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By Emil Gathmann

STEEL as it is poured, or teemed, into the mold for forming the ingot may be broadly separated into two divisions; i.e., effervescing or gassy steel, also termed evolution steel, and non-effervescing or killed steel, also termed solution steel. Between these primary divisions there are various types having the characteristics of both divisions but really not belonging to either; such steels are termed semi-piping, rising, or wild, as the type may be. True unkilled, or effervescing, steel should contain large volumes of gases, which are evolved while the metal is being teemed, or cast from the ladle nozzle into the mold, and while the temperature of the steel is being reduced prior to the solidification or freezing of the steel, the upper portion, or top, of the ingot remaining liquid due to the evolution of gases until an ingot skin of considerable thickness has been formed. These gases consist principally of hydrogen, carbon monoxide, nitrogen, and ammonia. It is generally understood that nitrogen gases are the first evolved and form the skin blowholes, at times troublesome, in the forming solidifying ingot. Ingots made of effervescing steel will always contain a large number of blowholes. Such blowholes are not deemed objectionable in various products if they occur well within the interior of the ingot where they will not be subject to oxidation upon the ingot's cooling and subsequent re-heating and rolling or forging. Very little top or bottom discard is taken from this type of ingot as pipes, or large shrinkage cavities, at the upper portion of the ingot do not usually occur, the difference in volume between the liquid and the solid steel (6 to 10 per cent.) being compensated for by the innumerable blowholes distributed throughout the body of the , ingot. Of the 40,000,000 tons of steel made in the United States during the year 1919, at least 35,000,000 tons of ingots were made of gassy or semi-gassy steel. Killed, or solution, steel is termed true piping steel from the characteristic pipe or shrinkage cavity that usually occurs in the uppermost central portion of the ingot.

Jan 8, 1920

Gach-Saran.—The most important development of 1937 has been the successful completion of initial exploratory wells in the Gach Saran (formerly known as Gach-i-Qaraghuli) field, about 125 miles southeast of Haft Kel. Two of these wells are rated at 33,000 bbl. per day at flowing pressures exceeding 800 lb. Drilling is proceeding with the object of delimiting the structure. Exploratory drilling is also being undertaken in several areas within the company's concession. In the producing fields the policy of controlled production has been maintained as in the past, and drilling has been limited to that required for maintenance of production and general control of the fields. Acid treatment to increase production when desired has continued to be successful in most cases. Table 1.—Crude Production in Iran Masjid-i-Sulaimana Haft Kel Total Year barrelsb Ton Barrelsb To Barrelab 1936 3,641,247 27,820,000 4,473,849 34,200,000 8,115,096 62,020,000 193P 4,375,112 33,110,000 5,693,849 43,480,000 10,068,961 76,590,000 * Net production; i.e., excluding surplus products re-injected to reservoir. 6 To nearest 10,000. " Correct to November, with an added estimated figure for December. Masjid-i-Su1aiman.—There have been no new developments in this field. The policy of returning, as and when necessary, surplus products to the reservoir has been maintained. Haft Ke1.—Drilling to explore deeper formations has been undertaken, but has not progressed far enough for conclusive results to be drawn. Gasoline retention in the crude by means of multistage pressure stabilization has been continued as in past years. Separation pressures are as follows: well-head separators, 500 lb.; central battery, 190, 85, 40, 20 and 10 lb. per sq. in., respectively. The stabilized crude is delivered to pipe line at atmospheric pressure, or ex the 10-lb. stage, in accordance with refinery requirements.

Jan 1, 1938

By Lawrence K. Jetter, Robert F. Mehl

Some advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory. Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selectcd for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatome tric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system—a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation; there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type—the ideal case which Becker6 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1943

By Lawrence K. Jetter, Robert F. Mehl

Some advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory. Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selectcd for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatome tric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system—a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation; there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type—the ideal case which Becker6 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1943

