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By John Mark Patek

Knowledge of the relative floatability of silicate minerals is increasing in importance as flotation is being applied to the concentration of nonsulfides. Many silicates are in themselves commercial products amenable to concentration by flotation. Moreover, the selective flotation of other nonsulfide minerals, such as cassiterite, depends largely upon the floatability of associated gangue silicates. Differences in floatability existing between the various silicates have not- been sufficiently appreciated; for example, the feldspars that differ greatly in floatability have generally been merely treated as "feldspar." It was the purpose of the work described in this paper to determine by experiment the differences in floatability between silicates; to investigate the causes for such differences, and to discover a means of predetermining approximate floatability without the necessity of experimentation. Determining Floatability The relative floatability of 20 silicates so selected as to represent all of the more common silicate types1 was obtained by flotation tests enumerated in Table 1. The mineral to be floated was crushed dry on a steel plate, and screened repeatedly during crushing through an 80-mesh screen in order to produce a sand with all grains as close to 80 mesh as possible. The sand was placed in dilute (6N) hydrochloric acid until free of soluble foreign material, and then washed with tap water about ten times in order to remove both acid and fines. The resultant product, which averaged 82 per cent plus 200 mesh, was floated in 50-gram charges in a 50-gram Denver celluloid flotation machine with 0.008 gram of terpineol, and from 0.01 to 0.05 gram of oleic acid in a solution acidified with sulfuric acid. The degree of separation of one mineral from another was determined by counting under a nlicroscope the grains of each mineral, both in the concentrate and in the tailings, and comparing their relative abundance in each. Unless the comparison showed a decided difference in amount,

Jan 1, 1935

Cyanidation and Concentration of Gold and Silver Ores. By J. V. N. Dorr and Francis L. Bosqui. Second edition, completely revised. Mc-Graw-Hill Book Co., New York. $8.50.-First issued 13 years ago, this book has become a milestone in the literature of mining and metallurgy. Mr. Dorr, with the assistance of F. L. Bosqui, has completely revised the book. Its comprehensive picture of ore dressing and hydrometallurgical methods are of importance to mining engineers and operators throughout the entire field. Operating data and methods, flowsheets, testing procedures, and many miscellaneous methods of extracting bullion are given. The book is divided into two sections, the first discussing principal unit processes involved in gold and silver recovery, and the second describing with flow diagrams a number of typical treatment plants selected from the more important gold and silver mining areas in various parts of the world. International Conference on Coal Preparation in Paris. English Language edition of transactions.-The transactions of the recent conference in Paris will be presented in the form of 6 issues of the revue de l'Industrie Minerale, and may be purchased for 3000 francs per set. About 60 papers were presented at the meeting, covering a wide range of interesting subjects. Ad- dress subscriptions to: Secretariat de la Societe de l'Industrie Minerale, 19 rue du Grand-Moulin, Saint-Etienne (Loire) France.

Jan 1, 1951

By J. E. Metcalfe

Proceedings of the Fourth Empire Mining and Metallurgical Congress, Great Britain 1949. Part II published at the Offices of the Congress in London, England, 1139 pp. The price of these proceedings is £ 2. The parts may be purchased separately at a cost of £ 1 each.-Part I of this book covers a report of the organizing committee, the inaugural meeting and presidential address, banquet at Guildhall, welcome by Sir Richard Livingstone at Oxford. and final session. Technical session and papers are also covered in Part I. Part II covers such topics as coal, present-day trends in mineral dressing and metallurgy. Mining Engineer's Survey Manual. By J. E. Metcalfe. Published for "Mine & Quarry Engineering" by Electrical Press, London, 1951. 341 pp., illus., charts, diagrs., tables, 8 ¾ x 5 1/ in., cloth, 30s., available from Percival Marshall & Co., Ltd., London, and British Book Centre, 122 East 55th St., New York 22, N. Y. Beginning with a brief treatment of surveying fundamentals and a discussion of the correlation of surface and underground surveys, this practical manual continues with descriptions of surveying practice both above and below ground including stopes, inclined shafts; etc. Space is devoted to sampling and valuation, geological considerations, and descriptions of modern surveying instruments. The organization of survey operations is covered in the last chapter.

