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By Carl F. Floe, John Chipman

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By E. H. Wells, A. Andreas

New Mexico retained its position as the sixth largest oil-producing state for the year 1937 with a total production of 38,484,630 bbl. This was an increase of 11,680,184 bbl. over the 1936 production of 26,804,446 bbl., or a gain of 43 per cent. The production for Lea County during 1937 was 35,961,056 bbl.; for Eddy County, 2,136,251 bbl.; and for northwestern New Mexico (San Juan and McKinley Counties), 387,323 bbl. The average daily non-marginal well allowable for Lea County on Jan. 1, 1937, was 92 bbl.; at the close of the year it was 67 bbl. The average daily pipe-line runs were less than the allocations of the New Mexico Oil Conservation Commission, but slightly in excess of the state allowables recommended by the United States Bureau of Mines. The average daily production for the year was 105,437 barrels. The total number of completions in the state was 742, of which 638 were oil wells; 19 hydrocarbon gas wells; 5 carbon dioxide gas wells and 80 dry holes. Of the dry holes, 46 were in proven fields. Of these 46 dry holes, 13 were in the Artesia-Grayburg-Jackson-Maljamar area, Eddy County, two in the Getty Extension field, Eddy County, 11 in the Red Mountain field, McKinley County, three in the Rattlesnake field, San Juan County, and nine in the Aztec-Bloomfield area, San Juan County. There were only eight dry holes in the proven fields in Lea County. Southeastern New Mexico Lea County.—The Monument field was the largest producing field in Lea County, with 10,945,788 bbl., closely followed by the Eunice field with 10,927,929 bbl. The Hobbs field, formerly the largest producing field in Lea County, was relegated to third .place, with 7,292,522 barrels. Drjlling during the year closed the gap between the northern part of the Eunice field and the southern part of the Monument field. The wells in this area were relatively small, because of decreased porosity in the lime. The greatest activity in Lea County was in the Monument pool, with 199 completions, 197 being oil wells, one a gas well and one a dry hole.

Jan 1, 1938

United Engineering Society WALTER H ALDRIDGE J VIPOND DAVIES I V N DORR Engineering Societies Library Board SYDNEY H BALL ALEXANDER C HUMPHREYS GEORGE C SLONE JOHN H JANEWVAY Engineering Foundation Board H M BOYLSTON J VIPOND DAVIES GALEN H CLEVENGER Society for Promotion of Engineering Education WILLIAM KELLY ALLEN B ROGERS American Engineering Standards Committee GRAHAM BRIGHT GEORGE C STONE GEORGE E THACKRAY Alternates-RICHARD L LLOYD and HARLOWE HARDINGE

Jan 1, 1923

By Henry Fay

The erosion of guns is a complex problem which can be solved only by a detailed study of all the factors involved. In the present paper it is proposed to submit the results of observations and experiments which have extended over several years. Certain facts have been established and preliminary reports have been published.' Conclusions have been reached since then which, it is believed, are worth presenting for the purpose of promoting discussion, and with the hope that ultimately the whole truth will be known. The particular phase of the problem which will be presented here is the hardening of the inner surface of the gun tube. It has been known for a long time that after firing a large caliber gun for some time, the surface of the metal becomes hard and brittle, cracks, and wears away.2 The character of this phenomenon may be learned by an examination of some results which are typical, obtained from a detailed study of a 12-in. gun. The gun was trepanned and rings representing various sections of the gun were cut out for examination. The first ring represented the metal at the muzzle end, and the other rings were removed at approximately 120, 240, 325 and 337 in., respectively, toward the breech end. The appearance of the surface of the metal in the different sections is shown in Fig. 1. The greatest amount of wear and maximum amount of hard surface layer was found in section marked E, which is nearest the powder chamber and at the beginning of the rifing; the maximum amount of cracking in D; the maximum amount of copper deposition in C. Section B showed heat cracks on both lands and grooves, and section A showed heat cracks on the driving edge of the lands only. There was much flow of metal in both sections E and D, and there was progressively less effect noticeable toward the muzzle end. The polished cross-section of these same pieces is shown in Fig. 2. The extent of the erosion is greatest nearest the powder chamber, and diminishes toward the muzzle end.

