been published, however, and the Journal of Geology. The Journal of Geology: A semiquarterly standard American publication in the geological field. $6 per year, single copies, $1, back numbers, within the past five years, $6 per volume Books on geology: The origin of the earth, by T. C Chamberlin, $2 50, Two solar families, by T. C Chamberlin, $2 50, Quantitative classification of igneous rocks, by W. Cross, J. Iddings, L V Pirsson and H. S Washington, $1.75; Studies in minor folds, by C. E. Decker, $1 50; An introduction to the study of ore deposits, by F. H Hatch, $3, A descriptive petrography of the igneous rocks, by A. Johannsen, $4 50, Essentials for the microscopical determination of rock¬forming minerals and rocks, by A. Johannsen (revised ed ) $3, Outlines of geologic history, with special reference to North America, edited by R D. Salisbury, 8150

Jan 1, 1933

By J. H. Allport, C. Garnsey

During the latter part of 1916 and the early months of 1917, due to war activities, there was a threatened shortage of coal which resulted in panic among consumers and a rush to obtain coal at once at any price. As a result of this insistent demand for immediate delivery, prices were bid up by the consumers to unprecedented heights; spot coal which had previously been selling at from $1.50 to $2 per ton was bid up to $5, $6, and, in exceptional cases, as high as $7.50 or more per ton. Then when the April, 1917, contract period arrived, contracts could be made only at prices ranging from $3 up to $5 and $6 per ton for the year's delivery. This condition caused such a demoralization of the business, and SO much complaint, that some action to regulate prices was considered essential by the National Administration. Lane-Peabody Agreement In May, 1917, a committee under the chairmanship of F. S. Peabody, of Chicago, was appointed by the Council of National Defense, through Mr. Lane, to consider the whole question of bituminous coal. This committee, with the Secretary of the Interior, Mr. Lane, after numerous meetings and long negotiations with the operators throughout the country, announced on June 29 an agreement between the Committee and the producers, fixing a tentative maximum price for bituminous coal throughout the country at $3 per net ton f.o.b. mines, to which was added 25 c. for selling commission to wholesalers. This plan was based on the idea of fixing a maximum price, high enough to greatly stimulate production, with the expectation that the laws of supply and demand would, with ample production, operate to maintain fair and just prices for coal throughout the country.

Jan 1, 1920

By H. W. Maynor, C. J. McHargue

DURING the course of an investigation of materials suitable for use as thermocouples at elevated temperatures by one of the authors, several nlolybdenum-rhenium alloys were prepared. Micrographs of an annealed alloy containing 25 pct Re (intended concentration; analysis not obtained) showed a number of twins, Fig. 1, suggesting a face-centered cubic structure. This note reports the structure and recrystallized wire texture of an alloy containing 25 wt pct Re. Alloys were prepared from 99.9 pct Mo (Fansteel Metallurgical Corp.) and rhenium obtained from the University of Tennessee (purity unreported). Powders were combined and briquetted at 56,000 psi and sintering was carried out at 2400°C for 5 hr in vacuum. Ingots so prepared were swaged at 982.2" to 1037.8oC into wires 0.036 in. diameter, a reduction in diameter of 85.6 pct. These wires were vacuum-annealed 1 hr at 2000°C. A North American Philips 114.59 mm powder camera and nickel-filtered copper radiation were used for structure determination. For the texture determination a Laue-type camera was used with zirconium-filtered molybdenum radiation and, because of the high background, aluminum foil was mounted next to the film. Exposures were taken with the wire perpendicular to the X-ray beam and tilted by 10". It was found that the X-ray pattern could be indexed on the basis of a face-centered cubic structure. Because of difficulties associated with obtaining a good X-ray pattern for this material, accurate parameter determinations were not made. An indicated parameter value of 3.70A was obtained. The X-ray data are given in Table I. The annealed wire texture was observed to be a sharp [111] texture. The spread about this fiber axis was k8" at the surface of the 0.036 in. wire. The annealed wire textures of aluminum have been reported as retention of the [Ill] deformation texture for anneals below 500°C and a new [1121 texture for anneals above 600°C.1 In copper wires, with a [Ill] plus [loo] deformation texture, results indicate a retention of this texture for annealing at lower temperatures and new components or the disappearance of components for annealing at higher temperatures.' The presence of the strong [I111 texture in the molybdenum-rhenium alloy after a 2000 °C anneal suggests that the deformation texture was the same. Acknowledgment The wires used in this study were prepared and heat-treated at the Institute for Atomic Research, and Ames Laboratory, Iowa State College, and the authors wish to express their thanks to the Institute for allowing the use of the material and permission to publish the results.

