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By C. R. Ince

THE term "differential flotation" is used to denote a flotation operation in which separation is effected between two or more minerals of the same class; e. g., lead sulfide from zinc sulfide, pyrite from blende, chalcopyrite from pyrite, chalcopyrite from blende. At present, so far as published work shows, there seem to be two theories as to the mechanics of differential flotation. The earlier and more generally accepted theory is that the so-called depressing agents alter the surface of one or more of the sulfides in the ore, either by chemical action or adsorption, so that it is no longer amenable to flotation, but that these depressed sulfides can be revived, after the unaffected sulfide has been floated, by reagents which react chemically with the altered surface and make it amenable to flotation. More recently, Professor Taggart1 has advanced the theory that slime adsorption is an important factor in differential flotation. He believes that, with the proper use of a class of agents, which he calls .dispersion agents and which include practically all the depressing agents, one can cause the slime to adsorb differentially on sulfide surfaces. A gangue-slime coated sulfide surface will act as a gangue particle and will not float. If, subsequently, an agent that will remove the gangue-slime coating is added, the sulfide again assumes its original surface and can be floated as an ordinary sulfide. This-is the basis of the slime theory of differential flotation. Timber Butte mill at Butte, Mont., is a typical lead-zinc flotation concentrator. Neihart ore, chosen for investigation in this work, is one of the custom ores treated at that mill. Practice at Timber Butte mill in February, 1928, was as follows: A combined lead-zinc concentrate was first made using 0.2 lb. per ton on the ore of potassium xanthate and 0.03 lb. per ton of Cleveland Cliffs oil after 1.5 lb. per ton of lime and 1 lb. per ton of calcium chloride has been added just before the ball mill. The concentrate was then thickened to 70 per cent. solids. Potassium cyanide to the amount of 0.3 lb. per ton and zinc sulfate in the quantity of 0.5 lb. per ton were added to the thickened pulp and the whole

Jan 1, 1929

By N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts' law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts' law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

PRACTICAL designs for good "home made" molybdenum furnaces are hard to find in the literature. The one described briefly below left something to be desired but was good enough to operate as a rather long (30 in.) two-zone furnace for periods of over 2 months at temperature (1400° to 1600°C) without shutdown. The principal problem in our application was to establish a temperature profile with two distinct constant-temperature zones and no dip between the zones. This and other problems mentioned below would not arise, however, if both zones were operated at the same temperature and if a shorter furnace were acceptable. Since molybdenum windings oxidize very rapidly when heated in air, impervious refractory tubes were used for both the furnace core and the outer jacket tube shown in the accompanying figures. A protective atmosphere of forming gas (10 pct H2, 90 pct N2) was continuously passed through the gas-tight annular volume between the core and outer jacket. The water-cooled copper ends shown in Figs. 1 to 3 sealed the ends of the tubes. Annealed molybdenum wire (40 mil) was wound on the recrys-tallized alumina core (35.5 mm OD by 28.5 mm ID by 30 in.) at a spacing of 0.36 in. The spacing was reduced to 0.29 in. close to the ends to partially compensate for end heat losses. Fig. 2 shows two molybdenum-ground lead taps off the center of the winding to produce the two independect temperature zones. The ground lead was insulated with 1/4-in. alumina tubing and connected to the grounded copper end by passing the wires through the gas port tube and crimping each wire into notches cut at the mouth. To prevent sagging of the core at high temperatures, refractory "troughs" were cut from alumina and mullite tubing to cradle the core. The support "troughs" which were 6 in. long and located about 5 in. from each end of the annular volume also served as radiation shields. In view of the different expansion coefficients and operating temperatures of the core and outer jacket (3.5 in. OD by 3 in. ID by 30 in.), the ends of the tubes were smoothed and squared to produce good sealing surfaces, and the core was ground 1/32 in. shorter than the outer tube. The power terminals were passed through their respective conductor ports which were internally lined with alumina tubing and sealed with Armstrong adhesive A-6 leaving about 1 in. of protruding lead wire for external connections. (Adhesive A-6 is a two-component system consisting of an epoxy-type resin with a mineral fibrous filler and an amine catalyst.) Figs. 1 and 3 show the entire assembly of concentric refractory tubes, copper ends, and sealing o rings, held together with two brass flanges and 3/8-in. bolts with heavy springs for dimensional flexibility. The furnace shell (19 by 19 by 30 in.) consisted of a steel frame with sheets of transite forming a box. The copper ends protruded through two 3.75-in. circular holes cut at the center of each transite square end. Thermal insulation next to the transite exterior was effected by K-23 B&W bricks alld in a central volume of approximately 9 by 9 by 30 in. a row of K-30 bricks was lined up to support the hot assembly. The rest of the volume around the outer