Jan 1, 1917

By Lucius W. Mayer

The iron-mines of the Ilsede Hutte Co. are at a town called Peine, about 20 miles east of the city of Hanover, on the railroad to Brunswick (Braunschweig). Hanover, the capital of the province, is a military city, of approximately 250,000 inhabitants, and Brunswick, 33 miles to the westward, has half this number. The mines here described are located in a hamlet called Bulten. The Ilsede Hutte Co. operates two mines, 1.5 miles apart, in this district, Gruber Bulten Adenstadt and Gruber Lengede Bodenstadt. It also operates an iron-mine north of Hanover, known as Eiserhaven, and one in the Harz mountains, the Georg Friedrich, at Grauhof. At Bulten a coarse conglomerate, a, Figs. 1 and 2, contains nodules of limonite, cemented together by calcium phosphate. The ore contains Fe, 25 to 45; Mn, 3 to 4; P, 0.6 to 1.4; '5, 0.02 to 0.09; and CaCO,, 40 per cent. Directly above the conglomerate is limestone, 6, followed by a mixture of clay and sand, c. Below the conglomerate is a hard clay floor, d. The ore-body, from 10 to 12 km. long, and from 3 to 4 km. wide, has a maximum thickness of 20 m. It dips approximately 10" S.E., and strikes K 45° E. Diamond-drill prospecting shows that the thickness diminishes to 1 m. as the end of the deposit is approached to the northward. At this point the deposit is 250 m. below the surface. In Fig. 2, the arrow, A, indicates the general direction of the work along the face, a, which is carried forward in a straight line for its entire length. At B, a train is approaching, which has come from the bench-track, shown at C, by a circuitous route, and is dumping the overburden behind the face, in the space left by the excavated rock. Formerly the work at this mine mas essentially open-cut, the deposit having a very strong outcrop. Figs. 1 and 2 show also

Jan 1, 1909

By L. J. Buck

Lead smelting in the ore hearth, first practiced in Europe, whence the traditional name "Scotch hearth, and later developed in America to its present efficiency, is based upon the roast reduction process and is applicable to relatively high-grade galena concentrates. The roast reduction process embraces not only the roast reactions: 2PbS + 70 = PbO + PbSO4, + SO2 PbS + 2PbO = 3Pb + SO2 PbS + 2PbSO4 = Pb + 2PbO + 3SO2 but also, by reason of the addition of extraneous fuel, the reduction reaction: 2PbO + C = 2Pb + CO2 Thus in the ore hearth the roasting of lead sulphide, forming lead oxide and lead sulphate, the reaction of lead oxide and lead sulphate with lead sulphide producing lead, and the reduction of lead oxide by carbon producing lead, go on simultaneously. The Ore Hearth Function of the Ore Hearth.—The ore hearth, through the roast reduction process, provides for the extraction of lead and the immediate disposal of the smelting products—fume, hearth slag and lead, all of which are subsequently treated as follows: the fume is recovered in the flue system and baghouses, mixed with concentrates, and returned to the ore hearth in the form of ore mix; the hearth slag is smelted in a blast furnacc for the further recovery of lead; and the lead is refined and cast into a marketable product. Concentrates Amenable to Ore-hearth Smelting.—Only concentrates that are high in lead content, 70 per cent or more, are ordinarily considered amenable to ore-hearth smelting. Silica should not exceed 2 per cent and iron is allowable only to 4 per cent. These slag-forming constituents occlude both sulphide and mctallic lead, prevent the elimination of sulphur and decrease the lead extraction. Lime and magnesia are beneficial in that both favor a dry slag, promote elimination of sulphur, and prevent occlusions of metallic lead.

Jan 1, 1937

By Alfred R. Powell

Late in 1944 a group of petroleum and coal technologists was organized in Washington under the sponsorship of the Petroleum Administration for War and the U. S. Bureau of Mines. This group, known as the Technical Oil Mission, was placed under the authority of the Technical Industrial Intelligence Committee of the Joint Chiefs of Staff, which was then promoting the organization of other missions to be sent to Germany to obtain technical information regarding various industries in that country. The objective of the Tehnical oil Mission was to obtain technical data on German production of synthetic oil from coal and all other commercial practices and research projects connected with the oil industry. The primary purpose was to obtain such data as were immediately essential to assist the war against Germany and Japan, with secondary emphasis on technical information that would assist American industry after the end of the war. since oil-production facilities in Germany and the occupied countries controlled by Germany were the top targets for strategic bombing, the Technical Oil Mission was the first group under the Technical Induslrial Intelligence Com,mittee to enter Germany. A few members of the group flew to London in February 1945 and the majority of the remainder followed in March. In London they were joined by an equal number of British investigators and the combined mission was then sent into Germany under the authority of the Combined Intelligence Objectives Subcommittee (CIOS). A summary of the more important information gained by this combined British and American mission is presented below. German Oil Production The oil available to Germany, both natural and synthetic, and including production from occupied countries, reached a peak in late 1943 and early 1944 Production at this time was at the rate of 1,200,000 metric tons Per month, equivalent to 100,000,000 bbl. per year, or about 7 per cent of the wartime production in the United States. Of this production, jo per cent was crude oil from Romania and Hungary, 12 Per cent was crude oil from Germany itself, including Austria, 9 per cent cumprised coal-carbonization products, that is, tar and light oil, and only the remaining 29 per cent was synthetic liquid fuel made from coal or tar. Synthetic liquid fuel made in Germany was equivalent therefore to less than 2 per cent of wartime production of crude oil in the United States. The success of the strategic bombing campaign against German oil-production facilities is demonstrated by the fact that by September 1944 the Ploesti fields of Romania and much of the syrlthetic oil production had been eliminated, so that the amount of oil available to the German war machine was only 25 per Cent of the peak qualltity mentioned above. By early 1945, when the combined British and American oil mission was entering

