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WE the undersigned, being all persons of full age and citizens of the United States and a majority residents of the State of New York, desiring to form a corporation pursuant to the provisions of the Membership Corporations Law for the purpose of incorporating, as provided in Section 5 of Article I. of said law, the existing unincorporated association known as American Institute of Mining and Metallurgical Engineers, Incorporated, do hereby make, acknowledge and file this Certificate for that purpose, and do Certify as follows: I. That the American Institute of Mining Engineers is an unincorporated association organized and existing with the object of promoting the arts and sciences connected with the economic production of the useful minerals and metals and the welfare of those employed in these industries by means of meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publications among its members and associates the information thus obtained.

Jan 1, 1937

WE the undersigned, being all persons of full age and citizens of the United States, and a majority residents of the State of New York, desiring to form a corporation pursuant to the provisions of the Membership Corporations Law for the purpose of incorporating, as provided in Section 5 of Article I. of said law, the existing unincorporated association known as American Institute of Mining Engineers, do hereby make, acknowledge and file this Certificate for that purpose, and do Certify as follows I. That the American Institute of Mining Engineers is an unincorporated association organized and existing with the object of promoting the arts and sciences connected with the economic production of the useful minerals and metals and the welfare of those employed in these industries by means of meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publications among its members and associates the information thus obtained.

Jan 1, 1923

By W. H. Justice

Cycling operations have been successfully conducted in the La Gloria Zone for eight years. The cycling of this zone is now virtually completed. It is proposed that this report shall review the cycling operations of this reservoir so that the industry can more accurately evaluate the cycling process as a production method. The La Gloria project is one of the largest cycling operations in the State of Texas. The gas rights in the field are unitized in three operating units. By mutual agreement Magnolia Petroleum is the designated operator of the project for the 12 operators owning the gas rights. The La Gloria Corp, is the owner and operator of the cycling plant. The development and operation of the field are under the direction of an Operators Committee comprised of a representative of each operator. The Operators Committee is assisted by an Engineering and Geological Sub-Committee. The La Gloria gas field is situated approximately three miles north of Fal-furrias, Tex., and lies principally in the extreme south end of Jim Wells County, with its outer limits extending into the north end of Brookes County, Tex. It is a simple elliptically-shaped dome which has a closure of 350 ft. The field encompasses a surface area of 5,500 acres. The gas reserves are found in 20

Jan 1, 1950

By Thomas M. Drown

ZING is, as is well known, very brittle at a temperature of about 210' C. (410' F.), and may then be readily pulverized in a mortar. By sifting it may be obtained of uniform grain. I have been accustomed to prepare products passing through 40, 60, and 80-mesh sieves, and also by bolting through a fine handkerchief. The principal analytical uses to which I have hitherto applied this material are to the reduction of iron directly from the ore by heating it with the pulverized zinc, and the reduction of ferric to ferrous compounds in solution. In the first case the pulverized ore, 0.5 gram or less, is intimately mixed with about ten times its weight of the pulverized zinc (the finer the zinc the better), in a porcelain crucible, and this mixture is covered with about the same amount of zinc. The crncible is then heated at the top of the flame of a Bunsen bhrner, at a dull red heat, for about ten minutes. The crucible should not be covered. When cool, the crucible, with its contents, is placed in a flask treated with hot dilute sulphuric acid, and brought quickly to a boil. The zinc and reduced iron are dissolved in a few minutes and the flask is then tightly corked and allowed to cool. When cool, the iron is directly titrated by potassium permanganate.

Jan 1, 1879

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By J. T. Crawford

COAL-CLEANING plants using the launder process generally wash the fine coal (minus 3/8 or minus 5/16-in.) separately in a plant consisting of washing launders or troughs placed one below another and sometimes supplemented by additional washing equipment such as tables and jigs. The coal and its associated impurities enters the feed end of the top launder, with a current of push water. As the material moves along the impurities, being heavier than coal, settle toward the bottom of the launder and are drawn off, with some coal, through "free discharge" boxes to the launder below. These boxes were given their name because their discharge falls freely; that is, it does not discharge into a water seal. Thus the impurities are progressively concentrated in the lower launders until box products are sufficiently free of coal to be discharged to refuse. The overflows of the upper launders go to clean coal while the overflow of the lowest launder, and perhaps that of the one immedi-ately above, is usually recirculated to the plant feed. Thus the bulk of the clean coal is removed rapidly and the impurities are concentrated more slowly. The chief purpose of this paper is to present the cleaning data of such a plant under different operating conditions.