Jan 1, 1965

By C. R. Ince

The term "differential flotation" is used to denote a flotation operation in which separation is effected between two or more minerals of the same class; e. g., lead sulfide from zinc sulfide, pyrite from blende, chalco-pyrite from pyrite, chalcopyrite from blende. At present, so far as published work shows, there seem to be two theories as to the mechanics of differential flotation. The earlier and more generally accepted theory is that the so-called depressing agents alter the surface of one or more of the sulfides in the ore, either by chemical action or adsorption, so that it is no longer amenable to flotation, but that these depressed sulfides can be revived, after the unaffected sulfide has been floated, by reagents which react chemically with the altered surface and make it amenable to flotation. More recently, Professor Taggartl has advanced the theory that slime adsorption is an important factor in differential flotation. He believes that, with the proper use of a class of agents, which he calls dispersion agents and which include practically all the depressing agents, one can cause the slime to adsorb differentially on sulfide surfaces. A gangue-slime coated sulfide surface will act as a gangue particle and will not float. If, subsequently, an agent that will remove the gangue-slime coating is added, the sulfide again assumes its original surface and can be floated as an ordinary sulfide. This is the basis of the slime theory of differential flotation. Timber Butte mill at Butte, Mont., is a typical lead-zinc flotation concentrator. Neihart ore, chosen for investigation in this work, is one of the custom ores treated at that mill. Practice at Timber Butte mill in February, 1928, was as follows: A combined lead-zinc concentrate was first made using 0.2 Ib. per ton on the ore of potassium xanthate and 0.03 lb. per ton of Cleveland Cliffs oil after 1.5 lb. per ton of lime and 1 lb. per ton of calcium chloride has been added just before the ball mill. The concentrate was then thickened to 70 per cent. solids. Potassium cyanide to the amount of 0.3 lb. per ton and zinc sulfate in the quantity of 0.5 Ib. per ton were added to the thickened pulp and the whole

Jan 1, 1930

By W. L. Phillips

Nickel alloys containing approximately 0.5, 2.0, and 6.0 at. pct of Os, Pd, Ru, and Rh were Prepared by vacuum melting. Tension tests were carried out at 25°, 500°, 800°, and 1000°C; stress-rupture tests were carried out at 650° and 800°C. The room- and elevated-temperature tensile strength, as well as the stress-rupture life, increased for the same atomic percent in the order palladium, rhodium, ruthenium, osmium. The ductility decreased with increasing concentration or temperature for a given concentration. The results are discussed in terms of solid-solution theory. BOTH solid-solution strengthening and weakening have been observed in alloys. The simple rules which have been suggested to explain alloy strengthening are subject to several exceptions and deviations based on atom size and valency effects. The purpose of the present investigation was to extend the knowledge of the effect of solid-solution alloying on the mechanical properties of several Ni-Pt group metal alloys at room and elevated temperatures. The platinum group metals, osmium, ruthenium, rhodium, and palladium were chosen as the solute elements because of their different valencies and atom sizes. Nickel was chosen as the base material because of the large amount of previous literature available on nickel alloys. EXPERIMENTAL PROCEDURE Grade A Carbonyl nickel powder having the following composition: C, 0.07 pct; Fe, 0.013 pct; Mn, 0.0005 pct; Si, 0.016 pct; Mg, 0.0003 pct; S, 0.003 pct, was purchased from the International Nickel Co. The platinum-group metal powders were purchased from A. D. Mackay Co. The powders were weighed, cone-blended for 4 hr, and vacuum-melted into 1-in.-diam billets, approximately 2 in. long. The ingots were homogenized for 5 hr at 1800°F before being extruded into 1/4-in. rods at 2100°F. The alloy compositions are shown in Table I. Typical impurity values were not significantly different than that of the as-received nickel. All alloys were single phase. The lattice parameter of each alloy after the heat treatment described below is also included in Table I. Each alloy was annealed at 2200°F for 1 hr and air-quenched to comparable grain sizes (ASTM G.S. No. 4-5). The rods were then machined into test samples 0.160-in. diam and 0.750-in. gage length. Tension testing was carried out in an In-stron tension-testing machine at a strain rate of 0.02 in. per in. per min. An extensometer was used to determine the room-temperature yield stress. Stress-rupture testing was carried out in an Arc Weld stress-rupture unit. All testing was performed in air. EXPERIMENTAL RESULTS A) Room-Temperature Mechanical Properties. The 0.2 pct yield stress, ultimate tensile strength, and elongation for all alloys tested at room temperature are plotted as a function of atomic percent solute element in Fig. 1. The ultimate tensile strength for the same atomic percent increases in the order palladium, rhodium, ruthenium, osmium. The yield strength at low concentrations, -0.5 at. pct, increases in the order osmium, palladium, ruthenium, rhodium. At higher concentrations, 3.0 and 10.0 pct, the yield strength increases in the same order as the tensile strength. Both yield strength and tensile strength increase rapidly ini-