Jan 1, 1947

By Alfred R. Powell

Late in 1944 a group of petroleum and coal technologists was organized in Washington under the sponsorship of the Petroleum Administration for War and the U. S. Bureau of Mines. This group, known as the Technical Oil Mission, was placed under the authority of the Technical Industrial Intelligence Committee of the Joint Chiefs of Staff, which was then promoting the organization of other missions to be sent to Germany to obtain technical information regarding various industries in that country. The objective of the Tehnical oil Mission was to obtain technical data on German production of synthetic oil from coal and all other commercial practices and research projects connected with the oil industry. The primary purpose was to obtain such data as were immediately essential to assist the war against Germany and Japan, with secondary emphasis on technical information that would assist American industry after the end of the war. since oil-production facilities in Germany and the occupied countries controlled by Germany were the top targets for strategic bombing, the Technical Oil Mission was the first group under the Technical Induslrial Intelligence Com,mittee to enter Germany. A few members of the group flew to London in February 1945 and the majority of the remainder followed in March. In London they were joined by an equal number of British investigators and the combined mission was then sent into Germany under the authority of the Combined Intelligence Objectives Subcommittee (CIOS). A summary of the more important information gained by this combined British and American mission is presented below. German Oil Production The oil available to Germany, both natural and synthetic, and including production from occupied countries, reached a peak in late 1943 and early 1944 Production at this time was at the rate of 1,200,000 metric tons Per month, equivalent to 100,000,000 bbl. per year, or about 7 per cent of the wartime production in the United States. Of this production, jo per cent was crude oil from Romania and Hungary, 12 Per cent was crude oil from Germany itself, including Austria, 9 per cent cumprised coal-carbonization products, that is, tar and light oil, and only the remaining 29 per cent was synthetic liquid fuel made from coal or tar. Synthetic liquid fuel made in Germany was equivalent therefore to less than 2 per cent of wartime production of crude oil in the United States. The success of the strategic bombing campaign against German oil-production facilities is demonstrated by the fact that by September 1944 the Ploesti fields of Romania and much of the syrlthetic oil production had been eliminated, so that the amount of oil available to the German war machine was only 25 per Cent of the peak qualltity mentioned above. By early 1945, when the combined British and American oil mission was entering

Jan 1, 1947

By Gerald J. Anderson

The Marquette District of Central Northern Michigan is the oldest of the Lake Superior iron districts with a mining history dating from 1852 up to the present. The total production of all types of ore through 1965 was 338,120, 146 long tons. Emphasis up to the 1950's was on mining the direct shipping ores; however, demands for higher-grade and better-structured ores in the last decade has resulted in a complete shift in emphasis to beneficiating the lowgrade Negaunee Iron-formation to produce high-grade iron ore pellets. The Precambrian sediments of the Marquette Range have been correlated with the Animikie Series of the Thunder Bay District, Ontario, and are contained in a westward plunging synclinorium that is approximately 3 3 miles in length and 3 to 6 miles in width. -The rock unit of major economic importance is the Negaunee Iron-formation that reaches a thickness of 2500 feet near the City of Negaunee. The primary iron content of the Negaunee Iron-formation averages 26 per cent, whereas the altered iron-formation approximates 31 per cent. The Negaunee Iron-formation has been divided into three principal types: diagenetic, oxidized, and metamorphic. The ores produced to date fall into four categories: high-grade soft ores, high-grade hard ores, siliceous ores, and concentrates and agglomerates (pellets). The soft ores generally are found in synclines and in fault-trough structures, bounded by mafic dikes along at least one side, and are mainly found in the basal portion of the Negaunee. In contrast, the hard ores occur in the uppermost portion of the Negaunee and are controlled by structural features such as folds, faults, and dikes. Iron-formation that has undergone diagenetic and metamorphic alteration makes up the main beneficiating ore types. Studies on the Negaunee Iron-formation have played an important role in the formulation of many of the theories on the origin of the Precambrian iron-formations.

