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By N. Schapiro, R. J. Gray, G. D. Coe

A petrographic and chemical investigation was conducted to determine the occurrence and distribution of the organic and inorganic forms of sulfur in various size and specific gravity fractions of a high volatile, A-rank, Pittsburgh seam coal. The investigation was conducted to aid in the resolution of the problem of how metallurgical coke of lower sulfur content can be produced from high sulfur coals. The Pittsburgh raw coal contains about 2.4% S in two dominant forms: pyritic and organic. Pyritic sulfur constitutes about 57% of the total sulfur in the raw coal and occurs in macroscopic and microscopic-size particles. A plant cleaning process mechanically separates between 50 and 60% of the pyritic sulfur, mainly the macroscopic particles. The organic sulfur constitutes 41% of the total sulfur in the raw coal and 55% of the sulfur in the washed coal. Thus, organic sulfur is not reduced by physical methods of separation. Organic sulfur occurs in all the coal entities, but in general, increases as the exinoid content of the coal increases. In this study, it was found that carbonizing certain selected low gravity coal fractions containing an average of 0.45% pyritic sulfur and 1.01% organic sulfur produced cokes containing an average of 0.22% pyritic sulfur and 0.91% organic sulfur. However, the organic sulfur in the coke is probably derived in part from the heating of pyrite in the presence of carbon. Thus, the total sulfur in the coal carbonized is the most important factor affecting the sulfur content of the coke produced. Concentration of microscopic pyritic and organic sulfur in the middling-type coal indicates the necessity for rejecting as much of this material as is economically feasible. Most of the sulfur introduced into the blast furnace originates from the coke. Although the sulfur content of the hot metal can be controlled by the addition of flux, the flux used restricts the productivity of the furnace by displacing ore and requires first to be smelted; therefore, low sulfur coke is highly desirable. Since the sulfur content of coke is dependent upon the sulfur content of the coals from which the coke is produced, low sulfur coals are required to produce low sulfur coke. In the western Pennsylvania area, large quantities of good coking coal are available from the Pittsburgh seam, but this coal unfortunately contains relatively large quantities of sulfur. To provide information that might be useful in reducing the sulfur content of this coal in the cleaning process, an investigation was conducted to determine the physical and chemical forms in which this sulfur occurs and with what petrographic components it might be associated. The Pittsburgh seam coal, like most other coals, contains two dominant forms of sulfur: one occurs as the minerals pyrite and/or marcasite and is referred to as pyritic sulfur; the other is combined with the coal substance and is called organic sulfur. Pyritic sulfur is amenable to physical methods of separation, whereas organic sulfur is not. Pyritic sulfur particles must be freed from the surrounding coal if they are to be removed in the washing process. Generally, this requires crushing; the required degree of crushing being a function of the size and distribution of the pyrite. The present investigation was conducted to 1) determine the size, distribution and association of sulfur-bearing minerals in the coal and 2) to determine whether the organic sulfur has a preferential association with specific coal entities. If a preferential association exists, this knowledge may be useful in devising a method for organic sulfur reduction. In addition, a study was made to determine the extent to which pyritic and organic forms of sulfur in the coal contribute to the sulfur in the coke produced from this coal. A representative 3%-ton sample of raw coal was crushed to —3 in. and screened into square-mesh sizes: 3 to 1 in., 1 to % in., % to % in., % in. to 10 mesh, 10 to 35 mesh, and 35 to 200 mesh. Separate samples of the -200-mesh fraction and the all-size composite were also collected. Each size fraction (except the -200 mesh) was fractionated on heavy liquids of the following specific gravities: 1.280, 1.300, 1.325, 1.350, 1.375, 1.400, 1.425, 1.450,

Jan 1, 1963

By N. A. Gokcen

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

Jan 1, 1954

By R. B. Snow

THIS paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents-lime (CaO), tricalcium silicate (3CaO•SiO2), dicalcium silicate (2CaO-SiO2), monticellite (CaO•MgO-SiO2), or forsterite (2MgO•SiO2), with especial emphasis on the mineral merwinite (3CaO-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, "FeO," MnO and SiO2, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as aluminates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + MgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO2 is more than 2 to r. When sufficient lime is available it combines with the silica to form dicalcium silicate (2CaO•SiO2), which contains little, if any, MgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2CaO•SiO2) it combines with MgO to form either merwinite (3CaO•MgO.2SiO2) or monticellite (CaO-MgO•SiO2); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and MnO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as CaO-MnO•SiO2 and CaO-FeO-SiO2 are found only in slags in which the lime-silica ratio is less than 2 and are not observed in specimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of opaque or colored constituents. The indices of retraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3CaO•MgO.2SiO2) from its optical properties is usually difficult in the presence of dicalcium silicate (2CaO•SiO2). CaO, MgO, 3CaO•SiO2 and 2CaO•SiO2 in open-hearth slags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1947

