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By Walter V. Knopp, Laurence Delisle

The aim of this work was the preparation of nickel-steels from elemental metal powders by powder metallurgy techniques. It was known that plain carbon steels could be made from a mixtufe of iron powder and graphite and that the effect of carbon on iron in powder form was of the same nature as that produced in fusion metallurgy. The problem in making nickel steels from elemental powders consisted therefore in finding out whether sufficient diffusion of the nickel and other incidental metals . normally present in such steels could be induced in the solid state to modify the properties of plain carbon steels made from powders and produce the beneficial effect of alloying. The composition selected originally was that of an S.A.E. 2330 steel. Metal powders, in the proportion correspending to that composition, were mixed with graphite, pressed, and heated at different temperatures for different periods of time, to produce bonding of the metal particles and mutual diffusion of the various elements without melting. Temperatures up to 1325°C and sintering periods as long as 6 hr were first investigated because it was expected.that such conditions would produce maximum diffusion with an accompanying improvement in the properties of the alloy. It was found that, although diffusion proceeded to a large extent under the conditions investigated, it would not be complete unless sintering were carried out at a high temperature for much longer than 6 hr. Relatively high temperatures and long sintering times are objectionable from a practical point of view, particularly when a low COSt material is to be produced, because they necessitate the use of special, costly equipment. Work could be done to improve the diffusion of iron and nickel by changing conditions other than the sintering temperature and time, that is, finer primary or alloy powders could be used. However, a marked change in the properties of the steel had been observed even with only partial diffusion. It was thought, therefore, that instead of trying to improve the diffusion, advantage might be taken of its incompleteness to produce a special structure consisting, in the unquenched condition, of a hard constituent, rich in nickel, dispersed in a tough pearlitic matrix. Steels with such a structure, not readily obtainable by fusion, should have desirable mechanical properties. Besides, it should be possible to prepare them from elemelltal powders under economical conditions. This latter alternative was therefore adopted for the second phase of this work. This report is divided into four parts: I. General Procedure. 2. Effect of Sintering Temperature. 3. Effect of Varying the Nickel Content. 4. Effect of Alloying Elements. General Procedure The general technique of cold pressing as used in powder metallurgy was applied.

Jan 1, 1949

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nu-cleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of cleation,gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz. METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on p. 701. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.2 The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited" to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SCV which may lead to contamination with sulfur, or CO," which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents: which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere." It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution cohposition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farbenm claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic. antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373"C), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred. probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

The Institute has no available copies of Bulletin No. 7, January, 1906, and Bulletin No. 105, September, 191.5. The sum of 30.50 per copy will be paid for these Bulletins.

Jan 6, 1917

References are in all cases to the earliest known editions. In the few cases where the first edition has been unavailable for consultation, the particular one studied is indicated. English translations are included when known, but not others. [ ]

Jan 1, 1942

By H. C. Babbitt

The Effect of Arsenic.—A question involving the temperature of precipitation of ammonium phospho-molybdate, which was brought to my attention some time ago, led to the following experiment :*

Jan 1, 1893

By D. H. Bacon

Our Transactions contain so many suggestions of apparently trivial, yet really important, contrivances for the saving of time and

Jan 1, 1893

Following the declaration of a national emergency by the President on Dec. 16, 1950 the Office of Defense Mobilization was established with Charles Wilson as director. It has been obvious since the entry of Red China into the Korean War that the previous defense setup was not adequate for accelerated mobilization.