Jan 1, 1940

By A. B. Boghani, R. H. Trent

A computer program has been developed to simulate evacuation of a mine in various configurations. The simulation input variables include characteristics of the mine, expressed in the form of a network of passages, properties of hoists and hoisting strategies, initial miner positions, ventilation and compressed air velocities, stench warning system and self rescuer capabilities. The simulation can be carried out for cases in which there is no fire, i.e., fire drill simulation, or for cases in which there is a fire at any arbitrary location. The fire is assumed to generate gases which impede movement of miners in the gaseous region. However, the thermal effects of the fire are not considered. The simulation output include the evacuation time for each miner, movement of the hoists, propagation of smoke through the mine passages and smoke exposure of the miners. Several illustrative simulations have been carried out to verify validity of the program and to demonstrate its capabilities. The computer program has been able to predict evacuation time, within 5 percent, for an actual fire drill. It is believed that this program can be used to evaluate evacuation performance of a mine, identify problem areas and demonstrate improvements due to the recommended corrective actions.

Jan 1, 1977

By C. M. Marquardt

The minerals industry in general should bow in homage to the uranium milling industry. Those in the uranium milling industry have "spark- plugged" more progress in the application of instrumentation and control in the last 5 years than has been made in 50 years by the industry in general. Part of this real progress in the application of instrumentation and control has been born of necessity because milling processes are more complex. A lot of the impetus for instrumentation and control has come from the fact that the industry is new, the processes are new, and there are no hide-bound conventions to overcome. Part of it comes from the fact that much of processing is more chemical than metallurgical and the thinking of the process chemist has carried over into the plants. One need not elaborate on what instrumentation has done for the process chemical industries. Each new mill that is constructed, if of appreciable size, seems to employ more instrumentation than the previously completed plant. Plant A makes a break-through in the application of instrumentation to a particular part of the process and Plant B accepts this and goes one step farther, while Plant C, anticipating Plant B, makes two or three more steps before Plant B is entirely leveled out.

Jan 9, 1958

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

By J. Menashi, D. A. Douglas, A. S. Rappas

Aqueous solutions of Na2Cr04 are reduced with CO to produce hydrous Cr2O3 and NaHCO3/Na2CO3. CH3OH, HCOO- and HCHO in the presence of CO2 also reduce Cr(VI) and yield similar products. It is shown that the rate of Cr(VI) reduction can be represented by the expression -d [Cr(VI) ]/dt = k[Cr(VI)]0.5[R], where [R] is the aqueous phase concentration of CH3OH, HCOO- or CO. With these three reductants, the activation energies for the reduction processes are comparable and are of the order of 100 kJ/mol (43,000 Btu per lb mol). Rapid reduction rates are attained at temperatures in excess of 220°C (428°F). With these three reductants, a green acid-insoluble readily filterable hydrous Cr203, is formed. With HCHO, significant reduction of Cr(VI) occurs at about 80° to 100° C (176° to 212° F). The product is an acid-soluble violet modification of hydrous Cr203. Solutions of Na2CrO4 contaminated with Mo(VI) and W(VI) can be reduced to yield a Cr2O3 product with significantly reduced contaminant levels.

Jan 1, 1986

By J. Kent Smith

Vanadium is generally spoken of as a rare element; but, even in the light of our resources as known a couple of years ago, this description could be accepted in a qualified sense only. In fact, vanadium is very widely distributed, being a constituent of most clays, while even caustic soda has been shown to contain almost regularly a minute proportion of it, although the quantity in each case is so small as to render impracticable the extraction of the metal therefrom with profit. The opening-up of a large deposit of vanadium sulphide ore in South America has put a new phase on the commercial outlook of vanadium, the technical value of which for the improrement of steel has been proved by rigorous scientific investigation. This sulphide ore has the following analysis: Per Cent. Vanadium sulphide,.39.84 Molybdenum sulphide,.1.57 Nickel sulphide,.........1.49 Iron sulphide,.........4.07 Arsenic sulphide,.. nil. Copper sulphide,.. nil. Manganese sulphide,..nil. Free sulphur,..30.57 Phosphorus,...nil. Silica,....13.60 Alumina,..........2.46 Combined water, 5.00 Carbonic acid, Lime, magnesia, potash, soda and unaccounted for, 100.00 Being a free-burning ore it is calcined with ease, losing 45 per cent. of its weight in the process. The calcined ore has the following analysis:

Jan 1, 1908

By A. M. Gaudin, Olav Mellgren, P. L. De Bruyn

In commonly used to prepare the surface of the mineral to be floated so that attachment to air takes place. The quantity of agent required to make the mineral hydrophobic is usually very small, of the order of 0.1 to 0.25 lb per ton of mineral. Details of the mechanism of pyrite collection are for the most part unsettled. Adsorption of collector has long been believed to involve an ion exchange mechanism as demonstrated for galena' and for chalcocite. In the work on chalcocite it was also demonstrated that a film of xanthate radicals unleachable in solvents that dissolve alkali xanthates, copper xanthate, or dixanthogen was formed at the surface of the mineral. The unleachable product increased with increasing addition of xanthate up to a maximum corresponding to an oriented monolayer of xanthate radicals. Pyrite is extremely floatable with xanthate if its surface is fresh,,' but the floatability decreases rapidly as oxide coatings increase in abundance. Pyrite shows zero contact angle when in contact with ethyl xanthate solution at pH higher than about 10.5; at neutrality. a contact angle of 60° is obtained at a reagent concentration of 25 mg per liter. Alkali sulfides and cyanides are pyrite depressants.

Jan 1, 1956

By George Beavers

FLASH roasting of iron concentrate is in the experimental stage at Copperhill. The problem is peculiar in that the iron concentrate is predominantly pyrrhotite; the ratio of that mineral to pyrite being 5 to 1. Results so far indicate that the heat, generated in roasting a material containing 52.0 per cent iron and 38.0 per cent sulfur, requires special handling and for this reason the installation costs per ton of roaster feed may be too great to compete with hearth roasting. Interesting features of flash roasting at Copperhill are: 1. The sulfur dioxide content of the roaster exit gas can be varied between wide limits. Eight per cent sulfur dioxide gas, with 1.30 per cent sulfur in the calcine, has been common practice and gas up to 13.0 per cent sulfur dioxide has been possible. 2. Temperatures of the exit gases are very high. When roasting 60 tons or more of iron concentrate per 24 hr. in a modified Wedge roaster, the temperature in the roaster rises to 2000° F. and the calcine is lowered to 0.20 per cent sulfur. If the entire roaster system could be constructed to withstand such temperatures, ideal roasting conditions would obtain as regards sulfur elimination and tonnage roasted.

Jan 1, 1934

By the courtesy of Sir Robert Hadfield, we have received the fol¬lowing communication relating to the development and encouragement of science and research in Germany at present. These statements have been translated by Sir Robert from various German sources, and are presented here as an indication of what Germany is doing not only to further her military power, but also to prepare for the period of trade rehabilitation to which she is looking forward after the close of, the war. KAISER WILHELM TRUST FOR PROMOTION OF WAR SCIENCE The Kaiser has approved the foundation of a Trust with the name given above. The aim of the Trust is to further the development of scientific and technical aids to warfare, by uniting the scientific and the military forces of the country for work together. The scientific Work is to be carried on by the following technical committees (or commissions) (1) Committee for the chemical raw materials, for the production of munitions-manufacturing materials. (2) Committee for chemical war materials (powder, explosives, gas, and the like). (3) Committee for physics, including ballistics, telephony, telegraphy, determination of targets and distances, measurements, and the like. (4) Committee for engineering and communication. (5) Committee for aeronautics. (6) Committee for obtaining and preparation of metals.

Jan 8, 1918

By R. C. Hall

DEVELOPED to grow single crystals of alloys of high hardness and high melting points is a simple but effective apparatus described in this note. Growth from the melt, that is, by the Bridgman technique, hay be applied to metals or alloys which are physically hard as long as no phase transformation occurs on cooling to room temperature. The present apparatus was employed to grow single crystals of the ferromagnetic AI-Fe alloys above 1 wt pct Al and the Si-Fe alloys above 3 wt pct Si. Single Crystal Growth In a simple form, the method for growth of single crystals from the melt requires a molten metal charge in a pointed crucible which is slowly low-ered through a heated zone into a colder zone. Solidification starts at the bottom point and continues up the charge as the crucible is lowered through the heated zone. If a single crystal nucleates at the bottom, one crystal may grow throughout the charge under ideal conditions of slow growth.4,5 The presently developed method of growth was designed so that the chances that more than one crystal would grow were small. The single crystals were growth by the apparatus illustrated in Fig. 1. The charge was in the form