Jan 1, 1954

By David R. Mitchell

The mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during wartime, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for sepa- rating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concen-trating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435.000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PyRite Production According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By David R. Mitchell

The mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during wartime, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for sepa- rating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concen-trating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435.000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PyRite Production According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By David R. Mitchell

THE mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during war-time, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for separating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concentrating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435,000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PYRITE PRODUCTION According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By Arthur La Motte

I NDUSTRIAL explosives, as distinguished from military explosives, include high explosives and blasting powder. The high explosives which are best known are straight dynamite, gelatin dynamite, ammonia dynamite and permissibles. There are two kinds of blasting powder, saltpetre blasting powder and nitrate of soda blasting powder. Blasting powders are mechanical mixtures of nitrate of potash or nitrate of soda with sulfur and charcoal, highly compressed, granulated and glazed. They ignite from a spark and burn with relative slowness, the rate of burning and hence the rate of conversion into gases depending upon the size of the granulation and upon the degree of. confinement under which the powder is placed. High explosives, on the other hand, are chemical compounds which detonate; that is, when the explosive is subjected to a violent shock, provided in practice by a blasting cap or an electric blasting cap, the molecule of the essential ingredient, usually nitroglycerin, is disrupted and the energy and heat released cause any other explosive ingredients which may be present, such as ammoniuin nitrate or T.N.T., to decompose with a resultant evolution of gases at an extremely rapid rate varying from 6000 to 20,000 ft. per second.

Jan 1, 1924

By J. E. Schiller, S. E. Khalafalla

To improve technology for treating process water, US Bureau of Mines research has shown that magnesium oxide (MgO) has many advantages over lime or caustic soda for precipitating heavy metals. Sludge produced by MgO occupies only 0.2-0.3 times as much volume as the precipitate made wing a soluble base. While a settled, lime-formed precipitate is easily resuspended, the MgO-metal hydroxide sludge becomes cemented together on standing. Settling of the metal hydroxides from a dilute suspension is more complete than precipitates formed with other bases. Virtually any metal that can be precipitated by raising the pH can be treated using MgO. A three fold to fourfold stoichiometric excess of solid reagent is added. The mixture is reacted for five to 10 minutes. Polymer is added, and settling or filtration completes the process. Because of the greater cost of MgO compared with lime, large-scale practice of this technology will probably be limited to water containing 50 mg/L (3 gr per gal) or less of dissolved metals. For such dilute solutions, chemicals are not a large fraction of total treatment costs, so more desirable sludge properties might justify higher chemical expenses. While the MgO process is technically suitable for widespread application, the extent to which it is adopted will probably be determined by a trade-off between the greater cost of MgO compared with lime and the superior properties of the precipitates and their corresponding ultimate disposal costs.