Jan 2, 1951

By S. B. Christy

The fact that many millions of gold have been extracted by the cyanide process, during the last five or six years, from South African tailings which could not be profitably worked by any other method previously tried upon them, lends a peculiar practical interest to this branch' of metallurgy. Numerous writers have recently made valuable contributions on the process without exhausting the many complexities of the subject. Among the first American writers on the subject in its modern aspect were two former students of the University of California, Mr. Louis Janin, Jr., and Mr. Charles Butters. Young Janin was one of the first to enter this field, and performed much useful experimental work in the early stages of the history of the process. At about the same time, Mr. Charles Butters, who had left California to erect chlorination works for the Robinson mine at Johannesburg, became interested in the cyanide process, and, after getting the chlorination plant in working order, put up, for working the tailings from the Robinson mine, a cyanide plant which achieved the first large-scale success ever made with this process. The papers which Charles Butters, together with John E. Clennell and Edgar Smart, have contributed on the chemistry of the process, were among the first to give any adequate idea of its nature.* Another important contribution to the literature of the subject is the paper of Dr. A. Scheidell, published in 1894 as a " Bulletin of the California State Mining Bureau." This contains an admirable summary of the state of the art at the time of its publication.

Jan 1, 1897

By James Gayley

The atmosphere, which plays such an important part in the manufacture of iron and steel, is the most variable element involved in its several processes; and particularly is this true of the blast-furnace process, which consumes air in large quantitiee. At no time since the blast-furnace became an important and widely used apparatus—even when it was operated in the most crude manner—have the variations in composition of the raw materials used been as frequent and as great as the variations in humidity of the atmosphere. Important improvements have been made in the blast-furnace and its accessories, such as the hot-blast stoves, the increase in size and change in the shape of the furnace, more efficient blowing-engines, the increased protection given to the bosh-walls, and the careful preparation of the raw material, all of which have exerted a pronounced influence on the furnace-operations from a metallurgical standpoint. But during the past eight years little advance has been made in this direction; the fuel-consumption has not diminished, nor has there been any material increase in production. Within that period, however, there has been witnessed the greatest development in appliances for the economical handling of material. So complete has been the work in this direction, that, except in isolated cases, in this country at least, a further extension does not hold out much promise of a satisfactory return on the investment required. It seemed that, with the exception of the gas-engine, we had about reached the limit, for like a strong wall, the atmosphere, with its humidity as variable to-day as when first blown into a primitive blast-furnace, appeared to stand as a barrier to

Jan 1, 1905

By Nathan C. Rockwood

LIME is a very general term applied to products of limestone, in popular treatises often incorrectly, including ground or pulverized limestone used in agriculture. When used without qualifying adjective, the term usually means burned or calcined limestone, or quicklime, or calcia. The corresponding calcined product of magnesite is magnesia. If the calcined rock is relatively pure calcium carbonate, the resulting lime is a "high-calcium" lime; if the rock is dolomite, or a combination of calcium and magnesium carbonates, the lime is a "dolomitic" or a "high- magnesium" lime. There are various grades in between, depending on the percentage of magnesium carbonate and other ingredients in the raw rock. For some industrial purposes only high-calcium limes are suitable; in other processing-as, for example, neutralizing acid wastes -the relative percentages of magnesium and calcium carbonates in the raw material are not important. Limestone is burned (roasted or calcined) in furnaces known as lime kilns by direct exposure to the hot gases and flames. When heated to incandescence, the carbon dioxide content of the rock is expelled, leaving calcium and magnesium oxides, according to the formula usually written: [ ] This thermal reaction is reversible, which requires that the lime be withdrawn from the "calcining zone" of the kiln about as fast as made. Pure calcium carbonate would lose 44 pct of its weight in the calcining process; dolomite, 48 pct. Generally, the lime will retain the approximate size and shape of the piece of rock from which it is made but some few limestones tend to break down into granules or dust. Hence lime (quicklime) comes from the kilns in lumps or granules and normally is packed in water- tight containers in these forms, or is pulverized after calcination.