By George M. Fowler

THE Tri-State district, as outlined in this paper, refers to the entire mineralized area in southwestern Missouri, southeastern Kansas and northeastern Oklahoma (Fig. 1). The part of the district in Missouri and near Galena, Kans., is still sometimes referred to as the Joplin district (Fig. 2). The Picher-Miami area is that part of the Tri-State district located contiguously in Kansas and Oklahoma in the vicinity of Baxter Springs, Picher and Miami. This paper is confined almost wholly to the ore deposits of the Tri-State district and particularly to the Picher-Miami area. Our study of the ore deposits of this district dates from late in 1925 (by Fowler) and early in 1927 (by Lyden) to the present. Our work has been confined almost entirely to the search for ore for numerous companies and individuals. It was not possible for us to undertake numerous highly interesting investigations which presented themselves but which would not immediately help in finding ore. We particularly refer to the general structural geology of the Ozark uplift, the genesis of the ore, and other problems of a similar nature. The local and general structural problems of the district are being solved gradually as the work progresses. The factors that control the loci of the several orebodies are evident. This paper is based almost exclusively upon our own observations. Most of the important mines in the Picher-Miami area were studied in detail. A map (Fig. 5) is included which shows this area and the properties we have examined to date. When it was convenient we visited, studied and compared structural relations in numerous mines in states outside the district. Some of these observations are noted in this paper.

Jan 1, 1932

By Milton H. Fies

Although pig iron from iron ore and red cedar charcoal preceded the mining of coal by many years, for tradition says that Alabama iron was used to shoe the horses of Andrew Jackson's soldiers, coal was not produced until 1830. In that year, coal was mined in Tuscaloosa County, in the vicinity of what is now the University of Alabama, and shipped on flat boats (obviously during the wet season, for there were many shoals) down the Warrior River to Mobile. About that time, the first railroad, the Decatur & Tecumseh, was being constructed in northern Alabama to overcome the obstructions to freight traffic caused by the now well-known Muscle Shoals in the Tennessee River. This railroad was patterned after a railroad at Mauch Chunk, Pa., which was used for hauling anthracite from the Panther Creek valley. The Alabama railroad, which required about four years to complete, was 46 miles long and was used solely for the transportation of cotton. Although it was a failure, it demonstrated the practicability of the undertaking, and the succeeding railroads, which were begun in 1834, 1848, 1852, and 1853, added immeasurably to the development of the coal resources of the state. Between the years 1830 and 1860, practically all the coal mined in the state was dug from the outcrop near the river or from the river beds, and shipped by boat to Mobile. Transporting coal down the Warrior River was an undertaking of great risk, required much skill, and frequently had heavy losses. It is recorded that this coal was sold to the gas company in Mobile in 1844; it was most likely mined from the Black Creek Seam. In 1914, on the completion of Lock 17, the Warrior River became a navigable stream from 9 miles above Cordova, Ala., to Mobile and offers a great opportunity for the future development of the coal resources of the state. Coke for foundry use was first made in Alabama in 1855. It was 21 years later, however, in 1876, that pig iron was made from Alabama ore with Alabama coal.

Jan 1, 1925

By A. E. Wheeler, H. Y. Eagle

The copper industry in the Province of Katanga, in the Belgian Congo, which is now controlled and operated by the Union Minére du Haut Katanga, had its inception many years ago in the vision of a Scotsman, Robert Williams, now Sir Robert Williams, Baronet. He it was who personally negotiated the mineral concession with King Leopold of Belgium, sent in the prospecting parties who located most of the present mines of the company, later arranged for the Belgian participation from which the present company was formed, and has been its active mentor ever since. The idea back of his efforts was the establishment of an industry on the Congo-Zambezi divide, of sufficient importance to draw up to it the head of the Cape to Cairo Railroad, the dream of Sir Cecil Rhodes, and the consummation of which he had left as a legacy to Mr. Williams, his successor. The reports of the prospecting expeditions showed that copper in profitable quantity was there, but many difficulties lay in the way of the establishment of the infant industry. The isolated location of the mines, various tribal wars, the Boer War, and many other factors contributed to making progress very slow. However, in spite of these difficulties the railroad was finally built and a blast-furnace plant erected at Lubumbashi, near Elisabethville, the capital of the Province. Operations of this plant were started in 1911, treating high-grade oxidized ores and producing pig copper by a reducing smelting. Production has been continuous since that time and the company has grown so that at present it ranks as the largest individual copper producer in the industry. It is a fitting monument to the foresight, optimism and driving force of its founder, and the progressive policies of his Belgian colleagues. In January, 1914, the Union Miniere du Haut Katanga engaged as its consulting engineer, Archer E. Wheeler, metallurgical engineer, at that time general superintendent of the Great Falls plant of the Anaconda Copper Mining Co. Mr. Wheeler was commissioned by the Board of Directors to proceed into Katanga, and make all necessary investigations to enable him to report on a comprehensive development program, and to recommend a scheme of treatment particularly for their low grade

Jan 1, 1934

By Cyril Wells, Robert F. Mehl

The purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2o C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made2. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsenl that variations as great as 30' C. exist in the reported data on the A3 temperatures in iron-carbon alloys. Fortunately, the Aa temperature in pure iron is now known to be 910" C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato5 on both hypoeutectoid and hyper-eutectoid steels. Esser made a dilatometric and magnetic study of iron and iron-carbon alloys containing 0.06 to 0.86 per cent C, for which a high purity is claimed. Presumably the electrolytic iron was reasonably pure, but the alloys contained considerable impurities, on the average totaling 0.35 per