By Don H. Baker

THE need for new or improved refractory materials has caused metal phosphides to be given renewed scrutiny. Some metal phosphides show high-temperature inertness, are exceptionally hard, and exhibit a marked resistance to chemical attack. Various metal phosphides have been prepared for study by direct combination of the elements,'-' by reaction of metal or metal compounds with phosphine or phosphorus trichloride,'"' by thermal decomposition of a metallic phosphate or phosphite,"-'8 and by molten salt electrolysis.19 Electrolytic preparation of phosphides of titanium, manganese, and chromium from their oxides is reported in this paper. An externally heated 3-in.-ID by 6-in.-deep graphite cell, that served as the anode as well as a container for the electrolyte, was used in these investigations, and a suspended, centrally positioned graphite rod served as the cathode. A closely fitting silicon carbide furnace liner minimized atmospheric oxidation of the crucible. Electrolyses were performed for predetermined periods and current settings. Preliminary research had indicated the more efficient current and potential settings that could be used. Upon completion of the deposition period, the deposit was hot-stripped from the cathode. The mass of crystalline deposit, plus occluded and adhering salt, was crushed to minus 10 mesh and hot-leached in dilute hydrochloric acid. The leached crystalline material was water-washed, dried, and sampled for analysis. Products were identified by X-ray diffraction and standard analytical procedures. Electrochemical studies were initiated to establish the optimum conditions necessary to produce manganese phosphide (MnP), titanium phosphide (Tip), and chromium phosphide (CrP). Among the factors studied were the operating temperature, the imposed current, and the electrolyte system. If the temperature, or imposed current, was too high, deposition of phosphorus resulted, and if either were too low, partially reduced lower oxides were deposited. The operating conditions established for repetitive high-quality production of metal phosphides of the MP structure are presented in Table I. The metal phosphide crystals varied in size, but all had a definite metallic appearance. Typical are the crystals of CrP shown in Fig. 1. Evaluation data and analysis of the crystals are presented in Table 11. Efforts to measure resistivity of these three compounds over the temperature ranges of 250o to 400°K were hampered by the small physical size of the crys-

Jan 1, 1968

By Eugene H. Cowles

The German silver industry of the United States amounts in value to upwards of $6,000,000 or $8,000,000 annually. Several thousands of people earn a livelihood pursuing it, and the beautiful goods and articles manufactured from this time-honored and valued alloy are everywhere visible. German silver enters largely into our street signs, harness and house hardware, and all manner of table-ware, solid or plated. There is scarcely an hour in the day that German or nickel-silver is not before our eyes. The composition of this alloy is a very uncertain thing, and depends largely on the honesty of the manufacturer and the price the purchaser is willing to pay. It is composed of copper, zinc and nickel in varying proportions. The best varieties contain from 18 to 25 per cent. of nickel, and from 20 to 30 per cent. of zinc, the remainder being copper. The more expensive nickel-silver contains from 25 to 33 per cent. of nickel, and from 75 to 66 per cent. of copper. The nickel is used as a whitening element; it also strengthens the alloy and renders it harder and more non-corrodible than the brass made without it, of copper and zinc. Moreover, it reduces the odor emanating from brass, which is so disagreeable if it occurs about the dining-table. Of all troublesome alloys to handle in the foundry or rollingmill, German silver is the worst. It is unmanageable and refractory at every step in its transition from the crude elements into rods, sheets or wire. As a white-headed furnace-man recently said to the writer, in one of our large mills, " you can put eight crucibles into the fire, each containing exactly the same mixture of German silver, and when you take them out and pour them into slabs for rolling, seven will be a mass of scum or slag, or the stuff will swell up like rising bread and overflow the moulds, and be so full of blow-holes that it will look like a sponge. The eighth crucible will contain perfectly good metal. On remelting the next day, the bad stuff will, in nine chances out of ten, come out just as good metal as the eighth pot the day before, and under apparently the same conditions." With nickel at seventy or eighty cents per pound, German silver