Jan 1, 1949

By Joseph S. Malesky

The discovery and development of explosives mark one of the most important findings in the history of civilization. Without explosives our vast economic enterprise concerning the mining of coal, copper, iron, aluminum, and various other ores could not function. Explosives are used in all kinds of construction works, in the razing of old buildings, blasting of trenches, driving of tunnels, and in many other instances common to our everyday life. For these reasons explosives are rightfully referred to as the forerunner of progress. An explosive may be defined as a substance (usually a mixture) that, when flame or shock is applied, yields readily to rapid combustion or oxidation, accompanied by the formation of such relatively large quantities of gases as to produce much violence and pressure which, in turn, react against their surroundings and cause what is termed an explosion. By their very nature the action of explosives is destructive and disruptive of adjacent materials. Decomposition of explosives can occur through deflagration, which is rapid burning or combustion, as in the case of black powder, or through detonation, which is an almost instantaneous disruption, as in the case of dynamites and blasting agents. HISTORY OF BLASTING WITH EXPLOSIVES At one time workmen obtained stone blocks for building by grooving the rock with crude picks, driving wooden wedges into niches in the rock, and pouring water on the wedges; the swelling of the wood forced out the blocks. As late as the 17th century, fires were placed against the face of rock to crack it, and water was sometimes dashed on the heated rock to shatter it by sudden cooling. The progress of our country is synonymous with advancement of the improved manufacture and extended use of explosives. Coal had been

Jan 1, 1981

By H. W. Weart, D. J. Mack

SINCE the first recognition of eutectic solidification as the simultaneous formation of 2 solids from one liquid,1 many complex structures thus produced have been observed. Despite many attempts to ascertain it, however, the detailed mechanism by which these structures develop remains obscure. In an attempt to clarify the origin of eutectic structures, the study described in this paper was undertaken. The broad objective of the study was to investigate the effect of different solidification conditions on the structure of single eutectic grains. It was expected that the eutectic structure would thereby be isolated for study, but preliminary experiments revealed another structure within each grain. When a literature surveye revealed only 1 previous mention of the subgrain structure,' it was decided to determine the origin of the structure and to study its response to various growth conditions. Before presenting the details of the investigation, it is apropos to distinguish carefully among the 3 structures produced during eutectic solidification. This is especially desirable in view of the apparent confusion existing in the literature concerning the structures in a eutectic specimen. The confusion is due largely to the existence of the subgrain structure noted above which is easily mistaken for the grain structure. In the following paragraphs, an effort is made to distinguish the 3 structures by briefly describing their origin during solidification, even though the results are thereby anticipated slightly. The 3 structures produced during eutectic solidification are the grain structure, the colony structure, and the eutectic structure, each one contained by the one preceding it. The grain structure is analogous to the polycrystalline structure of a metal or inle-phase alloy in that each grain grows from a single nucleus. A somewhat broader interpretation is needed here, however, because of the presence of 2 phases in each grain. Since in most eutec-tics particles of 1 phase are dispersed in a matrix of the other, a grain may be taken to be the region in which the matrix phase is monocrystalline.*

Jan 1, 1959

By R. F. Mehl, G. V. Smith

THE decomposition of austenite in steels, because of its immense practical importance, has been subjected to extensive study in recent years from the point of view of the mechanism of the process.1-3 Although much information has been acquired a number of questions, principally of theoretical interest, remain. One is that of the atomic-crystallographic mechanism by which each of the various reaction products forms. The isothermal reaction products of the eutectoid decomposition in plain carbon steels (to which this study is restricted) have conveniently been classified in three general groupings-pearlite, bainite, and martensite. Of these several products, pearlite and martensite have been studied extensively, but bainite has received only scant attention. As a result, the mechanism of the formation of pearlite and that of martensite are now fairly well understood while a great deal of uncertainty exists regarding bainite. PEARLITE Pearlite forms from austenite by the precipitation of alternate platelets of cementite and ferrite, which grow into the austenite matrix.2-5 The rate of reaction may be described in terms of a rate of nucleation and a rate of growth 2 3 Mehl and Smiths have attempted to determine the lattice relationships existing between the ferrite in pearlite and the parent austenite. Using a pole-figure method of analysis, it was found that a limited number of ferrite orientations resulted from the decomposition of a single grain of austenite; it was not possible,[ ]decide between two assumed ideal relationships, both of which appeared to account for the experimentally determined pole figure. It was definitely shown, however, that the relationship obtaining was quite different from that determined for the proeutectoid separation of ferrite.7 No attempt was made to determine the habit plane (matrix plane to which the precipitate lies parallel) of the pearlite lamellae. Belaiew8 earlier had stated that the number of directions assumed by the pearlite lamellae in a single grain of austenite was 12 (no details were given) and concluded wrongly, as Mehl and Smith' have pointed out, that the lamellae delineate the {210} planes of ferrite.* MARTENSITE It is known that martensite is a transitional constituent of body-centered tetrag-