Jan 1, 1937

By Keijiro Nishio

At a time of great antiquity when our Yomato tribe had not yet found its way throughout the country, there lived in Japan barbarous tribes of the stone age, whose dwellings were vertical caves covered with roof's of twigs and weeds. In a cave lately discovered at the village of Morita, 10 miles west from the port of Aomori, there were found pieces of micaceous iron-ore and psilomelane, with oval holes pierced from both sides. Apparently these objects were regarded as ornaments or curios, without being applied to any practical use. Among the traditions given in the Nihonshoki, an ancient history of Japan, there is one relating to the mining industry. According to this tradition, in the mythological age Izanami-no-Mikoto gave birth to Kanayamahiko-no-Mikoto, god of mines, and Amaterasu-Okami (the sun-goddess) was armed with swords. It came to pass at one time that she concealed herself in Ama-no-Iwato ("Heavenly Cave"), and several gods made contrivances to entice her out. Among them, Ishikori-dome, a smith, made a mirror with copper obtained from the Ama-no-Kagoyama, by means of a pair of bellows known as the Ama-no-habuki, which was made of a deer-skin. It is recorded also that Susanb-no-Mikoto, her younger brother, observed the abundance of gold and silver in Korea, where his descendants were to reign, and urged them to provide themselves with boats to convey them across the Sea of Japan. In the course of time he accomplished his object, proceeding to Korea with his son, Isotakeru-no-Mikoto. These accounts

Jan 1, 1913

By B. E. Field

COBALT is a silvery white metal with a slight bluish cast, strongly resembling nickel in its appearance and properties, notably its resistance to corrosion, although its alloys with other metals differ quite decidedly in their properties from those of nickel. The name cobalt was derived from the German "Kobold" meaning goblin and this came to be applied to the cobalt minerals which, although they resembled ores, did not readily yield metal when smelted by the primitive processes available in the Middle Ages. Cobalt minerals were used as pigments by potters and glass workers before the Christian era. Cobalt blue glass was found in the tombs of the Egyptians and in the ruins of Troy, and many colors used by the ancient Greeks and Romans contained cobalt. The ancients were entirely unaware that the colors they used were caused by cobalt and the metal itself was only isolated about the middle of the eighteenth century by Brandt although the preparation of cobalt compounds had been carried on in a small way ever since the opening of the silver-cobalt deposits at Schneeberg, Germany, in 1470. The metal is fairly hard, with a density when pure of 8.81 in the cast state and 8.92 after working. The com¬mercial grade of cobalt has a density of about 8.75 in the cast state. The atomic weight is 58.97. The Brinell hardness of the pure metal is 124; that of the commercial grade varies from as low as 100 to as high as 138, depending upon the impurities present. Pure cobalt has a sharp melting point at 1478°C. The tensile strength of the pure metal in the cast condition is said to be higher than that of any other pure metal. Kalmus gives it as 34,400 lb. per sq. in. for cast unannealed metal; the effect of annealing at 850 to 900°C. is to raise the strength slightly. The yield point is close to the ultimate strength and the reduction in area and elongation are both low. Mechanical working raises the tensile strength of pure cobalt rapidly and in the form of wire it will be over 100,000 lb. per sq. in. The presence of small quantities of carbon in the commercial metal raises the tensile strength to as high as 61,000 lb. per sq. in., the reduction in area and elongation being raised at the same time to approximately 20 per cent.

Jan 1, 1933

By B. S. Norris, Charles R. Austin

The stresses which initiate deformation processes in metals are fundamentally important in the study of the mechanical properties of metals. A point of inflection in the load-elongation curves obtained for single crystals' has been rather too readily interpreted as a true yield point, and the critical resolved shearing stress on the plane of slip taken as a material constant. Even early work showed that the stress at this point varies with rate of loading, but it has not been generally appreciated that creep tests under static loads alone are suited for determining the existence or nonexistence of a yield point.* It has now been shown by Miller that single crystals of zinc3 when loaded statically begin to yield at loads too small to measure; as a result there is no case now known, apart from that cited in the present paper, in which a true critical stress for yielding has been demonstrated for single crystals of metals. The case of iron has especial interest: the existence of an upper and lower yield point and of an elongation at the yield point in ordinary iron and steel marks this substance as unusual, though the effects have been found to a very minor degree in other metals and alloys. $ Most alloys do not show such marked phenomena when appreciable yielding begins, and accordingly modern practice is to speak of the yield strength of such materials, a stress read from the load-elongation curve after elongation has begun, rather than yield point. The special behavior of iron suggests that it is more likely that single crystals of iron should have a true yield point than other metals. The study of the mechanical properties of metals and alloys requires a determination of the crystallographic mechanism of deformation, wlletller deformation proceeds by slip, twinning, or cleavage, or a combination of these, and a determination of the stresses that induce these modes of deformation. With this information, a study of the rates of work-