Jan 1, 1890

By R. E. Reed, C. J. McHargue

Single crystals of aluminurn were reduced 90 pct in diameter by extrusion at 296" and 77°K. The resultant double fiber texture had a strong (111) component with a weak (001) component. The relative anzounts of these components varied with starting orientation. Decreasing the Lemperatuve of defovtnation increased the amount of (001) texture component in crystals with inilia1 orientations near (111). The starting orientation and temperature of deformation strongly affected the morphology of the (001) component. The effects of orientation and Lemperatuve upon the distribution of the (001 ) texture component in extruded aluminum single crystals were rationalized on the basis of deformation band formation and interaction. MANY papers since the early 1920s have discussed the occurrence of the double fiber texture (111) + (001) in wires and rods of deformed fcc metals. Aside from the reporting of experimental results for the various metals under a variety of fabrication conditions, emphasis has been placed on two related problems. One problem deals with the prediction of ideal end orientations based on the glide systems and flow directions. The other problem seeks the reason why different amounts of each component may be produced by the same fabrication schedule for metals apparently having the same deformation systems. Some of the difficulties in developing a satisfactory explanation have their origin in the experiments themselves. One mistake has often been the assumption of an initially randomly oriented specimen or complete ignorance of effects of starting orientation. Recent studies by Grewen and Wassermann,1 Cullity and co-workers,2' and McHargue4 have shown that the initial orientation may be the most important factor in determining the final orientation. Hence only limited comparisons of data from different studies can be made unless all conditions of the initial material are specified. Another question has been the nature of the (001) component. Hibbards suggested that any (001) present was the result of re crystallization during fabrication. Although Fleischer6 found no (001) texture in aluminum swaged at room temperature, and Dayal 7 found that component to disappear at very high reductions, a double fiber texture has usually been reported for aluminum. Vandermeer and McHargue showed that, while some (001) in aluminum may be the result of recrystallization, much of this component has its origin in the deformation process. Ahlborn and Wassermanng found the (001) component in silver deformed at low temperature not to be the product of recrystallization.

Jan 1, 1968

By Nicholas J. Grant, Noboru Komatsu

Metallographic and X-ray studies were made of oxide dispersion strengthened Cu-12 vol pet SiO2 and Cu-3.5 vol pet Al2O3 alloys following time exposures at temperatures approaching the melting. point of the matrix metal. Changes in hardness, oxide particle size and crystal structure were studied to determine the time-temperature stability of these alloys. An interpretation of the mechanism of oxide agglomeration is proposed. One of the most striking features of dispersion strengthened metal-metal oxide alloys is their stability at elevated temperatures, both with respect to recrystallization and maintenance of mechanical properties after exposure at high temperatures. A small amount of work has been done on the re-crystallization phenomenon in dispersion hardened metal-metal oxide alloys'l and several theoretical treatments have been advanced regarding the stability of these alloys by Lenel and Ansell,8 and by Grant and his co-workers.9, 10 This paper reports on metallographic and X-ray studies following various heat treatments of Cu-AI2D3 and Cu-SiO2 alloys at elevated temperatures and the effect of subsequent cold work on the recrystallizalion temperature. An interpretation of the recrystallization behavior of this type of alloy, based on the decomposition and agglomeration of oxides, is proposed. EXPERIMENTAL PROCEDURE Cast ingot bars of copper-1.59 pet Si and Cu-0.77 pet Al, 7/8 in in diam, were annealed in argon for 80 hr at 1000CC for homogenization. The homogenized rods were machined into fine chips and ball milled. Milled particles in the range minus 20 to plus 60 mesh were separated for internal oxidation. The internal oxidation was accomplished by the same method used by Preston and Grant,9 except that the oxidalion temperature for the Cu-Si alloy was 750°C, and for the Cu-A1 alloy was 800°C. These powders were then hydrogen-reduced at 450°C, compacted in a copper container, evacuated at room temperature to 0.04 µ, and sealed for extrusion. They were extruded at 1400°F (760°C) with a ram speed of 55 in. per min for an extrusion ratio of 15.6 to 1 to give a rod 0.38 in. diam by about 3 ft long.

