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By C. W. Sherman, J. Chipman, H. I. Elvander

THE pronounced and usually deleterious effects of sulphur on all ferrous metals and the resultant necessity for its control in metallurgical processes have stimulated many investigations of the system iron-sulphur. The data required for thermodynamic study of the behavior of sulphur in molten iron and steel include the activity and free energy of the dissolved sulphur and its heat of solution. Such data are also of theoretical interest since there is all too little information available concerning solutions of nonmetallic solutes in metallic solvents. It was the purpose of this investigation to attack the problem very directly by a study of equilibrium at several temperatures in the reaction H2 (gas) + S = H2S (gas) [1] K1 = PH2S /PH2 as where the sulphur is present in the liquid iron in amounts up to several percent by weight. Such a method of attack is not new since several careful studies have already been reported. It is planned, however, to extend the study to other metallic solvents and particularly to determine the effects of the various alloying elements on the activity of sulphur in liquid iron. This paper presents the results on molten iron-sulphur alloys containing up to 4 pct sulphur in the temperature range 1530°-1730°C. Literature Review The significant researches on dilute molten solutions of sulphur in iron include those of Chipman

Jan 1, 1951

By U. K. Custred, E. W. Long, V. R. Degner

In 1973, the United States production of marketable phosphate rock set a record in excess of 42 million tons. This production rate is expected to continue to increase, due to the growing international requirement for fertilizer, at a rate exceeding 5% per year well into 1977. One approach towards increasing plant production capacity to meet the growing demand is through large-capacity flotation cells, provided they achieve metallurgical performance comparable to existing smaller cells. A 9-month evaluation test program recently completed at the Haynsworth mine at Bradley, Fla., demonstrated the feasibility of achieving economically acceptable concentrate grade and recovery levels using large, high-capacity flotation cells. The composition of the feed to the Haynsworth beneficiation plant is a typical Florida pebble phosphate matrix composed of phosphorite pebbles ranging in size from approximately 1-1/2 in. down to 150 mesh and intimately associated with a mixture of clay and sand (essentially silica). The feed contains approximately 22 to 28% phosphate reporting as tricalcium phosphate, Ca3 (PO,) 2, or "bone phosphate of lime" (BPL). The flotation section utilizes the double-float procedure typical of Florida plants. The phosphate is first floated away from the silica in the rougher circuit, using crude fatty acid, ammonia, and fuel oil or kerosene. Rougher conditioning is accomplished at 60 to 70% pulp solids with sufficient ammonia added to raise the pH to 9 to 9.5. Following coarse and fine rougher flotation, the concentrate (overflow) streams are joined and conditioned (sulfuric acid cleaned and washed) prior to entering the cleaner circuit where an amine float (cationic reagent and kerosene added in the feed box; pH 7.3 to 7.8) is employed to float the silica. The feed to the coarse rougher circuit averages 29% +35 mesh while the fine rougher feed averages 10%+35 mesh. Primary attention was directed toward the large rougher cell performance (recovery and grade) on coarse feed during the Haynsworth evaluation program. Flotation Cell Test Program A row of three No. 120 size (300 cu ft) WEMCO flotation cells was installed in parallel with an existing air-cell row. The total installed volume of the large cell circuit was 900 cu ft and required a floor space of 306 sq ft. This compared to the air-cell total volume of 200 cu ft and 152 sq ft floor space. (Both floor areas include feed and tails hoppers but exclude walkways.) Fig. 1 is a schematic cross section of the large flotation cell showing the relative location of key mechanism elements. In operation, the rotor generates a fluid vortex extending up along the walls of the standpipe and creating a sufficient vacuum within its core to ingest air into the standpipe/rotor cavity through the air inlet duct. The ingested air mixes with the pulp, which has been recirculated through the false bottom and draft tube, in the rotor. Further mixing occurs as the air and pulp move radially outward from the rotor, finally passing through the disperser into the flotation cell. Flotation is accomplished outside the disperser, where phosphorite laden air bubbles rise and the remaining pulp recirculates down along the cell wall to the false bottom and draft tube. Large-flotation-cell performance is influenced by the ability of the mechanism to (1) circulate, or suspend, the solids in the pulp; (2) ingest air into the rotor cavity; and (3) mix the air and pulp effectively. The proper balance between pulp circulation and air ingestion is a key consideration in achieving good recovery in a course feed application. Large-flotation-cell pulp circulation and air transfer characteristics are significantly influenced by rotor speed and rotor submergence; therefore, these two operational parameters can be used to "optimize" a particular mill application. Fig. 2 maps the hydraulic performance of the WEMCO No. 120 size flotation cell. This map can be used to relate the cell operational parameters which influence metallurgical performance. At a given rotor speed, power intensity (i.e., pulp circulation) is seen to increase, and airflow decrease, as rotor submergence is increased. The inverse relation between power and airflow is due to the two-phase air-liquid mixture density reduction accompanying the increased airflow rate. For any fixed rotor submergence, the power intensity (i.e., fluid circulation) and airflow both increase as rotor speed is increased. The selection of these two mutually related operating conditions (i.e., rotor speed and submergence) was a key consideration in the Haynsworth evaluation program.