Jan 1, 1938

By Russell W. Dayton

The metallurgical polarization microscope has been utilized in several researches in the last few years, thus attaining a fair degree of prominence, but little has been written in a manner suitable to a metallurgist concerning the theory of this instrument. In this investigation the theory was carefully studied, and the results are presented here in a detailed manner, yet as simply as possible. The theory is discussed with particular reference to the three chief functions of the instrument: (1) determination of anisotropy; (2) effect of strain; and (3) identification of inclusions. Each of these is investigated experimentally, with especial attention to the mechanism of producing any effect. Where possible, the discussion is supplemented by photomicrographs. The instrument used had numerous defects as a polarization microscope; these and their remedies are discussed. In the microscopic study of transparent mineral sections (chalcography) the use of polarized light has aided tremendously in the identification of a mineral. The determination of strain in transparent substances (photoelasticity) by the use of polarized light has lately become a commercial process, used in testing finished glass articles. The success of the use of polarized light with opaque materials has not been so great. The magnitude of the effects obtained is much less than that of the corresponding effects with transparent materials, and the mechanical difficulties are much greater. Königsberger,"' i in 1909, was the first to apply polarized light to the microscopic study of opaque substances; Endell and Hanemann(2) were the next, in 1913. In 1919 and 1920, Wright(3,4) prepared two papers on the subject. In the first he developed the detailed mathematical theory from the viewpoint of the electromagnetic theory of light, and in the second described the various methods in use, giving improvements of his own. Schwarz(5)

Jan 1, 1935

By Charles S. Barrett

This paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstruc-tures. About 1200 exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,' and a number of these have been selected to illustrate the results obtained. prints are also included showing the common types of falsities—to borrow a term from the biological field, the "artifacts." ln brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. In addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains, since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. Specimen Preparation and Photographs Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for these polishing and etching (each successive polish becoming less severe and each etch lighter), since the fina1 etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and 16, the replicas used were of silica, deposited upon polystyrene and floated from the polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1944

By Taylor Lyman, E. P. Klier

The structures formed when austenite is quenched to subcritical temperatures and allowed to transform isothermally have been the subject of intensive study since the work of Davcnport and Bain.' Isothermal transformation diagrams summarizing the results of many of these studies have become widely familiar to metallurgists. Of particular interest to metallographers are the dark-etchingl acicular products of transformation formed by isothermal reaction below the temperature of maximum velocity of the austenite to pearlite reaction. These products, the bainite structures, can he formed in a wide variety of steels. However, the constitution of bainite is not well understood and divergent views have been expressed as to its mode of formation. In this investigation a combination of dilatometric, microscopic and X-ray methods has been brought to bear upon the problem in the hope of some elucidation of the bainite reaction as it occurs in hypo-eutectoid steels. Mechanism OF Bainite Formation Davenport and Bainl considered the mechanism of bainite formation to consist of two steps—an allotropic transformation followed by precipitation of carbide. The separation in time of the two processes was considered to be very slight in the upper temperature range and very marked at temperatures just above the martensite range. This concept has been restated by Vilella, Guellich and Bain2 in the form of a definition of the acicular mode of transformation as: The successive, abrupt formation of flat plates of supersaturated ferrite along certain crystallographic planes of the austenite grains; this supersaturated ferrite begins at once to reject carbide palticles, (not lamellae), at a rate depending upon temperature In effect, this is the acicular mode of transformation, even though the temperature be such as to limit the actual life of the quasi-martensite to millionths of a second. The investigation of isothermal decomposition of austenite in certain alloy steels (notably those containing chromium or molybdenum) has revealed that there may be a range of temperatures between the pearlite and bainite reactions in which the austenite decomposes at a relatively low rate.3-6 Further, it is characteristic that in the second region of fast reaction the decomposition of the austenite is incomplete by one reaction but goes to completion by a second reaction. These observations led Wever7 to a description of the bainite reaction as follows: I. The reaction takes place by initial precipi. tation of a martensitic intermediate structure. 2. In the upper temperature range this structure readily decomposes into ferrite and cementite. In the lower range carbon separates in an unknown form. 3. In the upper temperature range the precipitated carbide nucleates the precipitation