Jan 1, 1985

By E. W. Davis

If the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indications that this new process may make commercially possible the manufacture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to magnetite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe203) to magnetite (Fe3O4) is easily accomplished by heating the ore to a dull red temperature in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900' F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1939

By E. W. Davis

If the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indications that this new process may make commercially possible the manufacture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to magnetite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe203) to magnetite (Fe3O4) is easily accomplished by heating the ore to a dull red temperature in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900' F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1939

By F. W. Glaser

Metal-carbon-boron powder mixtures were hot pressed and the resulting specimens were studied by X-ray diffraction. It was found that regardless of the starting combination of the metal, carbon, or boron powders, a metal boride phase was always the major component in these samples. In the absence of carbon the boride phase formed on hot pressing depended only on the amount of boron present. Two new phases of the system Ti-B were found. They are Ti2B and Ti2B5. The existence of a controversial face-centered cubic phase of formula TiB was confirmed. Electrical resistivities were measured for various boride phases. It was found that the diborides are generally better conductors than the monoborides of the same metal. THE carbides and borides of the transition elements have very high melting points, in the range 2500° to 4000°C, and are therefore of interest as high temperature materials. The literature on the stability or chemical reactivity of these carbides and borides is very scarce. Various investigators'-" have demonstrated a relative instability of certain carbide phases in the presence of boron or boron-containing substances. In a recent publication, Glaserl demonstrated the stability of zirconium-boride (ZrB,) in the presence of carbon at temperatures in excess of approximately 2900°C, while during a preliminary investigation of boride phases, Steinitz' concluded that the diborides are stable in the presence of carbon while the monoborides of the fourth and fifth group are not, forming diborides plus carbides instead. Nelson, Willmore, and Womeldorph" have elaborated on the reaction B,C + 2TiC = 2TiB, + 3C, which was known to occur because of a relative instability of B,C and the great tendency towards TiB, formation at relatively low temperatures (approximately 1200°C). A similar study, involving as starting materials TiO, and B,C and resulting in TiB,, was recently described by Honak4, who observed the beginning of an exothermic reaction of a Ti0,-B,C powder mixture, which, when preheated in a hydrogen atmosphere to approximately 950°C, was carried to about 1600 °C by the heat of reaction. To shed more light on reactions of this type (Metal-C-B), the final product apparently always resulting in a boride phase at the expense of a carbide phase," a systematic investigation was started * Boride phases of various metals, as reported to date, are listed in Table I. and the following is an account of some of the results that were obtained. Materials, Preparation of Samples, Testing Methods The raw materials employed for this work consisted of various carbide, boride, and metal powders. as well as of boron and graphite powders. In cases where commercial grades of carbides were considered unsuitable because of low purity or excessive amounts of graphitic carbon, such carbide powders were prepared by this laboratory. The procedure for the preparation of carbide powders (zirconium carbide, titanium carbide, tantalum carbide, and niobium carbide) consisted of mixing graphite and the respective metal hydride powders in stoichio-metric proportions and subsequent heating of such mixtures in a hydrogen atmosphere in carbon crucibles. The heating was by high frequency to temperatures ranging between 1700" and 2100°C. The resulting carbide was then comminuted and screened to the desired particle size. ZrB, and TiB, powders were produced by the electrolysis of fused salt baths, according to the method described by Andriex.. The borides of niobium, vanadium, tantalum, molybdenum, chro-ium, and iron were obtained by mixing the respective metal and boron powders in the desired proportions. Such metal-boron mixtures were heated in a high frequency furnace to form boride powders. For each metal-carbon-boron group (Tables I1 through XI) a metal, its hydride, carbide or boride were mixed with carbon, boron or boron carbide powders. The additions of carbon, boron or boron carbide powders to any of these metals or metal compounds were calculated to satisfy a particular carbide or boride phase that according to the literature (Table I) had definitely been established by X-ray diffraction work. Samples of powder mixtures were hot pressed in graphite molds that were heated by direct conduction. The specimen dimensions were approximately 2.5X1X1 cm. Hot pressing temperatures were measured optically and maintained for approximately 30 sec under a constant pressure of about 1.3 ton per sq in. Wherever possible, an attempt to obtain maximum specimen density was made by temperature variation. Electrical resistivity testing was done by measuring potentiometrically the voltage drop over a length of 1.5 cm for a current of 10 amp, at room temperature. To obtain electrical resistivities for specific carbide or boride phases, values were plotted as a function of the respective sample densities