Jan 1, 1958

By P. R. Sperry, M. L. Holzworth, P. A. Beck

The basic work of Z. Jeffries 1,2,3 has long ago established the main features of grain growth in the presence of a dispersed second phase. Working with sintered specimens of initially fine grained tungsten, to which various amounts of thoria had been added, Jeffries found that grain growth was inhibited, that is, practically prevented, up to a certain annealing temperature. When this temperature, which increased with the thoria content, was exceeded, extremely large grains developed abruptly from the fine grained matrix. such a a temperature" was later found by Gross-mann~3,14 in certain types of steel, while ~~i~ showed15 that in other steels grain growth was gradual, without inhibition and abrupt coarsening. Later work demonstrated the connection between coarsening and aluminum additions. The viewpoint that the direct cause of inhibition and coarsening in aluminum killed steels is a fine dispersion of aluminum oxide21 appears to be held quite generally, although some doubts have been voiced even very recently, 20 In steels with Ti additions the titanium carbide phase is considered responsible for the inhibition effects found.20 The coarsening temperature increases with the titanium content. That coarsening may occur, as a result of, certain heat treatments, even in low carboil rimmed sheet steel, was shown by Samuels. He also detected coarsening in a steel ingot of similar composition, after giving it the same heat treatment as that used by him for the sheet material. In this instance the identity of the inhibiting phase has not been determined. However, Tangerding found23 that even the few small carbide particles, which occur in carbonyl iron, have a very marked inhibitive effect. As a result of an oxidizing anneal at 850°C, large grains begin to form at the surface of the carbonyl iron specimen, and gradually grow inward as the subsurface oxidation of the carbide particles progresses and eliminates the obstruction. The carbide particles Can be removed also by annealing in hydrogen, with similar results. But if the oxidizing anneal of 10 hr at 850°C in air is followed between in hydrogen for 75 hr at the Same temperature, grain growth is more hibition usually the whole specimen is transformed into a single crystal (approx. 1.5 cm X 5 cm). The reversed procedure, that is, hydrogen annealing followed by oxidizing annealing leads to smaller grains. Tangerding arrived at the logical conclusion that there must have been in his specimens some additional obstruction to grain growth hibition from a minor impurity, other than carbon. It seems likely that this obstruction was caused by an oxide formed during the oxidizing anneal and gradually reduced rtain the subsequent hydrogen-annealing. Other instances of grain growth inhibition of varying severity, associated with a dispersed second phase, have been described by several authors. Notable examples: lead with 0.06 pet Cu or Ni,24 cartridge brass with 0.12 pct Cr,25 or with up to 0.15