Jan 1, 1968

By R. W. Gurry

In a series of charts this paper presents the composition of all gas mixtures, composed of the elements carbon, hydrogen, oxygen and nitrogen, which at temperatures from 1000° to 1800°F are in equilibrium with (1) austenite of various carbon contents, (2) iron and iron carbide, (3) graphite, (4) iron and its oxide. THIS paper presents the results of calculations made to determine the proportions of CO, CO2, CH4, H2, H2O and N2 in gas mixtures which, at temperatures from 1000" to 1800°F, satisfy, individually, the following conditions: (1) equilibrium with carbon steel of specified carbon content throughout the stable 7 iron region; (2) equilibrium with iron and iron carbide, both above and below the eutectoid temperature; (3) equilibrium with graphite; (4) equilibrium with iron and its oxide. From these data a new type of chart has been prepared which permits one to determine, from a room-temperature analysis of the furnace gas in question, the effect of the gas upon the steel at furnace temperature. Thus a guide is provided as to the carbon content which will result and as to the possibility of oxidation or sooting. All of the atmospheres commonly used in the commercial heat treatment of steel are composed of some or all of the simple constituents CO, CO2, CH4, H2, H2O and N2, and also in some cases oxygen or higher hydrocarbons. As the gas mixture is heated certain alterations in the proportions of the constituents take place, and at the temperature of the furnace the composition is, in general, not at all that of the entering gas. If equilibrium in the gas phase is presumed a calculation involving the use of certain fundamental data predicts for a certain temperature the carburizing, decarburizing, or sooting characteristics of a given atmosphere, and, upon the additional assumption of equilibrium between gas and metal, also the oxidizing ability of the gas and the ultimate carbon content of the steel. The extent to which these predictions are fulfilled will depend upon how closely the assumptions of equilibrium are realized in any particular case. Although at lower temperatures equilibrium is often not reached, there is considerable evidence indicating that above about 1000°F the approach to equilibrium in the gas phase is generally substantially complete, particularly in the vicinity of the steel which acts as a powerful catalyst in promoting reactions in the gas phase. The extent of the gas-metal reactions is commonly affected essentially by the sojourn at temperature; equilibrium with respect to carbon, for example, is accomplished simply by continuing the treatment long enough. However close the approximation of equilibrium may be in any instance, the above mentioned calculation indicates the condition of the steel at equilibrium, and at the present time this is the only basis of control of a furnace atmosphere. The effect at elevated temperature of a gas of a certain composition at room temperature upon a given steel has customarily been judged by first calculating from gas equilibrium constants the proportions of the gas constituents at the temperature of the steel, then comparing certain of these with the proportions known to be in carbon or oxygen equilibrium. This process is tedious and time-consuming, in particular because the calculation generally involves a series of successive approximations; and since some knowledge and familiarity with this type of computation are required, not everyone needing the information has been, in the past, in a position to obtain it. By making a series of equilibrium calculations, combining with fundamental data for gas-metal reactions, and plotting the results in a special way, a chart has been prepared which enables anyone

Jan 1, 1951

By T. Koulomzine

The theory of the Askania mag-netometer, as well as a complete discussion of all factors influencing magnetometer readings, is very ably described by J. Wallace Joyce.1 We will assume that the reader is thoroughly familiar with this theory and we will use whenever possible the same notations for the physical values involved in the theory. On the other hand, we believe that the principal formulas of the magnetometer can be deduced much more easily by the use of differential calculus than by the methods employed by Joyce. Consequently, we are presenting herewith a resumé of the theory of the vertical magnetometer in order to determine the correct formula of the temperature coefficient which we propose to compensate. Short Theory of the Vertical Magnetometers We shall accept the following notations: m = total mass of the magnet system, in grams. g = acceleration of gravity, in dynes. a = projection on the axis of the magnet system of the distance between the axis of support and the center of gravity of the magnet system, in centimeters. h = projection on the perpendicular to the axis of the magnet system of the distance between the axis of support and the center of gravity of the magnet system, in centimeters. M = 2pL = M, magnetic moment of the magnet system. Z = vertical component of the earth's magnetic field. ? = deflection angle of the magnet system. = focal length of objective lens in the optical system S = scale reading. In a vertical magnetometer the axis of the magnet system is kept horizontal within 2". Therefore, referring to Fig 1, we see that the magnetic torque of the magnet system influenced by Z must be counterbalanced by the gravity torque. MZ cos ? = mga cos ? + mgh sin ? or dividing by cos ? MZ = mga + mgh tan ? If we now move to another magnetic station and the temperature conditions change, the values of all the variables will change also: M, a, and h under the influence of temperature. 2, both with time and space. ? and S, as a result of all the above changes. Taking increments in Eq 2 we obtain: (Mo + ?M)(Z + ?Z) = mgao + mg?a + mg(h + ?h) tan (? +??) but tan (? +??), because ? is small, can be replaced by tan ? + tan ??; in fact tan (?+ ??) = sin ?.cos ?? + cos ?.sin ??/ cos ?.cos ?? — sin ?sin ?? but sin ? sin ???0 tan (8 + ??) ? tan ? + tan ??. Fur-thermore, neglecting all terms of the equation containing two differentials becomes: or a differential and a tan ??, Eq 3