Jan 1, 1944

By Nathaniel Arbiter, Norman L. Weiss

Factors now accelerating the trend to larger concentrators and larger equipment units are reviewed. After almost 40 years of stability with unit sizes less than 100 cu ft, 200 and 300-cu-ft flotation-cell units are now operating and a 500-cu-ft machine is being built. The design of these cells is considered, as is the design and operation of flotation circuits against the background of the need to achieve greater process efficiency while holding down operating and investment costs. Particular attention is paid to the scale-up problem. With the newer cells having five to ten times higher unit capacities, the advantages resulting from this in sampling, mill operation nnd control, testing and plant layout are indicated, as well as the broad direction for changes in the overall design of 50,000 to 100,000-tpd concentrators. A comparison is given of the available larger cells of U.S. manufacture with analysis of differences and similarities. After almost 60 years of application in this country, froth flotation is still by far the most important process for concentrating metallic ores as well as a number of nonmetallic ores including fluorspar, phosphate rock, and potash. Its use on iron ores and coal is increasing. In the metals groups, the largest plants and the greatest progress are found in copper and molybdenum mills, and the section of this paper that deals with applications will be found most pertinent to that field. During its long reign, the flotation process has passed through several phases of evolution and has achieved progress in economy, efficiency. and simplicity of operation. Much of today's success in the flotation of low-grade ores can be attributed to that progress. Even more important to us than our ability to cope with today's conditions are tomorrow's problems, which we can contemplate with some prescience and confidence. Our annual production of copper, lead, zinc, and molybdenum—to mention only the most important metals occurring in the U.S. as sulfides- must be held at a high level in the face of a declining grade of ore. It is probable that the tonnage of such ores mined and processed will double in this country before the turn of the century. Not only will many of the existing flotation mills be enlarged again and again, but larger mills will be built here and abroad to meet our needs. At this moment, in fact, there are at least three proposed new foreign mills or expansions that envision 100,000-tpd milling rate on copper ores. Table 1' shows the trend in copper ore grades in U.S. in recent years. Table 2' shows the projected annual growth rate of consumption 1966-1985. A study by one of the authors 25 years ago showed that of 32 copper mills in North America with more than 100-tpd capacity, only eight had capacities exceeding 10,000 tpd. The average for these eight was 25,000 tpd. These included the three giants of that day, Magna, Arthur, and Morenci; the other five averaged a little over 10,000 tpd. Today instead of the eight mills with capacities exceeding 10,000-tpd capacity we have 25, and the mill with less than 1000-tpd capacity is fast becoming extinct. Much less range is found in lead and zinc mills, which are still generally small except for the few with over 1000-tpd capacity in Missouri, Utah, and Idaho, and a few zinc ore mills in the same size category. Molybdenum and potash operations are the fastest growers in North America today, but when one considers the projected increase in consumption of copper together with the projected decrease in grade of ore (3% annually), he can foresee that copper ore milling will soon lead the list. Technological improvements to meet the challenge of lower-grade ores have taken the wholly predictable path toward bigger equipment. In mining, shovels, draglines, scrapers, and trucks have led the way; in ore processing, we have seen a rapid increase in size of grinding mills, flotation cells, and pumps. Twenty-five years ago, for example, the 10-ft-diam ball mills treating 2000 tpd at Morenci were considered the giants, but today some grinding mills in similar service have five times that capacity. The specific matters to be dealt with in this paper are 1) the underlying principles that affect flotation-machine design, and the conditions required to produce

Jan 1, 1971

By E. Bicknese, R. Clark

The mechanism and rate of reduction of FeO at conditions similar to those in the stack of a blast furnace have been determined for temperatures from 980" to 1165°C. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal in a static system (no flow of reducing gas) have shown that the CO2-CO ratio of the product gas depends upon the relative reactivities of the Fe2O3 and charcoal. In a systern with a "hot blast" of CO and Nz (simitar to dry bosh gas), synthetic FeO, and actiuated coconut charcoal, the rate of reduction was not sensitive to the flow of reducing gas, and the rate-controlling step alas the chemical reaction at the metal-oxide interface. Wherz solid carbon was not present, a critical flow rate of reducing- gas had to be met in order to prevent a lowering of the reduction rate. The effect of a less-reactive carbon (blast-jurnace coke) and of a "natural" FeO on the mechanistn and rate, and the mininum amount of carbon necessary in the charge to tnaintain the reducing potential of the gas phase, have been determined. THE importance of iron oxide reduction processes has encouraged many studies of the process reaction kinetics. Despite this, the mechanism is not well-understood and three main theories have evolved, which can be stated as follows: A) the rate-controlling step is diffusion, either gaseous diffusion of the reductant or product gas through a porous solid,' or solid-state diffusion of iron and oxygen atoms through the so1id.2 B) The slow step is diffusion of reducing gas through a stagnant boundary layer. C) The reaction rate is controlled by the chemical reaction occurring at the metal-oxide interface and is proportional to the area of this interface.3 By increasing the velocity of the reducing gas to a flow rate beyond which no increase in the reduction rate is observed, critical flow rate, it may be possible to eliminate B as the slow step. However, as warnere points out, the establishment of a critical flow rate may only assure that the reaction is not limited by a reduction in the reducing potential of the gas and that B may still be the rate-determining step. Edstrom and Bitsianes and Seth and Ross8 show that A and C may both be correct for the reduction of the same oxide, depending upon the stage of the reduction, and that the relative importance of the two mechanisms varies with the porosity of the oxide. Themelis9 has derived expressions which express A, B, and C in terms of the fraction reduction, Rx, of a spherical particle. Thus, in the case of A a plot of In (1 - Rx) vs time must be linear and the time to reach a given reduction is proportional to the square of the particle diameter. For B a plot of (1 - Rx) vs must be linear and the time to reach a given reduction is proportional to the square of the diameter. For C a plot of 1 - (1 - RX)1/3 vs f must be linear and the time to reach a given degree of reduction should be proportional to the diameter. In the case of mixad controlled reactions, none of the plots are linear over their entire length. The results of previous studies, in which the rates of gaseous reduction of iron oxide were measured in the absence of carbon, may not correspond to blastfurnace practice because they ignore the effects of the Boudouard reaction. CO2 +C — 2CO The presence of carbon may alter the mechanism or the rate of iron oxide reduction through an enrichment of the gas phase by Eq. [1]. In this case, the presence of and reactivity of carbon become important. If the Boudouard reaction has no effect on the rate of reduction, the reducing gas could be supplied by some means other than the gasification of carbon at the tuyeres and carbon could, theoretically, be eliminated from the burden. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal were made to determine if the reactivity (surface area) of the Fe2O3 had any effect on the product gas composition. Two size fractions of Fe2O3 were reduced with charcoal in a static system (no flow of reducing gas). In each case the charcoal was -100 + 325 mesh and was 25 pct of the total charge. One fraction of the reagent-grade Fe2O3 was submicron in diameter. The other fraction was -100 + 200 mesh and was prepared from the former by compacting, sintering at 1300°C, crushing, and screening. In each experiment, the reaction vessel was filled with a mixture of CO and CO, which would be in equilibrium with FeO and iron at the reaction temperature. A furnace was heated to the desired temperature, the vessel was placed in the furnace, and the gaseous products of the reaction were collected and analyzed. The results of these experiments, Fig. 1, show that the gas phase associated with the submicron oxide is more oxidizing than that with the -100 + 200 mesh oxide. Therefore, in a static system, the relative rates of the reduction reaction and the gasification of carbon depend upon the reactivities of the Fe2O3 and charcoal. The reduction of FeO to iron is the most important reaction occurring in the blast furnace and is probably the slowest of the several reduction steps. The mechanism and rate of reduction of FeO in a system containing carbon and a flow of dry bosh gas have been studied. TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AlME