Jan 1, 1964

By R. M. Bird

Few persons outside of the foundry trade have any conception of the great variety of sands now regularly specified and furnished, nor of the differences in foundry practice frequently resulting from apparently minor changes in sands. Conditions in each locality where the sands are mined and prepared necessitate special equipment designed to perform the work efficiently. The description that follows of the foundry-sand producing operations is typical of the areas in New York and New Jersey, and particularly refers to the operations of the George F. Pettinos Co. A few years ago the so-called Albany sands were dug by simple methods and hauled by horsecart to railroad. Depletion of sand near railroad sidings and extended use of automotive power have appreciably extended the area from which sand is now being dug. It is not unusual to haul 5 miles to the railroad. As stripping is quite shallow, 6 to 18 in., and the banks of usable sand generally run from 12 in. to 4 ft., it is economical to work the bank by benches so narrow that the overburden can be thrown by hand shovel to the exposed bottoms. In effect the top soil goes back to where it was, but on a lower level. Consequently the general surface appearance of a mined acreage is the same as before. This condition is in fact cutomarily required when a farm owner sells his sand in the ground. After such replacement, in the course of 3 to 5 years the soil is no less fertile than it was before mining. The sand itself varies as to grain and bond vertically and also along the breast. No mechanical equipment has been developed to compete with hand shovels and no machine has as yet been devised that grades the sand as required. Uniformity of sand, as shipped, depends first, last and all the time on the man on the job. Mixing equipment can change the appearance of the sand and mask its lack of uniformity, but it will never correct wrongly graded sand, dug from the bank. Modern methods of testing are helpful in setting up standards against which the man in the bank can compare his sands, but a good bank foreman is the only assurance that the sand, as dug, matches the required sample.

Jan 1, 1926

By Robert E. Tally

A recorded in the account of the Annual Meeting, on another page, the report of the tellers showed that all men nominated by the committee, which included Messrs. Wilber Judson, E. DeGolyer, W. A. Weldin, J. A. Norden, J. D. MacKenzie, Wilfred Sykes and S. Skowronski, were duly elected to the offices for which they were nominated. Robert Tally, who was elected to the presidency for 1931-2, is well known to all our members not only because he has served on the Board of Directors since 1928, but through a brief outline of his great achieve¬ments in his chosen profession pub¬lished in our issue of December last. The vice-presidents, Howard N. Eavenson and H. A. Guess, are also well known to our members. Mr. Eavenson has not only been chairman of the Coal Division since its organization, but was also a Director during 1917, 1918 and 1919., Mr. Guess was Director in 1926, was elected a vice-president by the Board last year to fill the vacancy created by the election of Mr. Bassett to the presidency, and is now elected to the usual three-year term.