Jan 1, 1962

By J. David Lowell

For his contributions to the field of mining geology, a striking example being his brilliant inte.rpretation of the complex geologic history of the San Manuel District (Pinal County, Arizona) which resulted in the discovery of the Kalamazoo orebody, and for his lecture, "Copper Resources in 1970." On a low desert ridge six miles south of Cairo lie the remains of the world's earliest known mining town, Maadi of predynastic Egypt. Copper artifacts, including ingots and an ax head which was spoiled in casting, indicate that copper ore was smelted in Maadi, and radiocarbon dating has placed the activity at least as early as 3300 B.C. This is the oldest documented date for the use of smelted copper, the first industrial metal used by man. Copper was mined and smelted almost as early in Asia Minor and on the island of Cyprus, but the greatest development of the budding copper industry was in Egypt, where specific historical records show that about 10,000 tons of copper metal were produced in the period from 1850-1580 B.C. Contrast this production of 35 tons per year with the present world production of about 7 million tpy. Evolution of the Copper Industry The copper ore mined by the ancients was high grade, and the copper produced was expensive. The copper industry began with narrow high-grade veins, but has evolved to the point where massive earth-moving equipment can be operated in huge, low-grade open pits. Indian pits dug before 3000 B.C. in the Lake Superior district were in ore which averaged 15% Cu. His- torical research done by Arthur Brant has shown that copper cost in the Middle East in 1840 B.C. in terms of 1970 labor dollars was about $25 per lb. The copper mined in northern Europe in 1540 in the time of Georgius Agricola averaged about 8% Cu, and the cost in 1970 labor dollars was about $10 per lb. Average ore grade had dropped to about 6% Cu in 1890, and the cost of copper in the U.S. in 1970 dollars was about 45¢ per lb. Butte, Mont., was a good example of the efficiently operated vein mines of this time. In 1906, Daniel Jackling made a dramatic entrance into the copper scene with the Bingham Canyon open-pit copper mine and proved that more profit was possible mining 2% porphyry copper ore on a

Jan 1, 1971

By R. M. Bird

Few persons outside of the foundry trade have any conception of the great variety of sands now regularly specified and furnished, nor of the differences in foundry practice frequently resulting from apparently minor changes in sands. Conditions in each locality where the sands are mined and prepared necessitate special equipment designed to perform the work efficiently. The description that follows of the foundry-sand producing operations is typical of the areas in New York and New Jersey, and particularly refers to the operations of the George F. Pettinos Co. A few years ago the so-called Albany sands were dug by simple methods and hauled by horsecart to railroad. Depletion of sand near railroad sidings and extended use of automotive power have appreciably extended the area from which sand is now being dug. It is not unusual to haul 5 miles to the railroad. As stripping is quite shallow, 6 to 18 in., and the banks of usable sand generally run from 12 in. to 4 ft., it is economical to work the bank by benches so narrow that the overburden can be thrown by hand shovel to the exposed bottoms. In effect the top soil goes back to where it was, but on a lower level. Consequently the general surface appearance of a mined acreage is the same as before. This condition is in fact cutomarily required when a farm owner sells his sand in the ground. After such replacement, in the course of 3 to 5 years the soil is no less fertile than it was before mining. The sand itself varies as to grain and bond vertically and also along the breast. No mechanical equipment has been developed to compete with hand shovels and no machine has as yet been devised that grades the sand as required. Uniformity of sand, as shipped, depends first, last and all the time on the man on the job. Mixing equipment can change the appearance of the sand and mask its lack of uniformity, but it will never correct wrongly graded sand, dug from the bank. Modern methods of testing are helpful in setting up standards against which the man in the bank can compare his sands, but a good bank foreman is the only assurance that the sand, as dug, matches the required sample.

Jan 1, 1926

By W. H. McFarland

The mechanical properties have been determined for a large number of alloy-free martensitic steels with carbon contents ranging from 0.08 to 0.20 pct and with manganese contents of about 0.4 to 0.5 pet. These steels were tested 1) as water-quenched, 2) after quenching, temper rolling, and tinning, and 3) after tempering treatments which involved temperatures from 400o to 1300oF and times from 1 min to 8 hr. The majority of these tests represent steel from commercial-size coils, i.e., strip 32 in. wide, coil weights up to 20,000 16, and steel thicknesses from 0.0055 to 0.024 in. As a result of these treatments, it has been shown that as-quenched low-carbon alloy-free steels can be produced with tensile strengths ranging from 140,000 to 220,000 psi and tensile elongations from 3.0 to 4.0 pet in 2 in. The tensile strength of the as-quenched martensites can be represented by the equation, tensile strength (ksi) = 119 + 560 (wt pet C). The response to tempering of these steels is related to previous work by Muir, Averbach, and Cohen and by Grange and Baughman. Strain aging of low-carbon martensite has also been investigated. If low-carbon steels are defined as those steels with a maximum carbon content of 0.2 pet, it is found that the literature on low-carbon, alloy-free martensites contains little data on the mechanical properties of these steels. However, the following facts concerning low-carbon alloy-free martensites seem firmly established:'-' 1) The major factors in controlling the strength of the martensite appear to be a) fine structure, b) the internal strain resulting from the transformation, and, particularly, c) the amount of carbon in solid solution. 2) In low-carbon steels, the martensite is auto-tempered and is in the form of needles with only minor amounts of internal twinning, whereas the martensite in high-carbon steels forms as plates which are internally twinned on a fine scale. 3) Care must be taken in comparing the results of work that has been done on low-carbon steels with varying amounts of alloying elements to data on plain carbon steels. As has been noted by Irvine, Pickering, and Garstone,6 alloying elements generally lower the martensite start temperature and, thereby, decrease the amount of auto tempering obtained during the quench. This makes it difficult to