Jan 1, 1967

By D. J. Weintritt, R. G. Hughes

Statistics show arz increase in the average depth of wells drilled in recent years. As a corollary to this trend, drilling fluids have been improved in an effort to meet the problems inherent at temperatures approaching 500°F. Of importance are (1) deterioration of mud components and (2) the effect of solids on filtration and rheological properties. High-temperature, stable water-base and oil-bare muds are discussed. Those areas in which differences exist are pointed out. Results are based on data taken from the Fann consistotneter, rheometer and shear-strength measurements, static and dynamic filtration tests, methy-lene blue test for bentonite solids and specific heat measLrrenlents of muds. INTRODUCTION Higher well temperatures go along with the fact that the average depth of wells continues to increase. Recent data by Gardner' lists 137 completions deeper than 15,000 ft for the first half of 1964 with a record second-half total of 167 wells drilling or proposed. In addition, there has been an increase in drilling for steam for power production or mineral recovery. In this application the depths are modest, but the mud may approach the critical pressure and temperature of water. Scearce and Magnon' report drilling mud used at temperatures of about 700°F in the Salton Sea area of California. Most deep wells have been drilled with water-base muds. In recent years, however, there has been a substantial increase in the use of oil-base muds because of technological advances in effective additives. The significance of this development was dealt with in considerable detail by Simpson and his co-workers.3 Additiona1 field data have now been obtained to indicate that oil muds are competitive in control, performance and cost with the best types of water muds for use at high temperaturc. This parallel offer of two very different fluid systems, each offering a similar variability in performance, cost and convenience, has created the need to evaluate the merits of these fluids under specified conditions so that the advantages and disadvantages of each can be weighed in relation to the over-all drilling program. This paper is not intended as a review of all the factors. Rather, it attempts to emphasize: (1) important condltions and facts peculiar to high-temperature drilling muds, (2) that more than one imposed test condition or testing method is necessary to describe the quality of a mud at high temperature and (3) that elaborate experimental precautions are necessary whenever laboratory data are used in selection of a mud for field use. WHAT IS A HIGH-TEMPERATURE DRILLING FLUID? For the purpose of this discussion, a high-temperature drilling fluid is any system so formulated or treated to economically minimize the effects of temperature on the properties of the fluid. Our experience in drilling fluids suggests that these effects become obvious for many mud materials at temperatures of 300F or higher. It is understood that hydrolysis of starches, depoly-merization of certain organic thinners, or irreversible chemical reactions (such as that of clay and lime) can affect filtration, viscosity and shear strength at less than 300F. However, the temperature level is not a serious point and in no way affects the precautions and techniques used in this study. An up-to-date review of the literature on high-temperature drilling fluids and the many variations was treated by Rogers'in 1963. EXPERIMENTAL REQUIREMENTS TESTING EQUIPMENT AND PROCEDURES With the advent of deeper drilling and increased demand for temperature-stable drilling fluids, new testing equipment and laboratory techniques were devised for the evaluation of drilling fluids subjected to elevated temperature and pressure. While the equipment has not been standardized, it is in widespread use. Milligan et al. Qescribe a filtration cell for determining the filtration properties of drilling fluids at temperatures in excess of 300F. They showed the effect of variations in temperature and pressure on oil and water muds filtered in the 300 to 400F range. The dynamic filtration apparatus described by Simpson6 permits the study of the filtration properties to temperatures of 350F for drilling fluids circulated over sandstone cores. Watkins et al.' describe the use of pressure bombs for studying the effect of prolonged periods of elevated temperature upon the gelation or solidification of drilling fluids. Chisholm et a1.' describe the use of a modified cement consistometer adapted for use in drilling fluid evaluations. A similar consistometer is used in this study, although the application and data-recording method have been changed. The consistency of a mud sample is measured by timing the movement of a soft iron bob which is magnetically moved up and down in the sample container.* Changer in the time of travel and the temperature of the mud at that moment are plotted with a two-point Brown Elec-tronik Recorder. A 10-in. chart with a speed of 4-in./hr is used. Fia.- 1 is a generalized internretation of the data ob-