Jan 1, 1952

By W. O. Philbrook, K. M. Goldman, G. Derge

T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer

Jan 1, 1951

By H. W. Hitzrot

SEPARATING a mixture of particle sizes of material suspended in a liquid medium is by no means an exact science. Selecting machines for individual classifying operations is even more difficult. The plant operator's own background is of course invaluable, and considerable help may be obtained from technical articles, talks with sales engineers, and handbooks on ore dressing. These several sources of information, however, are difficult to marshal in proper perspective for the major decision on classification units that an operator may be called upon to make. To the present writer's knowledge this assembly of facts is not available in handbooks, and technical papers are scarce on classification equipment developed in the past five or six years. It is believed that this paper will be helpful to users of classification equipment at this particular period in the development of hydro-classification. For easy reference the following classification units now available and in use in metallurgical and industrial operations are listed below, with a brief description of each. Unit-type classifiers, bowl classifiers, and bowl desiltors are all rectangular tanks, slightly tilted, with reciprocating rakes or screws to remove settled sands. The unit-type classifier, Figs. 1 and 2, is available in widths from 14 in. to 20 ft and lengths up to 40 ft. The shallow bowl of the bowl classifier, Fig. 3, equipped with rotating rakes, is superimposed on the lower end of the tank. Reciprocating rake compartments for this design range from 18 in. to 20 ft wide. Bowl diameters vary from 4 to 28 ft. The flat-bottomed bowl of the desiltor, Fig. 4, of relatively large diameter, is equipped with rakes rotating outward and partly over a pit, which is created by extension of the rectangular tank into and under the bowl section. Bowl desiltors are available with reciprocating rake sections 4 to 20 ft wide and bowls from 20 to 50 ft in diam. The bowl desiltor is used for applications beyond the range of the bowl classifier. The hydroseparator, Figs. 5 and 6, is a circular tank equipped with slowly rotating rake arms, set on a slope, with interrupted rake or spiral blades to move the settled solids to a central discharge cone. Tank diameters vary from 4 to 250 ft. Tank depths at center are 2 to 3 ft for small units and up to 25 ft for larger units. Hydraulic classifiers of the sizer and super-sorter types, Figs. 7 and 8, are narrow, deep, rectangular tanks divided by vertical baffles into a series of pockets. Hydraulic water is added near the bottom of each pocket. Perforated constriction plates, spiral flow arrangements, or jets are used to disseminate the water under pressure (hydraulic water) throughout the bed of material in the pocket. Discharge valves on each pocket are operated automatically by a pneumatic mechanism, a pincer-type mechanism, or a pressure control and motor combination actuated by a hydrostatic tube within the pocket. Hydraulic classifiers are available in 4, 5, 6, and 8-pocket units of varying constriction plate areas to suit conditions. There is now a jet sizer of unit pocket design that can be made up in 1 to 25 sections or more to accommodate sizing requirements. The hydroscillator, Fig. 9, is a rectangular tank set on a slope of 3 to 4 in. per ft. A bowl is superimposed on the lower end. The bowl bottom is an oscillating rubber-covered disk, perforated to allow hydraulic water introduced beneath the disk to set up a teeter bed and thus produce an oversize or rake product exceptionally free of slimes, and material minus the mesh of separation. A shallow dam at the periphery of the bowl allows the coarse or oversize fraction to spill over and drop down into the tank compartment, where it is moved up the deck by reciprocating rakes. The material, minus the mesh of separation, overflows a circular and stationary weir which is several inches higher than the dam on the oscillating disk. It is carried off in a circular launder in the usual manner. These units are available in bowl diameters from 4 to 14 ft and with reciprocating rake compartment widths to suit the tons per hour to be handled. Centrifugal classifiers include the solid bowl centrifuge and the cyclone classifier. The solid bowl centrifuge, Fig. 10, consists of a truncated cone fixed to a horizontal shaft and rotating at high speed. An internal spiral rotating at slightly less speed continuously removes solids deposited on the inner surface of the cone, or bowl. Feed enters the cone by means of the hollow center shaft. Overflow leaves through ports at the large end of the cone, and oversize solids, moved by the spiral, exit through ports at the small end. Centrifugal classifiers of this type are available in cone diameters from 18 to 54 in. The cyclone classifier, Fig. 11, is a stationary cone having a cylindrical upper section and a lower cone section. Feed is introduced tangentially into the upper cylindrical section under pressure from a hydrostatic head or by means of a pump. Centrifugal force thus induced effects a classification within the cone, the fine sizes being carried off in the overflow through an opening at the top of the cylindrical section. Coarse solids at relatively high pulp density exit through a control valve at the apex of the lower cone section. Cyclone classifiers are available in 3, 6, 12, 14, 24, and 30-in. diam. The cone classifier, Fig. 12, is a steel-plate cone with sides usually about 60" from horizontal. It contains no rotating mechanism. Feed enters a feed-well at center and classification is effected by gravity and pulp density. Fines are carried off in the flow over a peripheral weir at the top of the cone. Settled solids exit through an opening at the apex. An apex valve actuated through levers and rods by the pulp density in the lower cone section is usually supplied. Diameters are usually maximum at 8 ft.