Jan 1, 1976

Edward Keller, Baltimore, Md. (communicatioin to the Secretary*):—It is pleasing to note the increasing amount of work on metallurgical problems that is being carried on by exact scientific methods, and the results of such labor issued by the laboratories of our universities. Without doubt, Mr. Bolles's paper will be welcomed by all progressive practitioners. Many of the results which Mr. Bolles presents to as are new; and I take exceptioil to a few minor points only. The first of his concluding remarks is as follows: "Mattes are not homogeneous, but are composed of distinct mineral entitier, and may be likened to igneous rocks, in which the mineral constituents fall out upon the lowering of the temperature and ensuing solidification." He quotes an introductory remark to a paper1 of mine, as follows: "The true chemical character of copper-mattes does not yet seem to have been definitely determined, i.e, it is still more or less of an open question whether they are true chemical compounds, or mixtures, such as igneous rocks." This quotation, taken alone, would convey the impression that Mr. Bolles's conclusion is entirely new. Had he quoted also another paragraph from my paper in question, it would be clear that he was, to a certain extent at least, anticipated. I take the liberty, therefore, to state the substance of my own work. In the paper referred to, I showed the existence of the phenomenon of liquation in mattes, and, continuing, said: " A more direct method to test whether a matte is a compound sulphide or a mixture of individual sulphides was attempted by applying hydraulic separation. A clean piece of matte was selected containing practically no magnetic oxide and of the following composition: Cu, 37.96; S, 24.45; Fe, 33.63; Zn, 1.25; Pb, 1.02 ; Sb, 0.26 ; As, 0.065 ; insoluble, 1.15 per cent. ; Ag, 26.7 ; Au, 0.04 oz. per ton. For such a test it is essential to select a chemically uniform piece, other-

Jan 1, 1905

By Young C. Kim, Francis Martino, Ish Chopra

For the past two and one-half years, various emission control strategies were jointly developed by the University of Arizona and the Homer City Owners to com- ply with the clean air requirements at its Homer City Power Plant. Some of the available options for the SO2 emission control by the Homer City Owners were:l)cleaning of run-of-mine coal,2) scheduling of mining operations at its captive mines, 3) blending the captive mine coal with externally purchased low sulfur coa1,and 4) placing a partial FGD system. This paper describes two specific emission control strategies developed and implemented. These are: 1) production scheduling at the mining face to minimize sulfur variability, and 2) external purchasing of low sulfur coal for further blending. The main objective of this paper is to share our experiences on implementing the developed strategies. This paper emphasizesthe need for proper mine planning on a short-term basis, if the power plant is to meet the desired objective.