Jan 1, 1966

By Richard I. Petritz

A brief review of today's processing of integvated circuits is given. The major trends in the development of advanced integvated electronics are identified as 1) the broadening of the integvated circuit concept to a large class of circuit function, 2) the processing of more complex circuits within relatively small chips of silicon, and 3) the processing of very large electronic functions on complete slices of silicon. This latter trend, called array technology, is then developed in detail. Emphasis is given to defining the key tech-nological problems. Current progress being made is illustrated. THIS paper will endeavor to identify the major trends in advanced integrated electronics technology. One of these, array technology, will be developed in some detail. The array technology discussion will identify the key problem areas. Since it is the scope of the entire meeting' to present specific progress in the science and technology of integrated electronics, we shall indicate general directions being explored rather than discuss comprehensively solutions to the problems. In order to set the stage for the discussion of future trends in integrated-electronics technology, let us briefly compare the processes by which circuits are fabricated through discrete-device technology with that of integrated circuits technology. The reader is referred to the December 1964 issue of Proceedings of IEEE2 for a comprehensive review of integrated electronics. The article3 by Jay Lathrop is an excellent discussion of integrated-circuits technology. A discussion of the history of semiconductor technology is contained in Ref. 4. A) Current Status of Integrated Electronics. Fig. 1 (top) shows the process by which circuits are constructed from discrete devices. Key points are: 1) Slices containing large numbers of transistors or diodes are processed separately. 2) The slices are scribed into small chips (on the order of 15 mils on a side is about as small as can be conveniently handled) each chip containing one transistor. 3) Each device is specified separately—circuit -function specs are derived largely from device specs. 4) Circuits are formed by connecting together the discrete devices. 5) The number of circuit connections required is approximately equal to the number of devices. 6) There are potentially many more discrete devices per inch2 of semiconductor—only our lack of ability to handle them in discrete form prevents us from going to several orders of magnitude higher density iin Fig. 1, 400,000 transistors are discussed at 1.5 mils on a side). The bottom part of Fig. 1 illustrates the integrated circuit process. Key points are: 1) On the same slice of silicon, transistors, diodes, and resistors are processed grouped to do a complete circuit function. 2) While still in slice form, the components are interconnected into circuit functions by an evaporation process, eliminating the need for separate interconnection steps later. Dramatic improvements in cost and reliability are realized. With a simple flash of metalization thousands of interconnections are reliably made. 3) The slices are scribed into chips which contain complete circuit functions. 4) The circuit functions are specified-not each component in the circuit. This important point was missed by some of the early opponents to integrated circuitry. They argued that, with device yields at x pct, integrated circuit yields would be pct, where n is the required number of devices to make a circuit. This argument leads to extremely low yields for integrated circuits. The fallacy of the argument is that in integrated circuits each device is not specified separately. Furthermore, since a device is forever integrated into a specific circuit function, it need meet only the requirements for that particular function. Discrete devices, on the other hand, are tightly specified so that they can be applied to a variety of circuit functions. 5) Extremely high packing densities are achievable because one need only make the basic devices as large as the circuit demands. Their size is not dictated by handling requirements. A current example