Jan 1, 1950

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 C. D. Thompson, D. C. Violetta, C. A. Czako

The mechanics of the continuous sintering process are briefly reviewed and the application of this process for the beneficiation of principal minerals used in making cement is shown. Pilot plant tests using pyrobeneficiation techniques were conducted with mixtures of limestone and shale in various ratios. Results are illustrated and show the percentage removal of carbon, carbonates, sulfur, alkalies, and volatiles as a function of the limestone-shale ratio. Tests with varying quantities of solid fwls, added to mixtures containing limestone and shale in a 4 to 1 ratio, were made to attain optimum elimination of the volatile constituents. Experimental results show that 90 pct of these constituents were removed during the calcination sintem'ng process. The advantages of using the beneficiated material for making cement are discussed with regard to prepam'ng, handling, and clinkering operations. A sintering process for treating raw materials or kiln waste products which contain high amounts of alkaline materials is described. Tests were performed with a high alkaline waste dust mixed in a 1 to 1 ratio with raw cement meal. The data from these tests and others using different halides for aiding alkali removal are evaluated by the alkali content of the cement clinker. Test results showed that the Dwight-Lloyd process could be applied with facility in beneficiating raw materials for cement making. Substantial quantities of deleterious volutile constituents were removed by calcining and sintering techniques. The continuous sintering process has been applied for a number of years as a means of beneficiating minerals for subsequent conversion to merchantable products. The process was developed and first used for nonferrous metallurgical applicatfons. However, it has risen to prominence for ferrous metallurgical applications where last year in the U.S. and Canada nearly 40 million tons of iron ore were treated by grate firing processes. Through the years of process development many investigators have realized the versatility of the sintering process and have directed experiments toward the use of it for applications with nonmetallic minerals. These have included calcining limestone, carbonizing coal, expanding shale, and burning cement raw meal. Today commercial sintering plants produce cement clinker from mixtures of limestone and shale, lightweight aggregate from shale or clay, and calcined products from phosphate shale. The mechanics of the downdraft sintering process have been presented by many authors. In general practice the materials to be agglomated are mixed as moistened fines with a solid fuel and this mixture is spread uniformly on the grates of the sintering machine. The charge is then momentarily directed under an ignition furnace. After ignition a continuous downdraft of air promotes combustion of the fuel and through heat transfer particles become partially fused into a coherent mass. This is cooled from continued draft induced after combustion. Many investigators have shown that distinct zones are formed during the process of sintering iron ores. At the midway point of the sintering process these are prominent and are, respectively, from the top of the bed to the bottom, comprised of a cooling zone of sintered material, a combustion zone of sinter formation, a calcination zone, a drying zone, and a zone of unreacted materials. Completion of sintering occurs near the discharge end of the machine where the firing zone approaches either the grates or grate dressing material called hearth layer. Here the peak draft temperature usually can be noted in the windboxes. The zonal pattern has been illustrated with the use of graphs which show thermal gradients as they progress through the bed of materials during sintering. Fig. 1 shows, in simplified form, thermal gradients existing when clinkering cement on a sintering machine. The thermal gradients illustrated are for periods of initiation, midway and completion of the clinkering process. The occurrence of these zones has importance for the beneficiation of cement raw materials. A research program was performed at the Dwight-

Jan 1, 1961

H. H. Bleakney (Dept. of Mines and Technical Surveys, Ottawa, Canada)— The work of Dr. Machlin and his colleagues at Columbia University is so scholarly that one hesitates to take issue with them. Nevertheless the writer feels compelled to enter a demurrer to the mechanism of intercrystalline cracking proposed in this paper. The principal obstacle to its acceptance is found in its preoccupation with purely mechanical influences and its disregard for the chemical effect of impurities. The writer believes that the destruction of metallic cohesion by concentration of impurities at the grain boundaries is a necessary and sufficient condition for the development of intercrystalline cracking; and he believes that discussion of the numerous mechanical explanations proposed should wait until some valid objection to the chemical hypothesis has been advanced. It is nearly twenty years since Gillett" drew attention to the possibility that the chemical influence of precipitation might be the cause of intercrystalline cracking. As early as 1935, Greenwood'" remarked that grain-boundary precipitation of impurities in lead appeared to promote intercrystalline cracking. Again in 1939, Scott commented as follows on a paper by Thielemann and Parker:'" "There are at least two familiar phenomena that can influence grain-boundary cohesion: 1) intergranular oxidation; and 2) grain boundary precipitation. An important consideration in this work, therefore, is to determine which, if either, of these factors is responsible for the low values of cohesive strength observed." In 1952. the writer presented evidence," some original and some abstracted, which indicated that in copper, silver, aluminum, lead and iron, intergranular cohesion was a function of the purity of the metal. In 1954 Glen, discussing a paper by Ridley and Tapsell14 indicated his belief in a precipitation mechanism for the intercrystalline embrit-tlement of molybdenum steel and suggested that with an absolutely pure metal it would be almost impossible to obtain an intercrystalline crack. This suggestion has