Jan 1, 1955

By R. D. Russell, R. M. Farquhar

SOTOPIC tracers have become an important aid in following the progress of chemical processes in the laboratory. It has recently been found possible to utilize a system of naturally existing iso-topic tracers to obtain information about the geological history of lead ores. Common lead, such as is found in lead deposits, is a mixture of four stable isotopes having atomic weights 204, 206, 207, and 208. Of these, the last three are identical with the lead isotopes produced as stable end products of the radioactive decays of uranium and thorium: the first, lead-204, is not known to be produced on the surface of the earth by any process. Since uranium and thorium Occur in the surface regions of the earth in amounts comparable with lead, and since the half-lives of uranium and thorium isotopes are of the same order as the age of the earth, they produce the radiogenic lead isotopes in amounts comparable to the amount of nonradiogenic lead present. Every significant exposure of a sample of lead to uranium and thorium will therefore lead to the permanent alteration of the lead isotope ratios in that sample. It is this unique property of lead that serves as a means of tracing the history of a lead sample in terms of its contacts with the radioactive elements. If lead from a lead mineral has been analyzed with a mass spectrometer, the measured isotope ratios are determined entirely by the isotope ratios of primeval lead, which are identical for all minerals, and by the particular history of the sample. It follows that for samples from any particular geological area, observed differences in the isotopic composition are enough to distinguish different geological histories. An illustration of the qualitative application of this statement is given in Table I by analyses of some galenas from the western Cordillera. Samples from deposits in Pre-Cambrian sediments have very different lead isotope ratios from those of the ores in the Paleozoic sediments. Although the two types are associated closely geographically, it is apparent that they have had quite different histories and have probably been emplaced at quite different times, as the ideas outlined in the following section suggest. Even when applied quantitatively, a lead isotope analysis can never indicate a unique history of any lead sample. However, it greatly restricts the choices available and combined with other geological and geochemical data can lead to a much better understanding of the genesis of lead ores. General Character of Lead Isotope Variations: Early isotopic analyses of common leads by Nierl showed that geologically younger leads were generally richer in isotopes of masses 206, 207, and 208, with respect to that of mass 204. This regularity of measured lead isotope ratios can be easily observed by plotting each of the ratios Pb207/Pbm and Pb205/ Pb204 against the ratio Pb206/Pb204. In both graphs the points lie scattered closely about a well defined mean curve. It was immediately supposed that this regularity resulted from the growth of all leads from a common primeval lead present at some time, To, early in the earth's history. Lead in the outer part of the earth would become continually enriched in the radiogenic isotopes as a result of the uranium and thorium intimately associated with it. The subsequent extraction of some of this lead and formation of a lead mineral free of the radioactive parents provide samples of lead existing in the earth at the time of mineralization, T. Younger leads in general will be richer in the radiogenic isotopes because they have been associated with uranium and thorium for a longer time. Then lead ratios would be given by the formulae: (Pb206/Pb204)YTPb^/Pb204) +f "(u201) kdt T (Pb207Pb204)r = (Pb208/Pb204)T0 + J (U295/Pb204) k' dt T (Pb208/Pb204) t = (Pb208Pb204 + J (Th204) A." dt [1] where A, A', and A" are the decay constants of U238, U285 and Th232. Summaries of measurements of radioactivity of surface rocks, such as given by Faul,2 are of limited