Jan 1, 1967

By W. A. Hutchins

Water laws important to the mining industry are those which govern or affect the right to use water, to dispose of water after using it in mining or milling, and to discharge waste material into watercourses. They include statutes and court decisions having general applicability, as well as others that pertain specifically to mining. THE INDUSTRY'S CONTRIBUTION TO WESTERN WATER LAW Despite sharp differences of opinion, the water law the Spaniards brought to the Southwest appears to have included some form of appropriation of water. The Mormons, who settled in Utah in the mid-nineteenth century, also developed a system of appro-priative water titles. But by far the most profound impact on western water law was made by the gold-seekers who flocked to the Sierra Nevada foothills of California after the discovery of gold in 1848. Much of the gold was extracted from the ground by hydraulic or placer mining, and so the miners' rights to the use of water became fundamentally important. Since there was no organized government in the foothills and no laws other than those made by the miners, they helped themselves to the land, the gold, and the water needed to work their claims.1 They established and enforced regulations governing the acquirement and holding of mining claims and their rights to the water they needed.' In 1879 Justice Field, former Chief Justice of the California Supreme Court, spoke for the U. S. Supreme Court in saying that the miners were "emphatically the law-makers, as respects mining, upon the public lands in the State."" Rules of the California mining camps were based on two essential principles: 1) priority in discovering claims and appropriating water by diverting it from streams and putting it to use, and 2) diligence in working claims and applying water in mining. The customs so developed, which were copied in mining areas of other states and territories, were enacted into law in one western jurisdiction after another. They form the basis of what is called the arid-region doctrine of prior appropriation of water, which received the attention of Congress in legislation recognizing and protecting appropriations of water for mining, agriculture, and other purposes on the public domain.' In several western states a great number of water cases decided in the early years involved relative rights to the use of water for mining purposes or for milling connected with mining." The miner's inch, the customary unit for measuring water in the mining camps, is still used in various western communities, although its relation to the cubic foot per second varies from one area to another. Undoubtedly, the miners of a century ago made the major contribution to the appropriation doctrine as it is now recognized and applied throughout the West. What inspired the California gold-seekers to develop these principles? Thoughtful writers have pointed out that their regulations and customs were strikingly characteristic of much earlier mining enterprises in the Old World.D It is said that the right of free mining and free use of flowing water therefor —so similar to the California conditions and practices—-was a part of the customs of Germanic miners in the Middle Ages, that it spread from middle Europe to other countries and colonies, and that the doctrine of prior appropriation was widespread in the important mining regions of the world. Certainly the Forty-niners came to California from many countries. It does not tax the imagination to consider that they may have brought with them some knowledge of the old Germanic customs and applied this knowledge in their new environment. RIGHTS TO USE OF WATER IN GENERAL In the West, rights to the use of water of watercourses fall into two categories—appropriative and riparian. The doctrine of prior appropriation is recognized in each of the 17 western states. The riparian doctrine is recognized concurrently with the appropriation doctrine in some of these states but has been abrogated in the others. The riparian doctrine prevails generally throughout the East, although there is now considerable interest in developing something else. Generally speaking, the appropriation doctrine has been highly developed in the West, whereas the principles of riparian doctrine have been comprehensively established in only a few states throughout the country. The subject of water rights is a big one. Space permits no more than a brief discussion of aspects that bear upon the title of this article. RIGHTS OF PRIOR APPROPRIATION Fundamental to the doctrine of prior appropriation is the principle first in time, first in right. Although in some states there are statutory exceptions. the original and still generally prevailing rule is that the first one who initiates a right to divert and use water of a stream, and who completes his undertaking with reasonable diligence, acquires thereby the first right of appropriation of the specific quantity of water involved. Each succeeding right in point of time is junior to all earlier rights but senior to all later ones. The practical effect of this priority system is that when the water supply is not enough for all, the earliest rights must be fully satisfied before any water may be taken by those later in time. Acquirement of Appropriative Rights: Each of the 17 western states has a statute under which water may be appropriated pursuant to a prescribed procedure. Generally, the first step to be taken by the intending appropriator is to file application in the office of the State Engineer for a permit to make the appropriation. In most but not a11 states, valid ap-

Jan 1, 1961

By H. G. Moulton

THE INCREASING scale of mining operations over the past decade, particularly in connection with the exploitation of large bodies of comparatively low-grade copper ores, has made necessary the study of the behavior of rock under failure. When extractions of as high as 40,000 tons a day are reached in steam-shovel operations and as high as 20,000 tons per day in underground mining operations, it is evident that excavations soon become of such size that the behavior of the rock will often be dependent on fundamental principles applicable to more or less homogeneous materials under stress, rather than on weathering or local planes of weakness. In the ordinary rock excavations encountered in civil-engineering practice, such as excavations for subways, highways, railroads, etc., rock faces are not carried to depths sufficient to develop any pressures, or consequently any failures, except those due to loose masses resulting from local planes of weakness. When, however, orebodies whose tonnage is measured by hundreds of thousands are to be extracted by steam-shovel operations in open pits, it is necessary to determine if possible in advance the slopes that the sides of the pits will assume, for these slopes influence the shape of the excavations and thereby the amount of ore that may be extracted by the open-pit method. When large orebodies are mined underground at depths of 300 to 500 ft. (91 to 152 m.) by caving methods, the surface subsiding as the ore is withdrawn, it is necessary to determine in advance the outermost limits of fracture in the subsiding surface, for on the delineation of these limits depends the location of surface improvements, mills, smelters, etc. and also the location of development work, such as hoisting shafts, main haulage levels, and all other underground openings that must remain undisturbed during the period of ore extraction. Heretofore, in civil-engineering practice, it has been assumed that earth and rock behave differently in failure. For the calculation of earth

Jan 2, 1920

By Sidney Powers

CONTENTS PAGE Distribution of fields 4 History of development 6 Origin of oil 7 Structure, accumulation and migration 8 Reservoir rocks 9 Methods of drilling and exploration 10 Oil-field statistics : 12 Description by regions: United States: Appalachian region ; 12 East-central states 17 Kansas 18 Oklahoma : 19 Texas : 24 Arkansas : 32 Louisiana 33 Mississippi ....... 34 Rocky Mountain region : 34 California 37 Canada 41 Mexico 43 Cuba 46 Bibliography 46 THE purpose of this brief account- of the occurrence of petroleum in North America is to make available to those who have a knowledge of geology, but who are not engaged in the petroleum industry, a few salient facts about the location of oil and gas fields, their productivity, the important structural types of accumulation and the age of the rocks containing petroleum. A few useful data and statistics are furnished, yet not complete statistics that are available elsewhere. Geology has been treated in simple terms because the reader is presumed to have little interest in the names of formations and of oil sands. Mineral deposits are more or less analogous. Whether oil or metals, minerals are found in rocks, largely in sedimentary rocks which carry water or have at one time carried it. A genetic or accumula-

Jan 1, 1931