Jan 1, 1949

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By H. B. Probst

Mechanical twins were produced in zone-refined tungsten single crystals by explosive working at room temperature. These twins are parallel to (112) planes and have irregular boundaries rather than the classical plane twin boundaries. These boundaries aye grooved surfaces in which the grooves themselves are parallel to a <111> direction and the sides of the grooves appear to be par-allel to (110) planes. TWINS were produced in tungsten single crystals by explosive working at room temperature. These twins differ in character from any previously reported for tungsten; however, they are similar to those found in molybdenum after compression at -196°C.1 Deformation twins "resembling Neumann bands in ingot iron" have been observed in tungsten by Bech-told and Shewmon.2 This observation was made with sintered polycrystalline tungsten pulled in tension to fracture at 100°C and using a strain rate of 2.8 x 10-4 sec-1. More recently Schadler3 found deformation twins in zone-refined tungsten single crystals pulled in tension at -196"&apos; and -253°C. These tests were conducted using a strain rate of 3.3 x l0-4 sec-1, and the twin bands were found to be parallel to a (112) plane. Deformation twins in tungsten&apos;s sister metal, molybdenum, were observed by Cahn.4 These twins were produced by compressing small (0.7 mm) vapor-deproducedposited molybdenum single crystals at -183°C. The compression was performed &apos;by impact." By the use of precession X-ray techniques, Cahn was able to identify the twin plane as {112} and the shear direction as <1ll>. Mueller and Parker1 produced deformation twins in polycrystalline electron-beam-melted molybdenum by compression at -196°C. Their "loading rate" was 5000 psi per min which, judging from their stress-strain curve, corresponds to a strain rate of approximately 0.3 x 10-4 sec-1. These twin bands were found to be parallel to (1 12) planes; however, they differed in appearance from previously observed twins. In place of straight and parallel twin boundaries they were found to be irregular, jagged, and sawtoothed. The sides of the saw teeth were identified as (110) planes and irrational planes of a (111) zone. The twins observed in the present work in tungsten single crystals are similar in appearance to those of Mueller and Parker in polycrystalline molybdenum. The starting material used in this investigation was 3/16-in. diam commercial tungsten rod produced by powder-metallurgy techniques. This material was converted to a single crystal by the electron-bombardment floating-zone technique.= The process was carried out in a vacuum of 10-5 mm of Hg using a traversing speed of 4 mm per min. Segments (=2 in. long and 3/16 in. in diam) of two crystals (A and B) produced in this manner were studied. Crystal A received one zoning pass, while crystal B received two passes. The two crystals were explosively worked at Bat-telle Memorial Institute in the following manner. A 1/2-in.-thick layer of plastic was applied to the crystals to serve as a buffer in an attempt to prevent cracking. The composite, crystal and buffer, was then wrapped with 1/8-in.-thick DuPont sheet explosive EL506A2 and detonated in water at room temperature. Metallographic samples of the worked crystals were prepared, and back-reflection Laue X-ray patterns were obtained using unfiltered molybdenum radiation. RESULTS AND DISCUSSION Blasting the crystals as described above failed to prevent cracking. The crystals fractured into several fragments about 3/16 to 1/2 in. long; however, the fragments were of sufficient size to be useful for the subsequent study. The diamond pyramid hardness of the crystals after blasting was in the range 430 to 450 as compared with 340 for the as-melted material, which shows a definite hardening resulting from plastic deformation. These hardness values were obtained using a 1000-g load and taking readings only in sound portions of the crystals free of cracks. The crystals exhibited profuse twinning as shown in Fig. 1. No such structure is present in the as-melted condition. Most of these twins have jagged twin boundaries and are similar in appearance to those found in molybdenum by Mueller and Parker. The twins in both crystals were found to be parallel to {112} planes. This identification was made by using the conventional two-trace method. Subsequent efforts to describe these twins more fully were carried out on crystal A. If the longitudinal axis of crystal A is placed in the (001)-(011)-(Il l) basic triangle of the standard cubic stereographic projection, as in Fig. 2, then the two sets of twins shown in Fig. 1 are parallel to the (112) and (121) planes. Fig. 3 shows a schematic representation of a twin with jagged boundaries. This type of twin with a <111>

Jan 1, 1962

By H. I. Aaronson, C. Wells

Configurations of ferrite crystals have been found in a plain carbon steel which appear to have resulted from the nucleation of new ferrite crystals at the interphase boundaries of previously formed crystals despite the high carbon concentrations which necessarily develop at these boundaries. This phenomenon has been termed sympathetic nucleation. An attempt has been made to reconcile the occurrence of sympathetic nu-cleation with current nucleation theory. THIS investigation is one of a series on the formation of proeutectoid ferrite from austenite. From the viewpoint of chemical composition, this reaction consists of the nucleation and diffusional growth of crystals of carbon-poor ferrite within a matrix of carbon-rich austenite. The austenite adjacent to the austenite-ferrite boundaries will be greatly enriched in carbon, approximately to the value of the y/(a + y) equilibrium curve or its metastable extrapolation at the temperature of transformation. Those areas of austenite appreciably farther removed from the growing ferrite, on the other hand, will be relatively unaltered in composition, especially at the earlier stages of transformation. Since rates of nucleation are considered to decrease exponentially with decreasing supersaturation,&apos; the frequency with which ferrite nuclei appear at austenite-ferrite boundaries should be negligible in relation to that at which they form in other regions of the austenite. During this investigation, however, many groupings of ferrite crystals have been found which appear to have resulted from the nucleation of ferrite at austenite-ferrite boundaries. This phenomenon has been given the name of sympathetic 71.1tcleation. A number of micrographs of morphological configurations caused by sympathetic nucleation will be presented, after which an explanation for this reaction will be proposed in terms of current nucleation theory. Some of the structures to be considered are composed of bainite, an aggregate of ferrite and carbide, rather than of ferrite. Since ferrite and bainite differ only in that bainite forms under conditions which result in the nucleation of carbides behind the advancing austenite-ferrite boundaries,&apos; it will usually be unnecessary, for the purpose of this paper, to distinguish between the two reaction products. All studies were performed on an electric furnace steel (obtained from the Vanadium Alloy Steel Co.) containing 0.29 pct C, 0.76 pct Mn, 0.25 pct Si, 0.005 pct P, and 0.007 pct S. The alloy was cast as a 150 Ib, 7x7 in. cross section ingot and forged into bars 2x2 in. in cross section. These bars were homogenized for 48 hr at 1250°C in an Endo-Gas atmosphere. The depth to which decarburization penetrated during this heat treatment was determined by chemical and microscopic analyses and the affected metal was removed by machining. Specimens for isothermal transformation studies were cut from the remaining material; most of these specimens were 1/2x1/4X1/16 in., though some with a thickness of 1/32 in. were prepared for use at the shorter reaction times and lower reaction temperatures. Specimens were austenitized for 30 min at 1300°C, isothermally reacted for various times at temperatures ranging from 775" to 475 "C, and then quenched in iced water. The austenite grain sizes within individual specimens ranged from ASTM Nos. 1 through —4. A commercial heat-treating salt which was continuously deoxidized by an immersed graphite crucible served to minimize the loss of carbon during austenitizing; thick covers of powdered graphite and immersed graphite rods effectively prevented decarburization in the lead pots employed for the isothermal reaction treatments. The heat-treated specimens were sectioned and mounted in Bakelite. Following the completion of standard grinding and mechanical polishing procedures, the specimens were electrolytically polished with a Buehler-Waisman apparatus and etched in 2 pct nital. Experimental Results Rules of Evidence for Sympathetic Nucleation—On the basis of observations made on a single plane of polish, one precipitate crystal may be considered to have been sympathetically nucleated at the inter-phase boundary of another precipitate crystal when the following conditions are fulfilled: 1) The sympathetically nucleated crystal is not in contact with a grain boundary or a subboundary in the matrix phase. 2) The shape, size, and location of the crystal at whose boundary sympathetic nucleation occurred (hereafter termed the base crystal) and the crystal formed by sympathetic nucleation substantially pre-clude the possibility that the plane of polish em-ployed may have concealed the fact that both crys-tals actually nucleated at a grain boundary or a sub-boundary in the matrix phase.