Jan 1, 1959

By S. C. Schaeker, A. W. Schlechten, A. H. Larson

PARRAVANO and Malquori' studied the equilibrium of H2S-Hz with molybdenum and its lowest sulfide which they believed to be MoS2. Mc Cabe' has shown that its composition is actually Mo2S3 and determined its dissociation pressure by means of Knud-sen effusion measurements. Stubbles and Richard- son3 have recently studied the equilibrium of gas mixtures of H2S-HZ with the two-phase solid mixtures of Mo-MozS3 and Mo2S3-MoS2. The latter investigators found that M02s3 deviated slightly from the stoichiometric composition, but they did not determine the homogeneous region of the disulfide phase. Morimoto and Kullerud, studied the Mo-S system by quenching, microscope, and X-ray methods and concluded that the disulfide is stoichiometric. The present investigation was concerned with the measurement of the sulfur vapor pressure variation with composition at 1100°C in the homogeneous region of "MoS2". These measurements were made by reacting: 1) molybdenum powder (99.97 pct Moj with sulfur vapor, and 2) MoS1.g9 (formed by reaction of Mo + H2S) with sulfur vapor in a quartz capsule. Conditions were controlled to form an equilibrated phase within the homogeneous region of the disulfide. The quartz capsule was sealed off initially under a vacuum and the residual gases were gettered by titanium powder contained in one end of the capsule. A mixture of Mo + S or MOS,., + S was in the other end. The section containing the titanium powder was heated for 24 hr at 700°C and then removed by flame sealing. The end of the capsule containing the charge was then heated to 1100°C. The other end of the capsule was maintained at a temperature which would produce the desired sulfur pressure in the capsule (liquid sulfur distilled from the charge mixture was retained in this end). After equilibration, the capsule was removed from the heating assembly and rapidly air-cooled. It is assumed that equality existed between the total sulfur pressures (PT) in the two ends of the capsule and not between the partial pressures of the different molecular species (S, SZ, Three separately controlled heating elements were used to maintain the proper temperature gradient over the length (approximately 12 in.) of the capsule. A thermocouple-Wheelco "Capacitrol" system was used for temperature control of the two end heating elements within 2"C. The center heating element was controlled directly by a " Power -stat". Separate controlling and measuring thermocouples were used for both end heating elements. Pt-Pt(l0 pct Rh) thermocouples were used for 1100°C and Chromel-Alumel thermocouples were used for lower-temperature control and measurement of the assembly. Silver foil was wrapped around the end of the capsule containing the liquid sulfur to insure a constant temperature zone. The thermal gradient over the entire length of the capsule was measured to: 1) ascertain that the length of the constant temperature zone of the liquid-sulfur end and the sulfide end was sufficient, and 2) ascertain that the liquid-sulfur zone was the zone of lowest temperature. The data obtained in this investigation are shown in Fig. 1 and Table I. The total sulfur pressure (PT) and p(S2) were calculated from the data of Braune et UZ.~ The compositions of the equilibrated disul-

Jan 1, 1964

By Ian Wark

IN the paper on the development of the flotation process at Broken Hill (Australia) prepared by the Broken Hill Branch of the Australasian Institute of Mining and Metallurgy and published in its Proceedings for 1930 (N. S. 80), it is stated that the concentration of ores by flotation has been established on a commercial basis in Australia since 1904 and that differential flotation was practiced at Broken Hill in 1912. Since then, progress in flotation practice throughout the world has been rapid, and during recent years the knowledge of the reactions between comparatively modern so-called chemical promoters or collecting agents and the mineral surfaces has been broadened by the published accounts off many investigators, particularly those working in American universities. Because of the benefits the Australian mining industry has derived from the flotation process, it was felt that the industry should take some part in the efforts that are being made to extend the knowledge of the principles on which the flotation process is based. Accordingly, early in 1930, three Broken Hill mining companies-the Broken Hill South, the North Broken Hill, and the Zinc Corporation-together with the Electrolytic Zinc Co. of Australasia, Ltd., and the Mount Lyell Mining & Railway Co., established a laboratory in the chemistry department of the University of Melbourne for the purpose of investigating the principles underlying flotation. Subsequently, the Burma Corporation, Ltd., expressed a desire to cooperate. The two authors are directly employed and controlled by these six organizations, and the cost of the investigation is divided equally among them. The research has been carried out under the general direction and in close cooperation with Harry Hey, chief metallurgist for the Electrolytic Zinc Co. of Australasia, Ltd., and the authors desire to place on record their indebtedness to him for his ever willing help and constructive criticism.