Jan 1, 1958

By Waldemar Dyrssen

I CANNOT agree with the results obtained by the committee. The gas obtained per pound of coal is too high in calorific value and the amount of gas is too large. It should require about 190 cu. ft. of oxygen per 1000 cu. ft. of gas and not 75.14 cu. ft. as is given on page 35 of the report, or about 2.5 as much. Calculating the calorific value per pound of coal from the coal analysis given on page 34, according to Dulong's formula, the gross and net calorific heat are about 12,890 and 12,430 B.t.u., respectively, which is about 18,600 and 17,900 B.t.u., respectively, per pound of carbon in the coal. This is an unusually high figure, as ordinary bituminous coal has less than 18,000 gross B.t.u. per pound of carbon. Assuming, however, that the calorific values calculated are correct, the following results are obtained. On page 35, the net calorific heat in the gas per pound of coal is given as 12,856 B.t.u. and calculation for the gross value shows it to be about 13,950; in other words, the gas contains (13,950 - 12,890) ÷ 12,890 = 8.2 per cent. more heat than the coal on a gross basis and (12,856 - 12,430) ÷ 12,430 = 3.4 per cent. more on a net basis. The calculated amount of carbon in this gas per pound of coal gasified is about 0.688 lb., or nearly the same as in the coal (0.6972) and the gross and net calorific heat per pound of carbon in the gas are 20,300 and 18,710 B.t.u. which are 9.1 and 4.5 per cent. more than for the carbon in the coal. These calculations show that the results given in the report cannot be correct. There must always be some heat losses in the gasification of coal, in radiation from the producer, and in sensible heat in the gas; there must be some loss of carbon in ashes and in soot, and there are always tarry vapors in the gases that are condensed and do not appear in the fixed gases. From the excessive heat in gas per pound of carbon contained therein, it can also be concluded that the percentage of hydrogen in the gas is too high, from which it follows that the moisture decomposed is too high and that more free oxygen must be used.

Jan 11, 1924

By Nathaniel Herz

The use of zinc dust for precipitating the pecious metals from cyanide solutions is well established now in many places, and has many advantages over the shavings method of precipitation. Although much work has been done o,n methods of testing zinc dust, as yet. no absolutely positive test has been devised to determine the value of the material. Certain facts are known, but often it happens that results on a working scale are not as expected from the laboratory tests. The purpose of this paper is to record some obscrvations made while testing a large variety of zinc-dust samples in the laboratory. W. J. Sharwoodl has described standard analytical methods, which have been followed, with the changes noted. The regular determinations include zinc oxide, by solution in ammonia and ammonium chloride, lead, and precipitating efficiency. In some cases cadmium was determined by a method similar to that described by J E Clennell.2 I will discuss the precipitating-efficiency test in detail. The procedure is as follows: "A solution of potassium silver cyanide is prepared by dissolving 10 grams of silver cyanide (AgCN) and 5 grams of 99 %' potassium cyanide in a little water and diluting up to 1000 cc. It is then adjusted by addition of a little more XCN or AgCN until the solution indicates from 0.12% to 0.15% free KCN by titration with standard silver nitrate. The titration is best made by using a 10-cc. or 20-cc. sample, adding 1 CC. of 2 % potassium iodide, and a slight excess of ammonia, as the end point is then sharper. Or 15 grams of pure crystallized XAg(CN)2 may be dissolved in a liter of water and 1.5 grams XCN added. " Weigh out 0.5 gram zinc dust into a 300-cc. beaker. Add a few cubic centimeters of watcr and stir until zinc is well mixed, then pour in 250 cc. of the prepared solution, stirring vigorously. See that all lumps are broken up, and continue stirring for fully five minutes. Stir occasionally (at least every 10 minutes) until the end of two hours from the addition of the solution. Then filter upon an 11-cm. filter, wash precipitate thoroughly, sprinkle with test lead, wrap it carefully in the paper, place in a scarifier with about 20 grams test lead, burn paper cautiously in muffle, scorify five minutes, cupel at low temperature and weigh silver. Milligrams silver obtained from 0.5 gram zinc X 0.0606 = percentage precipitating efflciency."³