Jan 1, 1983

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By S. A. TAYLOR

AN EDITORIAL on the Strike Situation in the Coal mining industry in the New York Evening Post of Nov. 4, 1919, gave what purported to be statistics of the Department of Labor, for a period of two weeks, which showed an average for the year, based on these two weeks, of 32% hours per week. This mode of arriving at the number of hours per week, while not accurate, is not so far off from the facts as to call for any special comment. The report of the U. S. Geological Survey, Department of Coal Statistics, give so the number of days worked in 1917 as 243; reducing the same to hours per week, assuming 8 hours per day, shows a weekly operation of mines at an average of 36J4 hours. But this assumption is not exactly correct, for the reason that it is not very often that the miners work the full 8 hours per day. There are many explanations for this, but it is not pertinent to this statement to discuss them now, as the important thing to consider is whether a 30-hour week would be for the best interest of not only the men themselves, but the public or country in general.

Jan 1, 1920

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 William H. Baer, George M. Carlton, Blake M. Loring

IT is a well known fact that age-hardening alloys remain in a supersaturated, or partially supersaturated, condition only for limited periods of time at temperatures below the solvus. In order to develop optimum properties by subjecting the quenched alloy to precipitation or age-hardening treatment at a specified temperature, it is necessary that the cooling rate be sufficiently high to maintain the required degree of supersaturation of the solid solution. In practical applications the size and shape of the specimens obviously have considerable influence on the rate of cooling and there is need for more information on the effects of various rates of cooling. Cooling rates of quenched aluminum alloys generally have been established by the type of quenching medium, the temperature of the medium and the dimensions of the specimen.1,2,3 Except for the work of Roth3 little quantitative information is available on the measurement of cooling rates of aluminum alloys and the significance of the influence of various cooling rates upon the mechanical properties. The purpose of the present investigation was to study the use of the Jominy test for aluminum alloys (Table I). EXPERIMENTAL PROCEDURE The material for this investigation consisted of extruded rods 1 ¼ to 1 ½ in. in diam. The chemical compositions were as follows: [ ] The modified L-type Jominy specimen with dimensions shown in Fig I was selected as the most convenient means for obtaining a wide range of cooling rates. The standard Jominy specimen was not satisfactory because its cooling rate was not sufficiently high. The four flat surfaces machined at right angles along the length of the L-type specimen to a depth of 0-015 in. facilitated the hardness measurements. The specimens were machined from the extruded stock with no intermediate forging. New specimens were used for each aging experiment. The specimens were given solution treatments of 2 hr duration at recommended temperatures in a Hoskins furnace (Table 2). The temperature of the furnace was maintained constant to ±3°C. No protective atmosphere was necessary because the thin film of oxide that formed on the surface of the specimens had no effect on the hardness measurements.

Jan 1, 1948

By B. D. Cullity

INTRODUCTION THIS investigation of bismuth-selenium alloys was made in an attempt to find a suitable material for use in thermoelectric generators. These devices are simply thermocouple circuits designed for the efficient production of electrical energy from thermal energy, which may in turn be derived directly from solar radiation or from the combustion of fuels. The requirements of a material for use in a thermoelectric generator are obviously quite different from those of a material used in a temperature-measuring thermocouple. Naturally, for power generating purposes, the thermoelectric power (voltage produced per degree difference in temperature between the junctions) must be as high as possible. Furthermore, in order to obtain reasonably high power outputs, the materials used in the generator must have an electrical conductivity which is as high as possible. Finally, in order to minimize heat lost by conduction to the cold junction, the thermal conductivity must be as low as possible. The relation between these several factors and the efficiency of conversion of thermal into electrical energy-the thermoelectric efficiency-has been discussed by Telkes1 in a recent review of the subject. She gives the thermoelectric efficiency as: [ ] For many materials, some of the desired properties (for example, high electrical and low thermal conductivity) are almost mutually exclusive; the problem thus becomes one of finding a material which has the optimum combination of properties. BISMUTH-SELENIUM ALLOYS Work on the equilibrium diagram of the bismuth-selenium alloys has been reviewed by Hanson,2 who gives the diagram reproduced in Fig I. There are two intermediate phases in this system, BiSe and Bi2Se3. The existence of an alpha and beta modification of BiSe has not been demonstrated satisfactorily and the writer found no evidence of it in the present work. BiSe and Bi2Se3 have, like bismuth, a rhombohedral crystal