Jan 1, 1932

By David W. Brunton

From the old-fashioned " grab-sample " to the modern timing-device, which takes a machine-sample with mathematical precision, there is a wide gap, which was only crossed by many years of toil and unremitting endeavor. Even to-day, notwithstanding the advancement in the art, " grab-sampling " is still practiced—sometimes to afford the unscrupulous mine-promoter a basis for fairy-tales with which to entrap the too-gullible investor, and often by milling and smelting companies to determine the amount of moisture in custom-ores. The latter practice is almost as reprehensible as the former, and it causes more trouble and ill-feeling between seller and buyer than all other factors put together. -NO reputable concern to-day would think of attempting to determine by grab-sampling the amount of gold, silver, lead, or copper contained in an ore, and yet many buyers expect the miner to accept the results of grab-sampling in the determination of the amount of water contained in the ore, forgetting that accurate results are just as necessary here as in the determination of the metals, because the result determines the percentage of weight of the ore which shall be excluded and considered to have no value whatever. Samples for the determination of moisture should be taken with as great care as samples for the determination of metallic content, and in order to avoid the extra expense of a separate operation moisture-samples should be taken from the sample-safe. As the sample reaches the sample-bin in a smaller stream and by a more circuitous route than the " reject" travels in its path to the outgoing car, it loses more moisture en route, and a constant should be added to compensate for this difference. Carefullg ,con ducted experiments have shown that the differ.elice in loss of moisture between the two routes does not exceed 10 per cent. in summer and 7 per cent. in winter. For instance,

Jan 1, 1910

By W. W. Gerberich

SINCE the original formulation of fracture mechanics concepts,&apos;y2 relatively little work has related the fracture mechanics description of metal behavior on a gross, structural component scale to the behavior of its microstructural constituents. The purpose of this note is to suggest the utilization of fracture mechanics to describe material behavior on a microscopic scale. A Fracture Concept for Two-Phase Structures. A critical displacement concept considering the tough unidirectional phase in a relatively brittle matrix is first examined. It is assumed that a flaw exists at position 1 as depicted in Fig. 1. As the crack moves from position 1 to 2 the plastic zone could be of the shape described with the size approximated by the Dugdale3 model: where c is the half-crack length, OO is the applied stress, and oyS is the yield strength. Hahn and Rosen-field4 have presented a simple fracture criterion for homogeneous materials based upon the displacement at the crack tip. They also have shown the equivalence of the critical displacement, v*, to fracture toughness by Kc = (2v*oysE)1/2 [2] The displacement at the crack tip is given by and the displacement at any distance in front of the crack tip may be determined knowing the plastic zone size and utilizing the development of Goodier and Field.5 Recalling Fig. 1, the value of v* for fracture in material M1 may be calculated from Eq. [2] providing the critical stress intensity factor is known. As the material is loaded, when vc > vM1 the crack moves from position 1 to position 2 where it encounters the tough second phase. If vc2 < vm2, then the crack will be arrested providing the width of the M2 phase is sufficiently large. This condition is necessary since the displacement at position 2 has increased due to the longer crack length. Thus, the displacement at the distance X (representing the dimension of the second phase) in front of the crack may be larger than the critical displacement for failure in the brittle material. If v, > vm, then failure will proceed in the brittle material. The value of v, may be calculated as indicated above. This latter consideration is the same as predicting fracture of a brittle second phase at some distance in front of a crack located in a ductile matrix. Experimental Evidence. On a macrostructural scale, tungsten wires in a ductile Be-Cu matrix are seen to fracture well ahead of the main crack front in Fig. 2. Utilizing a Kc value of 14.2 ksi-in.1/2 obtained by Schroder et al.6 for as-received tungsten, the critical displacement 2v*, for fracture is calculated from Eq. [2] to be about 6.5 X 10-5 in. The crack tip displacement, 2vc, is calculated from Eq. [3] to be 0.0028 in. indicating that fracture would occur at a considerable distance in front of the crack tip. From the ratio of v*/vc and the plastic zone estimate of Eq. [I], the distance in front of the crack tip at which a tungsten wire should fracture is calculated to be about 0.195 in. As shown in Fig. 2, a fractured wire occurs at a distance of 0.140 in. (fractured in three places), not at 0.250