Jan 1, 1957

By John Wulff

In a previous paper Burwell and Wulff1 have shown by electron diffraction studies that allotropic transformations can be induced in 18-8 stainless steel by polishing to a depth of about 5 X 10-5 cm. The development of a successful etching technique, which removes accountable amounts of metal from the surface without pitting and without changing the root-mean-square profile as measured with an Abbot pro-filometer, led to the application of the whole technique and material to an investigation of various mechanical methods of surface preparation, such as grinding, lapping, superfinishing and cold-rolling. Ideally suited to such a study is 18-8 of low carbon and nitrogen content. The material can be heat-treated to produce a coarse-grained single-phase structure. On cold deformation there occurs not only a reduction in grain size but, at regions of maximum stress, a change of face-centered material to body-centered material, provided the metal is worked below about 200°C. When worked between 200"about and 415°C., diffraction studies evidence a reduction in grain size without the appearance of any new body-centered ferrite. Ferrite, which can be referred also to strains induced by carbide precipitation, is evident when the material is worked at temperatures between 4150 and 800°C. Stainless steel is advantageous because the usual surface-finishing operations do not readily oxidize it to any appreciable depth. In order to produce detectable oxide films on the surface of austenitic 18-8 in a time equivalent to that required to produce, for example, a fine ground finish on 1/2 sq. in., the sample must be held in a furnace or oxygen stream above 600°C. By using longer heating times, it is possible to achieve measurable oxide films on samples , whose surface temperatures exceed only about 250°C. Experimental Procedure The apparatus, material, and technique described in the previous paper1 were employed in this investigation. Samples of 18-8, I by I cm. by 4 mm., were carefully annealed in the austenitic range to produce a coarse-grained structure. They were then quenched and pickled to remove scale, On a lapping machine of the Graton2 type, both sides of each sample were polished to a a of 1/6 a wave length of sodium D light. Thereafter they were electrolytically etched to remove at least 1 X 10-3 cm. of the surface, a depth that is well below that of any defermations induced by surface preparation. samples of this material, carefully mounted in steel holders, were then sent to various industrial organizations known for special finishing techniques. In the instrue ment shops at the Massachusetts Institute of Technology check samples were finished by the same methods, as far as they were available. Abbot profilometer3 readings Were made on all the samples, which were then carefully degreased in double distilled benzine and alcohol, dried in a hot-filtered air blast, and kept in a desiccator. SUC-

Jan 1, 1941