Jan 1, 1965

By Jerome Strauss, Carl L. Shapiro

THIS is a critical examination of the theory that the amount of carbon necessary to form the iron-carbon (carbide) eutectoid is lowered by the addition of any carbide-forming element. Although this theory has been built up over a long period of years,, it appears, in the light of recent published investigations upon the ternary constitutional diagrams of iron with carbon and other alloying elements, to be no longer tenable. A survey of these new results, summarized below, shows that (as is known) some metals lower the carbon content of the iron-carbon (carbide) eutectoid, whereas others raise it, but (as not heretofore clearly set forth) some first move the eutectoid in one direction and then, at higher concentrations, shift it in the opposite direction. Moreover, these differences in behavior exist even among the common alloying metals classed as carbide formers. PART I INFLUENCE OF BODY-CENTERED CUBIC ELEMENTS The effects of the various body-centered cubic metals (chromium, tungsten, molybdenum, vanadium, columbium and tantalum) are reviewed individually. Iron-carbon-chromium System.-In the monograph on Alloys of Iron and Chromium, Kinzel and Crafts' concluded that the carbon content of the eutectoid is lowered by increasing the chromium content. The quantitative influence of chromium on the eutectoid point of iron-carbon alloys was shown by Monypenny2 (Fig. I) and no data have been forthcoming to refute his findings. Iron-carbon-tungsten System.-Gregg,3 in the monograph on Alloys of Iron and Tungsten, accepted the data showing that tungsten decreases the amount of carbon required to form the eutectoid. The influence of tungsten on the eutectoid percentage of carbon as determined by Oberhoffer and Daeves4 is shown in Fig. a; these results have received general approval. Iron-carbon-molybdenum System.-In the monograph on Alloys of Iron and Molybdenum, Gregg5 reviewed the work of Guillet,6 Swinden,7 and Reed,8 all showing that molybdenum lowered the carbon content of the eutectoid, whereas Takei9 contradicted this conclusion. Svetchnikoff and Alferova,10 a little later, showed that large additions of molybdenum shift the eutectoid to the right. These last-named investigators found that molybdenum, up to 1.2 per cent, shifts the pearlite point and the point of maximum solubility of cementite in the gamma phase only slightly in the direction of lower carbon content; on the other hand, increasing amounts of molyb-

Jan 1, 1943

By John F. Blandy

Every new mining district has had its own peculiar experiences in inventing and experimenting upon new methods for the various operations of mining, and more particularly in the processes of crushing and dressing ores. As a matter of course, during this period many old things have been reinvented, patented, and cast aside, there to remain until at a future day other geniuses shall bring them forth again as new. In this respect the Copper Region of Michigan has not been behind other mining centres, and probably in no other part of the country has more money been expended in devising new machines and improvements upon old ones for the crushing of the rock. The appliances for washing the sand have not been so varied, simply for the reason that, having but one mineral, or rather metal, of high specific gravity to separate from rock material which varies but little in its character in any one mine, it requires much less care than is necessary in most mining centres of the world. At the beginning of operations in that district most of the work was in the control of Cornish miners, who introduced the simplest of Cornish mills, namely, wooden stem pestles, with wooden shafts and cams. These were well suited to the small mines, and particularly to the limited means of transporting more expensive machinery. As these facilities improved, they were enabled to change to iron, and to vary their patterns of rods, shafts, cams, and mortars. The most approved pattern, finally obtained, is the square or round stem, with collar adjustable by means of keys. In its present form it is a bar of cold rolled shafting, an eye in the top, an adjustable collar with key-plate and keys, the head and a shoe of chilled iron. The stem is fitted into the head by a slight taper. The battery has heretofore been of wood, lined with chilled cast plates, and bed-plate of the same, but within the past year the California pattern has been introduced. The screens are of sheet-steel, drilled with 16 holes to the inch. During this period of trial and gradual improvement in the pestle stamps, in the years 1855-6, the Ball steam-stamps were introduced, and after years of labor and expense, have been made the most efficient and powerful machines ever yet used for the purpose. It is ostensibly the Nasmyth steam-hammer, and yet the