Jan 1, 1948

By G. T. Smith, R. C. Moyer

Cadmium, along with other impurities such as lead, gallium, germanium and indium, is characteristically found associated with zinc ores, the average ratio of zinc to cadmium being about 200 to 1. The increasing demand for cadmium has led most zinc producers to develop a means for its recovery. The separation and recovery of this byproduct constitutes an important development in the metallurgical field. Zinc sulphide concentrates, principally from domestic sources, are processed at Donora Zinc Works and they assay approximately 60 pct zinc, 30 pct sulphur, 0.37 pct cadmium, and 0.8 pct lead. Concentrates are roasted to convert zinc sulphide to zinc oxide. Sulphur evolved as sulphur dioxide is used to manufacture 60º Baume sulphuric acid by the lead chamber process. The roasted calcine is sintered to remove the remaining sulphur and volatile impurities. Fume from the sintering machines is collected by Cottrell pre-cipitators and sent to the Cadmium Department for cadmium removal. The sintered product, a crude zinc oxide, is then mixed with coke and salt and charged into horizontal retorts for reduction to zinc metal. Furnace residues are then passed through a Waelz kiln which recovers practically all of the remaining zinc as an oxide. This oxide is collected by Cottrell precipi-tators and returned to the sintering plant for further processing. The following discussion covers operating procedure, and equipment used in the Cadmium Department for the manufacture of cadmium and its byproducts. (See attached Flow Sheet, Fig 1.) The production of cadmium may be divided into several steps, each of which will be discussed separately. These steps are as follows: 1. Raw Materials—Sinter Plant Cottrell dust, acid sludge and sulphuric acid. 2. Sulphating—Separation of lead. 3. Purification—Separation of impurities other than zinc. 4. Precipitation—Separation of cadmium from zinc. 5. Briquetting—Preparation of sponge for charging to furnace. 6. Smelting—Distillation of cadmium metal. 7. Remelting—Casting into commercial shapes. 8. Recovery of Rare Metals—Separation of germanium, gallium and indium. Raw Materials The raw material, or Sinter Plant Cottrell dust, from which the cadmium is manufactured, is recovered by Cottrell units collecting fume from two Dwight-Lloyd sintering machines. An average analysis of this dust is 36 pct zinc, 1.5 pct sulphur, 17 pct lead, and 5.5 pct cadmium, with associated elements in smaller amounts. A lesser tonnage of material removed from the sintering machine fans, and called fan cleanings, is also treated for cadmium. It is lower grade material and analyzes approximately 41 pct zinc, 1.2 pct sulphur, 14 pct lead, and 4 pct cadmium. Cottrell dust and fan cleanings are delivered to the Cadmium Department by monorail crane in bell-bottomed dump buckets. Acid sludge and 60" Bauine sulphuric acid are received from the Acid Department. The acid sludge is a mixture of lead sulphate, sulphuric acid and zinc sulphate, and is recovered mainly from the floors of the acid chambers or storage tanks. The acid sludge is delivered to the Cadmium Plant in a lead lined bucket. The 60º Baume sulphuric acid is delivered through a lead pipe to a lead lined storage tank. Sulphating Four well ventilated lead lined sulphating tanks, 8 1/2 ft in diam by 12 ft deep, are used. These are steel tanks lined with 20 lb lead on the bottom and 16 lb lead on the ides, equipped with Hastelloy side agitators. 15 hp motors drive 24 in. propellers at 450 rpm. There are water connections to stuffing boxes to keep sludge from entering the bearings. The tanks are covered with removable wooden lids and are connected to marine plywood