Jan 1, 1968

By G. S. Cole, G. F. Bolling

A series of Al-Cu alloys has been cast from constant superheat to solidify either with a hot top or with a free liquid/air interface. All the other variables which affect relative fluid motions were kept constant except the imposition of slow rotations m oscillations of the mold. Depending upon the exact circumstances, evi-dence could be found for the nucleation of equiaxed grains from dendrite bits detached from the columnar zone, or from the free surface, or from solid bits induced at pouring; a special experiment showed the solute buildup during ingot solidification and by inference the reality of constitutional supercooling. All methods of grain nucleation are thus supported. When solidification is arranged in a static mold the columnar- to-equiaxed transition occurs by one of these nucleation paths, subject to the natural decay of temperature gradients which promotes nucleation or the survival of nuclei. But when solidification is forced under special fluid flows it may display odd transitions. In one of these the equiaxed zone is synihesized from. dendrite bits detached from the solid/liquid interface. These survive under the concurrent lowering of temperature gradients and eventually cause transition by impeding columnar growth. GRAIN structure control is desired because real experience shows that specific properties are associated with specific cast grain structures. But since control is thus a matter of need and does not require understanding, much of casting remains art. For example, the manipulation of relative fluid motions in simple ingots provides a control of grain structure development,1-4 but theoretical insight is not required in order to broaden its potential applicability. Fortunately, however, once a variable like fluid flow is recognized it can also provide paths toward new insight. New observations using this variable have provided an insight which is curious. All the theories or descriptions of the columnar-to-equiaxed transition (CET) seem to be supported as long as the appropriate experiment is carried out. In order to develop this idea, let us ignore segregation, the chill zone (until a later section of this paper), and the origin and development of the columnar zone.= The details of questioning how equiaxed material forms in a casting may be divided in two. The first part is simply a questioning of the origin for equi-axed grains: are there fresh nuclei from heterogeneous nucleation, or dendrite bits broken off or melted from the columnar zone or elsewhere,6 or other solid bits surviving from the outset of freezing? The second is more complex, a questioning of the CET: does columnar growth slow down and allow the dominance of equiaxed grains, however they are formed, or do equi-axed grains take over and force columnar growth to stop? This "chicken-or-the-egg" second question can be quite useful, especially because it allows us to delineate the ordinary or NATURAL EQUIAXED ZONE and the induced or SYNTHETIC EQUIAXED ZONE. A natural equiaxed zone occurs if solidification proceeds in the absence of disturbances or extraneous forces such as ultrasonics, stirrings, and so forth. Both the CET theory proposed by Winegard and Chal-mers, 7requiring constitutional supercooling, and the CET theory suggested by Chalmers,8 requiring nuclea-tion only on pouring, pertain to the natural equiaxed zone. The best collating evidence to date for both these theories is contained in the work by Biloni and Chal-mers;9,10 the former theory7 is supported by special versions of the unidirectional growth experiment performed by Plaskett and winegardl1 and the latter theory&apos; is supported in detail for the solidification of small ingots. An equiaxed zone can be synthesized when disturbances caused by forced fluid flows2-4 or other artificial means9,10 break off or melt off dendrite tips from an advancing solid/liquid interface,* if (and only if) temperature gradients in the melt are (forcibly) reduced enough to ensure the survival of these bits of dendrites, 2&apos;3 Willful disturbances even so trivial as those produced by rapping a mold might be included here; as will be shown for example, this follows Southin&apos;s suggestion that the free liquid/air interface

Jan 1, 1970

By A. P. Herring, S. F. Ravitz

Manganese dioxide reacts with sulfur dioxide solution in the absence of oxygen to form manganous ion and dithionate ion, together with a small amount of sulfate ion. The effects of SO, concentration, hydrogen ion concentration, stirring speed, and temperature on the rate of the reaction were studied. If it is assumed that undissociated SO2 molecules react rapidly with MnO, at active surface sites and that bisulfite ions react slowly, an equation can be derived that satisfactorily represents the observed reaction rates. For solutions in which the reaction with undissociated SO2 predominates, reaction rates and activation energies estimated from diffusion theory agree well with those found experimentally. Manganese dioxide dissolves readily in aqueous solutions of sulfur dioxide. The nature of the dissolution reaction was first investigated by Gay-Lussac and welter1 in 1819; they identified a new oxysulfur radical, the dithionate ion, S2O6, as one of the reaction products. Since then, the reaction has become a standard method of preparing dithionates in the laboratory and one of the more promising methods of leaching manganese from low-grade ores. In the "dithionate process" developed by the U.S. Bureau of Mines2,3, manganese-dioxide ore is suspended in a solution of calcium dithionate and leached with gas containing sulfur dioxide. The manganese is dissolved and the sulfur dioxide is oxidized according to the reactions:

Jan 1, 1965