Jan 1, 1916

By A. Szirmae, Hsun Hu

The early stages of recrystallization in a 70 pct cold-rolled Si-Fe crystal of the (110) (0011) orientation were studied with a Siemens electron microscope. Orientation studies based on electron-diffractzotz. patterns confirm the results of previous texture analysis. The driving energy for recrystallizatior and the critical radius for growth were calculated from the dislocation energy and the energy of the subgrain bourzdaries, and it was found consistent with the observed size of the recrystallized grains. The recrystallization characteristics of crystals with different initial orientations are discussed. The recrystallization of cold-rolled (110)[001] crystals of Si-Fe has been widely studied by various investigators.1-4 Their results on both deformation and annealing textures are in good agreement. The rolling texture after 70 pct reduction consists mainly of two crystallographically equivalent (111) [112] type textures and a minor component of the (100) [011] type. The latter is derived from the deformation twins, or Neumann bands, which are formed during the early stages of deformation and later rotate to the (100) [011] orientation upon further rolling reduction. Between the two main (111) [112] type textures, there is some orientation spread, because of which very low intensity areas appear in the pole figure. If these very low intensity areas are considered to be a very weak component in the texture, then a (110) [ 001 ] orientation may be assigned to them. When this rolled crystal is annealed at a sufficiently high temperature for recrystallization, the texture returns to a simple (110) [001]. The purpose of the present investigation was primarily to seek a better understanding of the recrystallization process by using the electron transmission technique. The (110) [0011 type of crystal was selected because orientation data for it are well known from previous studies with conventional techniques. Direct observations on the recrystallization of such a crystal have also been made by using a hot-stage inside the electron microscope, and the results will be reported in another paper. MATERIAL AND METHOD A single-crystal strip of the (110) [001] orientation was prepared from a commercial grade 3 pct Si-Fe alloy by the strain-anneal technique.= The strip was approximately 0.014 in. thick, and was rolled 70 pct at room temperature to a thickness of 0.004 in. Specimens were cut from the rolled strip and were annealed in a purified hydrogen or argon atmosphere. They were then electrolytically polished in a chromic-acetic acid solution to very thin foils. Best results were found by polishing first between two narrowly spaced flat cathodes with the specimen edges coated with acid-resisting paint, followed by polishing between two pointed electrodes until a hole appeared in the center as described by Bollmann.6 It was found that a thin transparent film always formed along the thin edges of the polished specimen. This film was then removed by rinsing the specimen very briefly in a solution of alcohol with a few drops of HF or HCl. RESULTS AND DISCUSSION 1) The Deformed Crystal. From the electron-diffraction patterns taken at various areas of an as-rolled specimen, the texture components as deduced - from ordinary pole-figure analysis were confirmed. Over most of the areas where orientation was examined, a (111) pattern with a [112] direction parallel to the rolling direction was obtained. This corresponds to the main deformation texture of the (111) [112] type. In a few areas the diffraction pattern was (100) [Oil], corresponding to the minor-texture component derived from the Neumann bands. The (110) [001] orientation, which corresponds to the very weak intensity area in the pole figure, was found infrequently. A typical example of the deformed matrix having the (111) type main texture is shown in Fig. 1, where (a) is the microstructure and (b) is the diffraction pattern taken from that area. It was also frequently observed that in other areas more or less continuous rings of weaker intensity were superimposed on the simple (111) diffraction pattern, suggesting the presence of a wide range of additional orientations. Other evidence indicated that the recrystallization characteristics are different in these two different types of areas. The hot-stage observations which provide this evidence will be discussed in another paper. AS shown in Fig. l(a), numerous dislocation-free areas of very small size are embedded in the "clouds" of high-dislocation density. This indicates that the deformation of a single crystal, even after a rolling reduction of 70 pct, is far from uniform on a micro-

Jan 1, 1962

By W. A. Mudge

This discussion will be limited to malleable, commercially pure nickel and some high-nickel alloys, containing more than 50 per cent of nickel, which are produced by The International Nickel Company, Inc. at its Huntington works, West Virginia, from electrolytic nickel or from a nickel-copper sulphide matte. The principal sources of nickel are sulphides of nickel, copper and iron, which are found in the large deposit of pyrrhotite-pentlandite-chalcopyrite ores in the Sudbury area of Ontario, Canada. Pentlandite, a complex nickel-iron sulphide, is the nickel carrier. These ores are concentrated, roasted, and smelted to remove considerable iron and sulphur and to produce a nickel-copper sulphide matte. Separation of the component sulphides of this matte, followed by electrolytic refining, results in the production of electrolytic nickel and electrolytic copper; direct refining of a selected portion of the matte gives the nickel-copper alloy, Monel. FUNDAMENTAL OPERATIONS Melting of the metallic materials is done in natural gas-fired, acid furnaces of the open-hearth, or reverberatory, type, having capacities of 6 to 20 tons; in three-phase, basic, electric-arc furnaces, having capacities of 7 to 20 tons; and in basic, high-frequency induction furnaces having capacities of ½ to 3 tons. Malleable, commercially pure nickel is melted in the acid open-hearth furnace. The charge is sulphur-free, electrolytic nickel, containing 99.9 per cent nickel* and clean mill scrap. Monel, containing approximately two thirds nickel and one third copper, is produced by roasting the nickel-copper sulphide matte to an oxide, smelting the oxide with charcoal in a 20-ton, acid open-hearth furnace, adding clean mill scrap, duplexing to a 20-ton, basic, electric-arc furnace, and refining in this furnace with a lime-fluorspar, carbide slag. Inconel, containing nickel, 80 per cent; chromium, 14 and iron, 6, is melted in the 7-ton electric-arc furnace or the 3-ton induction furnace. The charge is electrolytic nickel, ferrochromium and clean mill scrap. These are the fundamental operations. High-nickel alloys are produced from one of these three materials by additions of suitable amounts of manganese, aluminum, silicon or copper. For example, the age-hardenable alloy, K Monel, is produced from Monel by the addition of approximately 3 per cent of aluminum, and D nickel is produced from nickel by the addition of approximately 4.5 per cent of metallic manganese. For conversion to rods, bars, sheet, strip, tubing and wire forms, by hot-working and cold-working operations, the molten materials are teemed into ingots ranging in size from 14 by 14 by 60 in., 3300 lb., to 36 by 36 by 48 in., 18,000 lb. All ingots are overhauled mechanically before hot working.