Jan 1, 1950

By M. Dubrovsky, J. W. Evans

A laboratory scale cell (approximately 50 amps current) equipped with a fluidized bed cathode was used in a study of the electrodeposition of cobalt from acidified aqueous sulfate solutions The effect of current density (in the range 0.1 to 1 amp/cm2 of diaphragm), cobalt concentration (4 8 to 100 glliter) and catholyte pH (1 35 to 6 2) on current efficiency and energy consumption were determined. Generally the current efficiency increased with increasing current density and cobalt concentration Current efficiencies were comparable to those reported in the literature for conventional electrowinning

Jan 1, 1981

By NEWTON B. KNOX

CHILEAN mining in the public mind is rightly associated with copper. Chuquicamata with its great hill of copper-bearing granodiorite as well as Sewell and Potrerillos with mineralized volcanic necks together can supply a good proportion of the world's normal necessities of that metal. Chile is an extremely long and narrow country, averaging only 109 miles wide. Its eastern frontier is the Andes and it is on the western slopes of these mountains that the great copper deposits have been discovered. West of the Andes a great longitudinal depres sion has permitted accumulation of nitrates and other soluble salts in the arid north; in the north center it is hidden by a series of cross ranges, but in the center a moderate rainfall makes it the country's most important agricultural region. In the south this depression is drowned and gives rise to a series of straits and fiords. This enormous cleft in the earth's crust is separated from the sea by a coast range of moderate elevation which in the south is represented by a series of islands and mushroom-shaped peninsulas

Jan 1, 1945

By J. B. Neale

FRom the beginning of its activities, the members of the National Production Committee have felt that the following points were essential to the success of its work: The operators must feel that their operations were not 100 per cent. efficient; that they should be courteous and fair in their treatment of their employees; and that they should set an example of hard work and patriotic interest in increased production. Every move made must appeal to the sense of fairness of all parties concerned. The men must feel that in working more faithfully, and consequently producing more coal, they are rendering a distinct service to their Government in the time of its great need. As the workers feel that greater efficiency on their part results only in greater profits to the operators, the advantage to the operator should be lost sight of, as far as possible, and the advantage to the Government in fighting the war emphasized. Both operators and workers should know that the Government considered increased production an obligation, and opportunity for service, resting on both parties and not on the operators or the workers alone, and that both parties could very much better the efficiency of the pre-war period. Had the committee intimated that it thought the coal shortage was due entirely to the idleness and inefficiency of the workers, its campaign would have failed, for the men would have resented the charge because only too frequently their efforts to produce more coal were thwarted by bad management; besides, the operators would have lacked stimulus to better effort. On the other hand, had the impression been given that the committee thought that the coal shortage was due entirely to bad management, the operators would have resented the charge because only too frequently their efforts to produce more coal were thwarted by the idleness and inefficiency of the workers; and the workers, having been thus indirectly pronounced 100 per cent. efficient and patriotic, would have lacked stimulus to better effort.

Jan 1, 1920

By E. O. Lilge, H. Siebert

A design of a multiple-bomb leaching unit particularly suited for the study of heterogeneous reactions, i.e. sol id-liquid-gas interfaces at high temperatures and pressures is presented. The component parts and overall design are described and illustrated in detail. The system has been tested by a limited number of experiments and found to work satisfactorily. Heterogeneous reactions at solid-liquid-gas interfaces, at high temperatures and pressures, are studied in either autoclaves1'4 or bombs5'9. Autoclaves are usually fairly large vessels which have a stirring arrangement incorporated in the design. Mechanical design limits the use of these vessels to relatively low temperatures and pressures. They are particularly well suited to rate or kinetic studies. Bombs can be designed to be operated at high temperatures and pressures, and are smaller vessels; because of this, stirring arrangements are not easily incorporated. In this paper a multiple-bomb system is described, that has been designed to incorporate the desirable features of both the autoclave and the bomb. The described unit has flexibility for an over all study of leaching. Most of the component units in this assemblage are standard equipment, designed and produced by well known manufacturers. No claim is made to the design of this equipment, and although described in some detail, this is done merely for clarity in the elucidation of the system presented. The general layout of the multiple-bomb assemblage is shown in Fig. 1A and 1B. The basic units in this system are: 1) 6 stainless steel 100 ml bombs (Fig. 4)