Jan 1, 1931

By E. P. Whittemore

Experience with the ASC multipoint gas lift system was obtained in Colonia zone of the West Montalvo field near Oxnard, Calif. The wells in this pool produce from depths varying from 10,500 to 12,000 ft. Oil gravity is generally 14 to 15' API with a few extremes of 12 and 20" API. Some salt water is produced which causes some very viscous emulsions. Viscosities at 150F (which is the approximate wellhead temperature) vary from 5,000 to 100,000 SSU. Most of the production is by gas lift, although a few wells are produced by rod and hydraulic pump. About half of the gas-lift wells are on continuous flow and the remainder are on intermittent lift using large, ported, pilot-operated valves for single-point transfer of gas from casing to tubing. Gas-liquid ratios vary from about 6 to 10 Mcf/bbl of gross fluid lifted. Wells are produced to a 450-psi trap system. The following remarks will be confined to intermittent lift only, since this is the type of lift which has been achieved with the ASC valve system. The maximum gross fluid which has been produced by single-point intermittent lift is about 350 B/D in 3-in. tubing and 200 B/D in 21/2-in. tubing with gas-liquid ratios of approximately 7 to 9 Mcf/bbl. Some design changes could reduce this ratio. The ASC multipoint system has provided production as high as 480 BOPD in 21/2-in. tubing with gas-liquid ratios just under 4 Mcf/bbl. To be able to apply the multipoint system, it is recommended that a detailed explanation be obtained concerning transition-point pressure and stabilizer setting—what its significance is to the string design, how it may work for or against the operation of the well, how it is related to tubing sensitivity and how it affects the unloading operation. The unloading operation may only be of academic interest in a technical paper, but to the production foreman, unloading and setting the valves in operation is a very real problem and should be understood in detail. One item touched lightly in the paper was the unloading valve. This valve controls the maximum pressure at which the well can be operated. When lifting heavy viscous fluids, it is most important to set this valve for the maximum possible realistic operating pressure at the surface. If the well lifts easily, it is simple to set the ASC valves at a lower operating pressure and the unloading valve will remain closed; but if the well happens to be heavier to lift than anticipated, it may be desirable to operate on the unloading valve itself and use all the energy obtainable at the bottom of the hole. In the Colonia pool very heavy wet-gas gradients are experienced due to the viscosity of the liquid and the dense mist which is left behind a slug of fluid. There are many combination strings of 3- and 21/2-in. tubing. This aggravates the wet-gas gradient problem and provides wet-gas gradients of about 50 to 70 psi/1,000. An advantage which multipoint lift has provided is increased slug efficiency through better maintenance of pressure under the slug and decreased fall back as the slug passes up the tubing. By using multipoint injection, wet-gas gradients have been reduced to about 30 psi/1,000. This has reduced bottom-hole operating pressure and given a production increase. The ASC valve is not a simple device. It's operation is difficult to understand, and it must be understood to be used efficiently in gas-lift design. Operating problems are difficult to diagnose—whether they be caused by the fluid lifted, valve malfunction, lift gas rate, or operating pressure. Calculations and reasoning are required to find out what is causing the problem. Inherent in the ASC valve is the inability to create large pressure differentials across a slug. Large differentials may be required to overcome the inertia of very viscous fluid as it is being accelerated in the bottom of the hole. This is tied back to the design of the unloading valve and is one reason for the importance of setting the unloading valve for the highest possible operating pressure. ~u; to the narrow spread the ASC valves provide, it is impossible to cycle slower than about 24 cycles/day on choke control. If small production of 150 BOPD and less is expected, a surface time-cycle controller will be required if the most economical operation is to be achieved. To achieve a satisfactory operation, the operator must keep a record of any changes made in the operating pressure of the ASC valves. Anything which may cause changes in casing pressure in excess of the stabilizer setting will change the valve operating pressure, and if this is not noted from daily inspection of the well casing-tubing pressure recorder charts, the operator will lose control of the well. Significant results can be achieved using ASC valves; however, considerable knowledge is required to design with them, and attention to detail is required for satisfactory field operation.

Jan 1, 1965

By H. Foster Bain

Jan 1, 1910

By Will Mitchell, T. G. Kirkland, C. L. Sollenberger

R. S. Handy (Santa Rosa, Calif.)—It would be interesting to learn the comparative results of treating the Korean scheelite ore described in this paper according to the following procedure: I—Follow the procedure described in the paper to the recovery of the sulphides by flotation. 2—Dilute the residue from the sulphide flotation strongly with water and disperse the contained colloids by adding a mixture of 75 pct sodium silicate and 25 pct quebracho to dispersion point. 3— Settle the dispersed pulp and decant the supernatant colloids. 4—-Dilute, settle, and decant the pulp until the settled residue is crystalline. Not over 10 pct of the tungsten minerals should follow the colloids. 5—Treat the settled residue by flotation, having established the proper pH. Oleic acid homogenized with cresylic acid or kerosene is more selective for scheelite than is oleic acid alone. (The recovery of the contained tungsten minerals should be practically complete in this operation.) 6—Deflocculate the tungsten concentrate from step 5 with the same dispersion agents as in step 2 and treat the deflocculated pulp by gravity. The minerals that tend to float with scheelite are generally of low specific gravity and the separation is efficient. The heavier contaminants, such as pyrrhotite and magnetite can be removed magnetically, leaving a practically pure scheelite. E. J. Pryor (Imperial College of Science and Technology, London)—It occurred to me that instead of using temperature as a differentiating control, more precision might be obtained with a reagent of a type we developed here for the flotation of high grade fluorspar in cold pulps. This reagent, which is manufactured on a modest scale in England, is based on oleic acid, which has been modified by our patented process to ensure complete stable dispersion at any desired concentration in water. It thus becomes possible to utilise unimolecular layers with good selectivity. In the fluorspar flotation for which we developed it, it is possible to hold a tight control on depressing quebracho for the calcite without substantial loss of flu-orite, and recovery exceeding 99 pct is not uncommon in the mill where it is in use, even under wintry conditions. No attempt has been made yet to extend the use of the reagent, as we have not completely overcome