Jan 1, 1946

By R. W. Gurry

THERMODYNAMIC calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a. better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganeie, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B203 in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1943

By William J. Gillich, Gerald L. Moss

PREVIOUS studies of the shock loading of randomly oriented polycrystalline aggregates have firmly established that, after rather short load duration, hydrostatic compression closely approximates the shocked state.' However, McQueen deduced from pressure measurements with good time resolution that, during shock loading, metals begin to undergo a stress relaxation at the yield stress. He suggested that the relaxation is due to plastic deformation accompanying the change from a one-dimensional compression to a three-dimensional, hydrostatic, compression.' Stress relaxation may occur faster as stress is increased above the yield stress, but the existence of unidirectionally compressed states for finite times suggests that the concept of a unidirectionally distorted lattice should furnish considerable insight into the mechanical behavior of materials subjected to shock loading. Here, a crystallographic analysis is presented for the hypothetical situation where atom motion may be considered as unidirectional which, as indicated above, is a useful extension of the macroscopic concept of shock loading to the microscopic domain. Only motion caused by the com-pressive forces is treated; i.e., lattice vibrations upon which this motion is superimposed, as discussed by Fitzgerald, are ignored.3 The purpose of the analysis to be presented is to develop a description for single crystals of the lattice rotations that occur for idealized uniaxial strain deformation. The usefulness of such an analysis in realistic deformation is to give a method of specification of those properties of an initially distorted lattice which would affect the subsequent deformation. Non-axial complications that arise experimentally, such as off-axis rarefaction waves, must be treated in proper context. Consider the material element shown in Fig. 1 and let the compression be uniform at all regions of the element. Then, any interior point of the element is displaced in proportion to its distance from the base of the element. Accordingly, if the top of a unit element is displaced by an amount, (-K), with respect to the base, a point P(X, Y) will be displaced by (-KY). Crystal planes are, therefore, rotated by the compression. Analysis of this rotation may be accomplished from the geometry shown in Fig. 1 where the line OP is the edge of the plane {hkl} and N is its normal. The orientation of the crystal plane with respect to the shock direction is specified by the angle, before deformation. After deformation the edge of plane {hkl}

Jan 1, 1969

By M. B. Standing, D. L. Katz

Equilibrium data are reported on the composition and densities of coexisting vapor and liquid phases as a function of Pressure and temperature for four hydrocarbon systems prepared from crude oil and natural gas. The data were observed over a range of pressures from 1000 to 8220 Ib. per sq. in. and at temperatures ranging from 35' to 250°F. The compositions of the hydrocarbon systems were such that the critical temperatures of the mixtures were lower than the range of the investigation. Under these conditions, it is shown that the composition of the systems has a marked effect upon both the absolute value of the equilibrium constants and the change of the constants with pressure for the several components comprising the system. From weight-balance considerations, it has been possible to construct the partial phase diagram of a mixture of a 49.9" A.P.I. crude oil and natural gas having a gas-oil ratio of 3660 cu. ft. per barrel. Descriptions of the apparatus used, the analytical procedure, the material used, and the equilibrium measurements are included. A knowledge of the physical behavior of naturally occurring hydrocarbon mixtures is fundamental to the treatment of many problems in the production, transportation and rehing of petroleum. The recent discoveries of pools having formation pressures up to 7500 lb. per sq. in. and higher, and the development of full-scale equipment to operate at pressures of 5000 lb. per sq. in. or more have greatly increased the need for knowledge of the composition, temperature, pressure and density relationships of coexisting vapor and liquid hydrocarbon phases. The following paper presents the results of investigations upon 22 mixtures of natural gas and crude oil of known com~o~itio~ that had been brought to equilibrium under controlled conditions of temperature and pressure. Data are presented upon the densities and compositions of the coexisting vapor and liquid phases for four different systems containing hydrocarbon material having boiling points from minus 2 5S°F. to well over I000 F. The data were observed Over a pressure range from Iooo Ib. per Sq. in to 8220 lb. Per sq. in. and a temperature range from 35' to 2 50°F. The accepted method of computing the physical relationship between two coexisting phases of a hydrocarbon mixture is by use of the "equilibrium constant" K as proposed by Souders, Selheimer, and Brown. definition,