Jan 1, 1964

By J. J. Friel, E. S. Erickson

Dolomite-fluxed pellets of various compositions were made from magnetite concentrate, hematite concentrate and a concentrate containing a natural mixture of both. Physical properties and reduction test results were used to ascertain proper compositions and firing temperatures. These pellets were subjected to physical tests and to reduction tests. Petrographic and electron microprobe examinations were made to evaluate the effect of composition and fining on the phase assemblage. We interpreted our test results in terms of chemistry and microstructure and related these to properties. This approach enabled w to determine the composition best suited to each of the three concentrates. Compared with acid pellets, dolomite- fluxed pellets of the optimum compositions had similar physical properties but swelled less, softened at a higher temperature, and reduced faster and more completely.

Jan 1, 1983

By K. Mukherjee

Instantaneous resistance change during martensitic transformation in Fe-30 at. pct Ni alloy has been studied using a low-noise electronic system. The smallest signals recorded in this investigation were of the order of 10 pv. These small signals did not show the initial increase reported by earlier investigators to support a double shear mechanism.&apos; A variety of pulse shapes and sizes was observed during "burst" transformations, and these signals were neither a linear function of the size of martensite plates nor of the volume fraction transformed. Even the smallest signals, presumably from single plates, showed complications resulting from elastic and/or plastic deformation, shock wave propagation, and so forth, which are inherent in the growth process of a martensite plate. The time of formation and interface velocity determined froni this experiment agree very well with the pioneering work of Bunshalz and Mehl.&apos; AN Fe-30 at. pct Ni (c0.005 pct C) alloy was used to study the time of formation of martensite plates. Martensitic transformations, unlike the nucleation and growth processes, are usually characterized by an extremely fast reaction rate. During the transformation, the crystal structure changes and this change is propagated through a finite volume of the parent crystal lattice within a very short time interval. The interface between the two phases probably consists of moving dislocations, and the time of formation of the plate depends on how fast this dislocation interface can move. Knapp and Dehlin~er or Cottrell and Bilby mechanisms, or similar dislocation models, can be used to calculate the time of formation of a martensite plate of a given size. In the past, conventional photographic technique475 as well as electrical resistivity techniques"~-" have been used to measure the time of formation of a martensite plate. The specific resistance of the martensitic phase in Fe-30 at. pct Ni alloy is lower than that of the austenite phase. Therefore if a current is passed through a small austenite sample in series with a large external resistance, then one would observe a voltage change across the sample as martensite is formed. Such dc measurements are shown in Fig. 1. The initial large voltage drop in Fig. 1, at the M, temperature, is due to a "burst" transformation where a large number of plates are formed in a cataclysmic manner within a very short interval of time. Even during the later stages of transformation as shown in Fig. 1, one can observe discontinuous voltage changes due to small bursts. In order to resolve the time scale of such discontinuous stages, the voltage signals are amplified and fed into a highspeed oscilloscope. In this investigation a low-noise amplifier was used for the first stage of amplification. The signal to noise ratio was further improved by the design of a pulse transformer. This transformer was capable of amplifying the signal by a factor of six. Voltage signals were studied over a wide time scale ranging from 2 sec to 0.1 psec. I) EXPERIMENTAL PROCEDURE A) Specimen Preparation. Specimens were cut from induction-melted Fe-30 at. pct Ni (<0.005C) alloy and cold-rolled to 0.2 by 1 mm cross section and an average length of 5 cm. During mechanical shaping, the specimens were strain-annealed at 950°C for 24 hr in vacuum. Finally the finished samples were vacuum-annealed at 1000°C for 6 hr and water-quenched to room temperature. The average grain diameter was 0.02 cm. B) Cooling System. The M, temperature of the alloy was -55°C. Fig. 2 shows the arrangement which was used to cool the specimen at a slow rate. The specimens were mounted inside a i -in.-diam hole in the 2-in.-long section of the copper specimen holder. This cavity was filled with silica gel. A dummy specimen was used under identical conditions for