Jan 1, 1952

By E. J. Bartosh

In the brief period from November 1936 to September 1937, the Wilmington oil field developed far beyond all expectations. Decline in some wells appears very rapid, but it is too early to draw definite conclusions, as the majority of wells are maintaining very large and steady output. Heavy curtailment in the central area, which has developed the largest wells, makes it impossible to arrive at a satisfactory estimate of decline. The field is producing oil from the Repetto (lower Pliocene) and Puente (upper Miocene) formations, which are of the same age as formations producing at Torrance, El Segundo, del Rey or the marginal fields of the Los Angeles Basin. All of these fields are underlain by schist. The Long Beach field, northeast of Wilmington, is productive throughout 3000 ft. of Repetto-Pliocene series and also approximately 3000 ft. of Miocene formations, whereas at Wilmington only 700 to 800 ft. of Repetto and 2500 ft. of Miocene formations contain oil and gas. This paper gives a brief summary of the history and development of the field to Sept. 15, 1937, showing the subsurface conditions as they exist with the field only partly developed. History of Development The Wilmington oil field, 20 miles due south of Los Angeles, adjacent to Los Angeles harbor and about midway between the cities of San Pedro and Long Beach (Fig. 7), was producing oil as early as 1932 and only came into prominence as a major oil field of Southern California in the fall of 1936, when the General Petroleum Corporation of California completed Terminal well No. 1 from the upper Miocene, at a depth of 3625 ft., for a daily production of 1500 bbl., 20" gravity A.P.I., thereby establishing discovery of the Terminal zone. As early as 1925, or during the close of the development of Torrance oil field, a number of wells were drilled in the Main Street area looking for

Jan 1, 1938

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.' The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968

By E. T. Turkdogan

The activity of sulfur was determined as a function of composition of ferrous sulfide by equilibrating with hydrogen sulfide-hydrogen gas mixtures at 670° , 800°, and 900". The present results supplement the available data over the composition range from 36.6 to 39.5 pct S. The X-ray lattice spacing measurements made are in accord with the available data and indicate that the limiting composition FeSl.008 may be taken for the iron-iron sulfide equilibrium. The growth rate of ferrous sulfide on iron was measured by reacting iron strips or blocks in hydrogen sulfide-hydrogen gas mixtures. Owing to the slow approach to equilibrium between the gas phase and the surface of the sulfide layer, The sulfidation experiments were carried out for several days. It is shown that the growth rate ullimately proceeds in accordance wilh the parabolic rate law. From the parabolic rate constants and the thermodynamic data on iron sulfide the self-difiusivity and chemical diffusivity of iron in ferrous bisulfide are evalualed. The self-diffusivity of iron thus derived zs found to increase with increasing sulfur content. THE ferrous sulfide known as "pyrrhotite" is a non-stoichiometric phase having a wide composition range from about 50 to about 58 or 60 at. pct, depending on the sulfur activity. RosenQvistl studied the thermodynamics of this phase over wide ranges of temperature and composition. Hauffe and Rahmel' and Meussner and ~irchenall~ studied the parabolic rate of sulfidation of iron in sulfur vapor. By using markers, these investigators showed that the iron cations were the predominant diffusing species in iron sulfide. This is confirmed decisively by the self-diffusivity measurements of condit4 who showed that the self-diffusivity of sulfur in ferrous sulfide is several orders of magnitude lower than the self-diffusivity of iron. Although much has been learned from these studies about the Fe-S system, further research on this subject was considered desirable for better understanding of the physical chemistry of iron sulfide. This work was confined to the study of the kinetics of sulfidation of iron in hydrogen sulfide-hydrogen gas mixtures. The results of this study are given in two consecutive parts. Part I, the present paper, is on the parabolic rate of sulfidation of iron and the diffusivity of iron in ferrous sulfide. The second paper, Part 11, is on the kinetics of the surface reaction between hydrogen sulfide and ferrous sulfide. EXPERIMENTAL Three types of experiments were carried out: i) equilibration of ferrous sulfide with gas of known E. T. TURKDOGAN, member AIME, is Manager,Chemical Metallurgy Division, Edgar C. Bain Laboratory for Fundamental Research, U. S. Steel Corp., Research Center, Monroeville, Pa. Manuscript submitted March 6. 1968. ISD sulfur potential; ii) X-ray studies of ferrous sulfide; and iii) measurements of the parabolic rate of sulfidation of iron. Equilibrium Studies. About 1 g of iron powder or foil. contained in a small recrystallized alumina crucible ind suspended from a calibrated silica spring, was reacted with a hydrogen sulfide-hydrogen mixture of known ratio until no further change in weight was observed. %hen the gas composition was changed and the new state of equilibrium was established after several hours of reaction time. The composition of the sulfide was obtained from the initial weight of the sample and the weight after equilibration. X-Ray Studies. The lattice parameters of some of the equilibrated samples were determined using the General Electric XRD-5 diffractometer with a cobalt tube (no filter) set at 40 kv apd 10 ma; the CoK, radiation was taken as 1.79020A. Observed 220 and 311 diffraction peaks of silicon served as an internal comparison standard to correct for possible misalignment of the goniometer. The lattice parameters of the sulfide phase were calculated from the corrected Bragg angles of the 110 and 102 peaks. Rate Studies. In the initial experiments attempts were made to measure the parabolic rate of sulfidation by measuring the gain in weight of a thin iron strip, -0.05 cm thick, suspended from a silica spring in the reacting atmosphere. The preliminary experiments showed that this technique was not reliable for the measurement of the parabolic growth rate of the iron sulfide layer. In the subsequent experiments the data on growth rate were obtained by measuring, on a microscope stage, change in the thickness of the sample after reaction for a specified time in a hydrogen sulfide-hydrogen mixture of known sulfur activity. For each reaction time a new sample was used. Precision-machined iron blocks, 0.5 by 2 by 5 cu cm, were de-greased and annealed in hydrogen for several hours prior to the sulfidation rate measurements. The experiments were carried out at 670°, 800°, and 900°C in gas mixtures having the ratios, and 1.0 for periods of times from a few hours up to 8 days. Apparatus and Materials. A vertical globar tube furnace with a 3-in.-long uniform temperature zone was used. The glass tube fittings were fused on the zircon reaction tube, 1.5 in. diam. The temperature was measured with a Pt-10 pct Rh/Pt thermocouple placed in the hot zone of the furnace inside the reaction tube (an alumina thermocouple sheath was used). A separate thermocouple was used for the temperature controller which maintained the furnace temperature constant within about 2°C. Anhydrous liquid hydrogen sulfide and oxygen-free dry hydrogen from gas tanks were used in preparing the gas mixtures by the constant head capillary flow-meters. In all cases volume flow rate was 1000 cu cm per min at stp, corresponding to a linear velocity of about 6 cm per sec at 800°C; under these conditions