Jan 1, 1944

By M. B. Standing, D. L. Katz

Equilibrium data are reported on the composition and densities of coexisting vapor and liquid phases as a function of Pressure and temperature for four hydrocarbon systems prepared from crude oil and natural gas. The data were observed over a range of pressures from 1000 to 8220 Ib. per sq. in. and at temperatures ranging from 35' to 250°F. The compositions of the hydrocarbon systems were such that the critical temperatures of the mixtures were lower than the range of the investigation. Under these conditions, it is shown that the composition of the systems has a marked effect upon both the absolute value of the equilibrium constants and the change of the constants with pressure for the several components comprising the system. From weight-balance considerations, it has been possible to construct the partial phase diagram of a mixture of a 49.9" A.P.I. crude oil and natural gas having a gas-oil ratio of 3660 cu. ft. per barrel. Descriptions of the apparatus used, the analytical procedure, the material used, and the equilibrium measurements are included. A knowledge of the physical behavior of naturally occurring hydrocarbon mixtures is fundamental to the treatment of many problems in the production, transportation and rehing of petroleum. The recent discoveries of pools having formation pressures up to 7500 lb. per sq. in. and higher, and the development of full-scale equipment to operate at pressures of 5000 lb. per sq. in. or more have greatly increased the need for knowledge of the composition, temperature, pressure and density relationships of coexisting vapor and liquid hydrocarbon phases. The following paper presents the results of investigations upon 22 mixtures of natural gas and crude oil of known com~o~itio~ that had been brought to equilibrium under controlled conditions of temperature and pressure. Data are presented upon the densities and compositions of the coexisting vapor and liquid phases for four different systems containing hydrocarbon material having boiling points from minus 2 5S°F. to well over I000 F. The data were observed Over a pressure range from Iooo Ib. per Sq. in to 8220 lb. Per sq. in. and a temperature range from 35' to 2 50°F. The accepted method of computing the physical relationship between two coexisting phases of a hydrocarbon mixture is by use of the "equilibrium constant" K as proposed by Souders, Selheimer, and Brown. definition,

Jan 1, 1944

By G. Derge, Lo Ching Chang

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By G. Derge

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By Charles Austin

IT has been known for several years1 that certain alloys of the Konal type, containing commercial cobalt (99.32 per cent C0 and 0.42 per cent Ni) and varying amounts of ferrotitanium, exhibit very high tensile strengths at 600°C. However, their pro-portional limits and yield points are rela-tively low. Published data1 for the alloys quenched in water from 950°C. and then tested at 600°C. are summarized in the upper section of Fig. I. Similar specimens that were aged at 650°C. for 72 hr., after quench and prior to testing at 600°C., gave the results shown in the lower section of Fig. I. TABLE I.-Analysis of Material I Percentages Constituent Sample Sample Sample 3125 3124 3123 Si 0.25 0.51 o.6o Fe 4.15 10.70 13.17 Ti I.15 3.58 4.70 Mn 0.30 0.41 0.42 Co (by difference)^ 94.15 84.80 81.71 The cobalt from all three samples, united and tested for nickel, gave 0.54 per cent Ni based on the weight of cobalt. In the present work the investigation of the properties of these materials has been extended by a study of the tensile deforma- tion characteristics in moderately long-time tests at 600°, 700° and 800°C. after quenching from various solution tempera-tures. In addition, some metallographic studies have been made to correlate with the deformation tests, and to obtain in- FIG. 1.-EFFECT OF VARYING AMOUNTS OF FERROTITANIUM (FE2TI) ON PHYSICAL PROPER-TIES OF COMMERCIAL COBALT. (C. R. Austin.1) Upper section. Tested at 600°C. after water-quenching from 950°C. Lower section. Tested at 600°C. after water-quenching from 950°C. and aging 72 hr. at 650°C. FIG. 2.-PORTION OF QUASI-BINARY DIAGRAM COBALT-FE2TI AS DETERMINED METALLOGRAPH-ICALLY. formation on the quasi-binary system Cobalt-Fe2Ti. The material, very kindly furnished by the Westinghouse Electric and Manufac-turing Co. in the form of hot-swaged rods of 3/16-in. diameter, analyzed as shown in Table I. The alloys, when originally made up,1 were based upon an iron-titanium com-pound, Fe3Ti, as indicated by the work of