Jan 1, 1953

By P. T. Allsman

INTRODUCTION The honor of being the recipient of the Mining Society's Daniel C. Jackling Award for 1966 imposes on me the responsibility to search for the subject that I would be best qualified to discuss. It seems that my experience in the mineral industry — nearly 15 years in private and 30 years in public employment — should uniquely qualify me to comment upon the relationships between the mining industry, mineral engineering as a profession, and government, and the changing economic, technologic, political and social changes that dictate their relationships. Such conditions, the increasing knowledge of the world mineral resource base, the greater demands of an expanding population with a rising standard of living, shall be evaluated with respect to our profession — mineral engineering. In all of these forty or so years, I have been in close touch with many phases of the mineral and energy resource industries, especially those of the United States. Particularly during the past 10 years, I have had a ringside seat at the "goings on" in Washington. During all of this period I have observed and analyzed many of the problems of the industry and its relations with the government. During the past few years, I have had increased opportunity for doing research and have found a need to learn something about the mathematical techniques that are undergoing such a revival since electronic computers were developed. One of these techniques is multivariate analysis, which is a system for correlating a large number of complex variables. By applying this technique to the seemingly chaotic present-day situation, there emerges a course of steady improvement in the minerals resource industries that wars, depressions, and political strife have failed to obstruct for long. In short, I advocate a need for new concepts in mineral engineering to cope with the changes, pos- sibly adding many more specialized areas on one end of the spectrum, and broad engineer-generalist approaches at the other. The meeting place shall be where the intricate mineral resource problems at the frontier of knowledge merge into the socio-techno-logical problems of the world. HISTORICAL INVOLVEMENT OF GOVERNMENT IN MINERAL RESOURCE PROBLEMS Involvement of government in mineral resource problems undoubtedly is as old as government itself. But passage of the Mining Act of 1866, superseded by the Act of 1872, was the first major entry of our Federal Government into the problems of mining. Passage of the law was necessary to resolve many conflicting claims and disputes in mining. The General Mining Law of 1872 and the Mineral Leasing Laws of 1920 apply to millions of acres of public lands and to certain privately owned land on which the mineral rights have been reserved to the Federal Government. The extensive involvement of government in the mineral industry business today often comes as a shock to the mineral engineer who has begun to climb the ladder to the top in his company. He is often poorly prepared to cope with the situation and becomes frustrated and even hostile. Better knowledge of the role of government perhaps would ease his situation. In our political system, private industry is responsible for producing minerals. To make certain that the production is adequate for a peace-time economy, and to guarantee the Nation's security in an emergency, the Federal Government finds it expedient to develop policy and engage in regulatory, educational, and research activities. A few examples will illustrate the varied role of government in relation to mineral problems. In varying degrees many agencies of the Executive Branch of Government have responsibilities that influence the functioning of the mineral and energy industries. In addition, of course, Congress, the Judiciary, and State and local governments exercise great influence. The Department of the Interior is primarily responsible for activities to promote the development and conservation of mineral and fuel resources, and the

Jan 1, 1967

By G. R. St. Pierre, A. Ghosh

In the Si-C-0 system at temperatures of interest in process metallurgy there are four stable condensed phases—silicon, carbon, silica, and silicon carbide (Sic). Silicon melts at 1683oK1 and shows negligible solubility for carbon and oxygen at 1700°K. However, silicon dissolves approximately 1.5 at. pct C at 2500oK.2 Carbon in the form of graphite remains pure and dissolves negligible amount of silicon.' Silica (crysto-balite) melts at 2001°K' and is essentially a stoichio-metric compound. Silicon carbide is a solid and shows negligible deviation from stoichiometry up to approximately 2800oK.2 Besides the condensed phases there is a gas phase

Jan 1, 1970