Jan 1, 1969

By E. R. Borcherdt

RECENT years have seen great progress in drilling practices. The partial change from heavy drills and stopers to lightweight airleg machines has had great impact on stoping and drifting methods. The change was sparked, of course, when the Germans applied tungsten carbide to drill bits during World War II. This invention made it possible to drill nearly cylindrical blastholes, with a very mini- mum of drill steel changes, so that small fast-cutting bits* could be used without sacrifice of powder-loading density at the bottom of the hole. This is one of the few instances of increased efficiency through reduction in size. Usually the opposite is true. Application of these lightweight drills and small bits has lessened the vibratory stresses set up in the drill steel rod, and rod breakage has been greatly reduced. During the past several years phenomenal reduction in drill steel breakage has resulted from the use of carburized rods. These rods are now supplied by several manufacturers, with carburization of both the exterior and interior surfaces of the hollow drill steel. The rods are heat-treated over their entire length after the completion of bit connections, collars, or lugs (in the case of 7/8 Hex and round steel). This eliminates breakage from the usual metallurgical notch existing in conventional rods-there are instances of more than 2000 ft of drilling in hard ground before breakage. Steel rod failure results from fatigue checks, at right angles to the rod axis, progressing to a point where parting or breaking of the rod occurs. There are many of these checks in a used rod. Only the most advanced check causes the break, but with a small additional amount of drilling another check advances to the breakage point, and most of the value of reconditioning is lost. Since the development of carburized rods, the practice of discarding drill rods after the first break may be economically justified.

Jan 4, 1957

By D. I. Bardos

The occurrence of Laves phases (AB,) in various binary alloy systems has been reviewed in recent papers.13 Iron forms Laves phases with Sc-, Ti-, V- and Cr-group elements. However, two of the corresponding Laves phases with cobalt, namely MoCo, and WCo,, are missing. Nickel forms binary Laves phases with Sc and Y, but not with any Ti-, V-, or Cr-group element. These conditions are schematically illustrated in Table I. That electron concentration is a significant factor in determining which type of Laves phase is formed in a given case was recognized long ago by Laves and Witte,4 This concept has been more recently applied to Laves phases formed by transition ele-ments. It now appears that the average electron concentration (average number of electrons per atom outside of the closed shells of the component atoms) may be an important factor also in determining whether or not a Laves phase can occur at all in a given system. As shown in Table I, in the transition element systems considered Laves phases are absent at electron concentrations of 8, or larger (to the right and below the double line in Table I). These absences clearly cannot be accounted for on atomic size considerations, as evidenced by the many inconsistencies apparent in Table 11. While the ideal radius ratio for Laves phases is 1.222, in the systems which do have Laves phases the ratios of CN 12 radii range from 1.10 to 1.46. The consistent absence of Laves phases at RA/RB< 1.10 might be attributed to the low values of these radius ratios. However, Table II shows that absences also occur irregularly throughout the radius ratio range covered. In a previous paper7 it was concluded that, in transition element systems forming u-phases, silicon may act as an acceptor of electrons, thus stabilizing the u-phase at electron concentrations higher than