Jan 1, 1940

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By Graham Bright

Metal mines were developed long before coal mines and the early lighting of underground workings was effected by torches and candles. The early coal mines were outcrop workings and little trouble was experienced from gas, but as the mines became deeper and shaft mines were opened it became apparent that an open-fame lamp was exceedingly dangerous where gas occurred. No satisfactory way of lighting gaseous coal mines was found until Sir Humphrey Davy brought out his famous safety lamp in 1815. The introduction of the Davy lamp was a great step forward but it was unsatisfactory from a light standpoint because the gauze absorbed a large percentage of the light given out by the flame. Clanny corrected this by the introduction of a cylindrical glass lens, which not only permitted a free distribution of the light from the flame but added greatly to the safety by eliminating the possibility of the flame coming in contact with the gauze and by protecting the flame against air currents. A very complete story of the flame safety lamp since its inception is given in the U. S. Bureau of Mines Bulletin No. 227, by J. W. Paul, I;. C. Ilsley and E. J. Gleim, published in 1924. A little more recent publication, known as Safety in Mines Research Board Paper No. 4, entitled "The Light Power of Flame Safety Lamps," by R. V. Wheeler and D. W. Woodhead, was published in England in 1927. The flame safety lamp was the only lamp available for gaseous mines for about 100 years. Although the incandescent electric lamp has been in use over 50 years, it was not found safe to use this lamp from wired circuits in gaseous locations. The storage battery was advocated shortly after the development of the incandescent lamp but until the introduction of the tungsten filament in the miniature mine-lamp bulb, the battery lamp was not a real possibility because of the excessive weight of the battery necessary to produce a sufficient amount of light. The actual development of the electric-battery type of lamp took place largely between 1910 and 1915. In England and Europe, the developmenb was almost entirely along the

Jan 1, 1936

By Graham Bright

METAL mines were developed long before coal mines and the early lighting of underground workings was effected by torches and candles. The early coal mines were outcrop workings and little trouble was experienced from gas, but as the mines became deeper and shaft mines were opened it became apparent that an open-flame lamp was exceed-ingly dangerous where gas occurred. No satisfactory way of lighting gaseous coal mines was found until Sir Humphrey Davy brought out his famous safety lamp in 1815. The introduction of the Davy lamp was a great step forward but it was unsatisfactory from a light standpoint because the gauze absorbed a large percentage of the light given out by the flame. Clanny corrected this by the introduction of a cylindrical glass lens, which not only per-mitted a free distribution of the light from the flame but added greatly to the safety by eliminating the possibility of the flame coming in contact with the gauze and by protecting the flame against air currents. A very complete story of the flame safety lamp since its inception is given in the U. S. Bureau of Mines Bulletin No. 227, by J. W. Paul, L. C. Ilsley and E. J. Gleim, published in 1924. A little more recent publication, known as Safety in Mines Research Board Paper No. 4, entitled "The Light Power of Flame Safety Lamps," by R. V. Wheeler and D. W. Woodhead, was published in England in 1927. The flame safety lamp was the-only lamp available for gaseous mines for about 100 years. Although the incandescent electric lamp has been in use over 50 years, it was not found safe to use this lamp from wired circuits in gaseous locations. The storage battery was advocated shortly after the develop-ment of the incandescent lamp but until the introduction of the tungsten filament in the miniature mine-lamp bulb, the battery lamp was not a real possibility because of the excessive weight of the battery necessary to produce a sufficient amount of light. The actual development of the electric-battery type of lamp took place largely between 1910 and 1915. In England and Europe, the development was almost entirely along the

Jan 1, 1935