Jan 1, 1969

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. &apos;This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. &apos;This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By C. A. Stewart

I. INTRODUCTION AND GENERAL STATEMENT OF RESULTS. The field-work upon which this paper is based was done in the summer of 1910, and was made possible by the courtesy of the Imperial Copper Co., which gave me access to its property. For their kindness in this respect I wish to express my thanks to W. F. Staunton and Meade Goodloe. Moreover,. B. F. Smith and G. B. Gentry, mining engineers in the employ of the company, gave invaluable assistance by placing maps,. etc., at my disposal, and by discussing with me the problems of the district; and it is a great pleasure to acknowledge this indebtedness to them. In order that the significance of some of the details that follow may be better appreciated at first reading, a general outline of the conclusions reached is given here. In the Silverbell mining-district a series of Palaeozoic limestone blocks is completely surrounded by post-Palaeozoic igneous rocks, intruded in the following order: alaskite, alaskite-porphyry, biotite-granite, andesite, and quartz-porphyry. The biotite-granite is believed to represent a differentiation of the. magma from which the alaskite-porphyry came ; and this conclusion-has an important hearing on the origin of the ores. The intrusion of both alaskite-porphyry and biotite-granite was followed by the emission of magmatic waters, which sericitized and silicified the alaskite-porphyry and granite, and produced in the limestone, by the addition to it of silica, iron, and alumina, great masses of garnet, quartz, and wollastonite. Following close upon these solutions came metal-bearing magmatic waters, which impregnated porphyry, granite, and alas kite with cupriferous pyrite, and deposited in the garnet zones chalcopyrite and copper-bearing pyrite that make important bodies of contact-metamorphic ores. Secondary enrichment has taken place in the disseminated ores in the igneous rocks,. raising their copper-content to 2 per cent. in some cases,. and extensive drilling has been undertaken to block out these deposits. East of the contact-metamorphic deposits there is a fissure-vein of lead-silver ore in the quartz-porphyry. This rock is distinctly younger than the alaskite-porphyry and the granite; and the lead-silver ores belong, therefore, to a period of mineralization distinctly later than the copper-deposition.

May 1, 1912

C. A. ROSE, New York, N. Y. (written discussion *).-Without doubt the excellent results obtained at Ajo will cause surprise among metallurgists; 75 per cent. average capacity and 80 per cent. extraction during the first year of operation of a plant using a new metallurgical process are figures that speak for themselves. It is obvious that the most troublesome feature of the process is the fouling of solutions. The effects of this are most evident in the electrolytic tank house; but apparently the solutions are so heavily loaded with salts that their dissolving power is also impaired. This is indicated by the fact that copper comes into solution during washing after the leaching of the ore is completed, as shown by the decreasing ratio of acid to copper in the various washes tabulated in Table 4, and also by the fact that 4.9 per cent. of the total copper in the ore remains in the tailings in a soluble form. Even though the extraction in leaching and the ampere efficiency in electrolysis would be benefited by keeping the salts in solution at a lower concentration, it is doubtful whether it would pay to decrease these salts by discarding more electrolyte without other changes in the, process, since this would increase the amount of cement copper produced, which is already very large. If, however, it would not disturb the process otherwise, this object could be accomplished by increasing the range of electrolysis, so that solution going to the tank house would contain, say, 4 per cent. copper and 1 per cent. acid, and the solution returned to the leaching plant 1 1/2 per cent. copper and 4.8 per cent. acid, and by increasing the volume of solution to be discarded, this to be taken from the electrolyzed solution returned to the leaching plant. By this arrangement, more salts will be removed from the system per ton of cement copper produced; and if sufficient solution is discarded to keep the iron content down to 1 1/2 per cent. it would he feasible to recover the copper from

Jan 4, 1919