Jan 1, 1942

By John Chipman

IN the manufacture of rimming steel-which constitutes the bulk of the world's production of mild steel-the factors that determine the quality of the product are very closely associated with the pouring and solidification of the steel in the ingot mold. The behavior of the metal in the mold is, on the one hand, the resultant of the complex processes through which the liquid metal has passed, and, on the other, it is an indication of the probable behavior of the ingot during subsequent rolling and finishing operations. A detailed study of the mechanism of solidifica-tion of rimming ingots ought to yield information that will be useful iii controlling the structure of the ingot and the quality of the ultimate product. The first step in such a study is to determine the rate at which the solid shell of the ingot forms from the liquid metal in the mold. A knowledge of the rate of solidification will make it possible to correlate observations of rimming action and gas evolution with studies of the structure, porosity, and segregation within the ingot. Thus, if the metal in the mold is observed to fall, let us say one minute after pouring, the portion of the structure associated with this fall will lie located in the part of the ingot that is solidifying at that particular moment. The knowledge that the ingot solidifies to a depth of ¾ in. in the first minute enables us to locate in the ingot the structural features corresponding to the observed fall. Conversely, the blowhole condition associated with a rising or growing ingot will be found in the part of the ingot that is solidifying at the time the phenomenon occurs. The time required for the complete solidification of an ingot has long been a matter of speculation. It is of considerable practical importance in connection with charging and heating in the soaking pits. Too rapid handling of the ingot through heating and rolling processes has been thought to be associated-with excessive pipe and other internal defects, so that a further object of this investigation was to attempt to estimate the time required for complete solidification, or the minimum practical time within which the subsequent operations can be performed with the minimum hazard.

Jan 1, 1937

By L. R. Plitt, M. K. Kim

The collecting properties of the fatty acid type collectors for barite were studied using zeta potential measurements, infrared spectroscopy, and Hallimond tube flotation tests. Based upon the experimental results, an adsorption model has been formulated which emphasizes the predominant role of the hydrocarbon chain in collector adsorption.

Jan 1, 1975

By C. H. Burgess

ON June 5, 1947, Secretary of State George C. Marshall in a speech at Harvard University outlined a plan for the economic recovery of Europe. The plan contemplated that the United States should provide assistance which would enable the European nations better to help themselves and to help each other to reconstitute from their war-torn lands conditions which would make possible decent standards of living. The Foreign Assistance Act of 1948 was passed in April of that year, and established the Eco-

Jan 10, 1950

ALASKA Established November 19, 1947 Meets fourth Monday of each month at Fair¬ banks, Alaska J D CRAWFORD, Chairman BRUCE I, THOMAS, Vice-Chairman C D JERMAIN, Vice-Chairman for Southeastern Alaska EARL H BEISTLINE, Secretary-Treasurer Box 265, College, Alaska

Jan 1, 1952

Recognizing the fact that the problems of the committee named by the Board to prepare the "official ticket" for officers and Directors of the Institute are various and difficult; and desiring to assist this committee by setting forth some of the principles that should guide the committee and some of the qualifications that should be required of candidates, the following instructions are formulated and the Secretary is directed to publish them in MINING AND METALLURGY concurrently with the publication of the names of each newly appointed Nominating Committee and to send a copy to each member of the Committee

Jan 1, 1943

By E. A. G. Colls

Discusses corrosion in Trail chemical plants producing ammonia, sulphuric, nitric and phosphoric acids, ammonium phosphates, sulphate and nitrate, together with miscellaneous allied material problems and their solution using erosion or corrosion proof materials. Conclusion, that for work of this nature, most costly material may well be cheapest in the long run.

Jan 4, 1950