Jan 1, 1962

By H. H. Taft

The mining possibilities of the volcanic area south of Bel-mont, Nye county, Nevada, have long been known. Some of the old-time prospectors knew that gold existed there. Its remoteness from any source of supplies, its long distances from water, the absence of game, and more, perhaps, the lack of grass for animals to subsist upon, has made this an unattractive region in which to search for mines. The decline of the Comstock mines, the exhaustion of sundry large and rich ore-bodies, the high cost of mining, marketing, and, particularly, the ruinously high freight-charges upon refractory ore that had to be shipped to distant smelters, have kept investors out of Nevada for the last few gears; and mining people have hardly yet awakened to the importance of To-nopah, Goldfield, and perhaps the newer and less developed districts. The discovery of Tonopah by J. L. Butler, who located the Mizpah claim in May, 1900, and the fortunes soon realized there, attracted many people. As the boom declined, many went away, some scattering out into the surrounding country, and the population is now about 7,000. In the fall of 1902 a discovery of gold was made 23 miles south, in what is now known as the Sandstorm group, 4 miles NW. of Goldfield. In the winter of 1903—4 the Combination, January and Florence mines were discovered, and shipments of high-grade ore soon followed. In January, 1905, there were 10,000 people in Gold-field. In June, 1904, rich gold-ore was found 85 miles SE., at the foot of the south end of the Kawich mountains, but this discovery was kept quiet until a re-location could be made. On August 10, 1904, the Bullfrog claims, and a month later the Ladd mountain and neighboring claims, were located. The Shoshone group was located September 24. This district is

Jan 1, 1907

By S. C. Sun, T. Chao

The reaction of gaseous sulfur trioxide with different aluminum-bearing minerals for the conversion of their alumina content into water soluble sulfates has been investigated. Theoretical considerations indicate that this reaction is thermodynamically feasible and that preferential sulfatization can be accomplished. The five minerals tested were gibbsite, boehmite, diaspore, kaolinite, and halloysite. In general, over 90% sulfatization could be achieved in 1 hr when using sodium sulfate as an additive at a temperature between 500° and 600°C. It was found that sulfates of the light alkali and alkaline earth metals exhibited some effectiveness in promoting the sulfa-tizing reaction. Selective sulfatization of alumina in a mixture of calcined halloysite and ferric oxide was accomplished. The gas-solid type of sulfatizing reactions have become increasingly important in recent years for the treatment of the oxides of such nonferrous metals as cobalt,&apos; nickel,&apos; manganese,3 zinc, and copper.4-6 Similar reactions were attempted in the present investigation for the recovery of aluminum from the low grade aluminous ores. Unlike the Bayer process in which silica is a serious contaminant, or the acid processes whereby iron usually causes difficulties, the reactions between gaseous sulfur trioxide and various aluminous minerals could hopefully be selective for aluminum. THEORETICAL CONSIDERATIONS Reactions between aluminum-bearing minerals and gaseous sulfur trioxide have been shown respectively in Table I and Fig. 1 to be thermodynamically favorable for temperatures below 1000°K approximately. Calculations of the thermodynamic functions were where ?G, ?H, ?Cp and ?S are changes in free energy, enthalpy, constant-pressure specific heat, and entropy of the system under consideration, respectively; T is the absolute temperature, R the universal gas constant, and K the equilibrium constant. Thermochemical data so far available for these calculations were based on sources given by T. Chao.7 In Table I, the free energy values indicate that reactions between the gaseous sulfur trioxide and

Jan 1, 1968

Not many accounts of mining methods or labor conditions in the mines in early days can be found; all that have seemed to be authentic have been included in the preceding chapters. In practically every field opened before 18.10 the first coal was recovered by quarrying, or strip mining, the operations, of course, being by hand and on a very small scale; new places were opened as soon as mining became difficult or expensive. Where it became necessary to drift into the hillsides, the first coal was taken out by sleds, and later by small wagons, the power being supplied by the miner, often assisted by dogs. Wooden rails then came into use with small cars running on them. These cars were very small, usually holding only a few bushels; in the Belleville, Illinois field as late as 1863 cars having capacities of 10, 12, 14 and some as large as 30 bushels were in use. It was not until late in the 1830&apos;s that horses or mules came into use for haulage purposes in the Pittsburgh region, although some had been used in the Richmond, Virginia field at an earlier date. Coal was usually undercut by hand and wedged down, until explosives came into general use, and in nearly every field the coal was forked into the cars, the fine coal, or slack, being left in the mine. Hours worked were very long, but few records remain to show what they were at different places and times; there was undoubtedly a great variation between districts and mines. Roy stated a miner could often produce 5 or 6 tons in a day of 8 or 9 hours in a 5 or 6 foot seam, but in another seam possibly could mine only 3 1/2 to 4 tons. He estimated an average day&apos;s work in a four foot seam at about 3 1/2 tons.1 In a strike in the Belleville field in 1863 it was found that an average skilled miner in the field could probably produce 4 to 5 tons a day.2 This was only the coarse coal loaded and did not include slack. In 1873, a coal undercutting machine was tried at a mine about two miles from Brazil, Indiana, said to be the first coal machine ever invented in the United States. It was run by a 5 H.P. steam engine (later to be changed to compressed air), and consisted of an iron rim, four feet in diameter with movable steel teeth placed about one foot apart. The rim

Jan 1, 1942

By Kenneth Cottingham

The year 1941 brought a considerable increase in drilling activity in Ohio. In 1940, the total of wells completed was 1228, whereas in 1941 it was 1561, or an increase of approximately 27 per cent. Of the 1561 wells, 333 were oil wells, 701 gas wells and 527 dry holes. The completions for the past five years are shown in Table I; the number of productive oil or gas wells for the year 1941, arranged by producing formations, are given in Table 2; the number of wells, oil, gas or dry, completed in each county in 1941, in Table 3, and wells by sands in Table 4. The production of oil increased by about 500,000 bbl. in 1941, nearly all of the increase being in Pennsylvania grade. In 1940, the total production was 3,052,000 bbl. from 25,500 wells. In 1941 the total production was 3,547,534 bbl. from 24,801 wells. The increase in production is chiefly due to the Clinton pool in Clayton township, Perry County, which is briefly men- tioned later in this review. The number of oil wells, by grades of oil, and the total quantities produced are shown in Table ;. Annual oil production for five years is listed in Table 6. The average prices paid for crude in 1941 were slightly higher than in 1940 These 1941 prices, with dates of change, are shown in Table 7. The maximum production of natural gas in Ohio was in the year 1915, when the total was just under 80 billion cu. ft. The maximum consumption occurred in the year 1916, and was approximately 169 billion cu. ft. For the past several years, Ohio has ranged from eighth to eleventh, in order of gas production for the different states, being in tenth place in 1940. In the matter of consumption, however, Ohio remains in fifth place. Preliminary figures for 1940 indicate that production of natural gas increased II per

Jan 1, 1942

By Kenneth Cottingham

The year 1941 brought a considerable increase in drilling activity in Ohio. In 1940, the total of wells completed was 1228, whereas in 1941 it was 1561, or an increase of approximately 27 per cent. Of the 1561 wells, 333 were oil wells, 701 gas wells and 527 dry holes. The completions for the past five years are shown in Table I; the number of productive oil or gas wells for the year 1941, arranged by producing formations, are given in Table 2; the number of wells, oil, gas or dry, completed in each county in 1941, in Table 3, and wells by sands in Table 4. The production of oil increased by about 500,000 bbl. in 1941, nearly all of the increase being in Pennsylvania grade. In 1940, the total production was 3,052,000 bbl. from 25,500 wells. In 1941 the total production was 3,547,534 bbl. from 24,801 wells. The increase in production is chiefly due to the Clinton pool in Clayton township, Perry County, which is briefly men- tioned later in this review. The number of oil wells, by grades of oil, and the total quantities produced are shown in Table ;. Annual oil production for five years is listed in Table 6. The average prices paid for crude in 1941 were slightly higher than in 1940 These 1941 prices, with dates of change, are shown in Table 7. The maximum production of natural gas in Ohio was in the year 1915, when the total was just under 80 billion cu. ft. The maximum consumption occurred in the year 1916, and was approximately 169 billion cu. ft. For the past several years, Ohio has ranged from eighth to eleventh, in order of gas production for the different states, being in tenth place in 1940. In the matter of consumption, however, Ohio remains in fifth place. Preliminary figures for 1940 indicate that production of natural gas increased II per

Jan 1, 1942