By Geo Ashley

THE following paper is intended to be suggestive only, and to open the way for discussion and further observation. Its preparation was requested only two days before the time limit set for the submission of the papers comprising this symposium. Thus no time existed for detailed studies so it is largely a memorandum of such facts as have come incidentally to the notice of the writer in the study of coal in the field. The field study of sulfur in coal has received very little special attention or description from coal students. The presence of sulfur concretions is noted in hundreds of descriptions, and certain benches of a coal bed may be described as "sulfury" or the presence and position of sulfur bands may be noted in coal sections in connection with sampling. It may be accepted that some sulfur is present in all coal. The amount varies greatly in different regions, in different beds, and in the same bed in different areas. The anthracite of Rhode Island comes the nearest of any coal known to the writer of being free from sulfur, several analyses of that coal showing less than 0.1 per cent. Subbituminous coals in Colorado in a few places have close to 0.2 per cent. of sulfur on the dry-coal basis and in other states subbituminous coals approach this lower limit. Bituminous coals seldom run under 0.4 per cent. of sulfur on the dry basis, though in a few places dry bituminous coals in Colorado and Washington have between 0.3 and 0.4 per cent. The better known bituminous coals have almost everywhere over 0.4 per cent. The best of the Pocahontas and New River coals run close to 0.4 per cent., but there is very little commercial coal in Pennsylvania, Ohio, Indiana, Illinois, Kentucky, or the other states that runs under 0.5 per cent. on the dry basis. From these minimum figures, the amount will range up to 5 or 6 per cent. or higher if visible sulfur is not excluded. It must be remembered that the usual -analysis of a coal bed is not intended to give the total proportion of sulfur in the bed but the amount in the coal after the removal of the more obvious and larger sulfur masses.

Jan 9, 1919

By C. J. McHargue, J. C. Ogle

Lightly deformed columbiun single crystals which contained only parallel hoins or purullel and intersecting trains were annealed at 1000' and 1600"C. No re-crystallizntion occurred in specimens hawing only parallel twins. Only noncoherent twin boundaries nzipated at 1000°C but both coherent and noncoherent ones moved al 1600°C. Recrystallization occurred within a few minutes at twin intersections at 1000°C. The orientation 01 the recrystallized grains differed front that of both the matrix and deformation twins, but could he derired by (110) and/or(112) rotations. ALTHOUGH twinning in metals has been extensively studied, there have been no definitive studies of the annealing behavior of crystals containing deformation twins. Some effects observed after annealing deformation twins have been summarized by Cahn1 and Hall2. Any or all of these phenomena are observed: 1) The twins may contract so that the sharp edges of the lens become blunted, and eventually the twin may disappear entirely. 2) The twins may balloon out at an edge, giving rise to a large grain having the same orientation as the twin. 3) The specimen may recrystallize; i.e., new grains are nucleated and grow at the expense of the twins and the crystal immediately adjoining the twin. Such grains have orientations which are not present before. Contraction has been observed in iron,3 titanium,3, 4 beryllium,5 zinc,8, 7 Fe-A1 alloy,' and uranium.9 Long anneals at high temperatures are required to have any appreciable effect in these metals and only thin twins are absorbed. Lens-shaped twins are absorbed from the edges: the thin, almost parallel-sided twins are usually punctured in several places and each piece contracts independently. Absorption is very gradual and no sudden cooperative jumps have been observed. The expansion of a twin into a larger grain of identical orientation is unusual, but such growth has been observed in iron,"'" zinc,6 and uranium." Crystals which have been deformed simultaneously by slip and twinning recrystallize first in the area adjacent to the twin. New grains appear faster where the twins intersect: but isolated twins, especially if thick, can also give rise to new grains. This type of recrystallization occurs in zinc.6, 7, 12, 13 and beryllium.14 Reed-Hill noted, in a single crystal of magnesium, the nucleation of a recrystallized grain at a twin intersection which had the same orientation as the second-order twin and which grew into the highly strained matrix.15 Short-time annealing has been reported to cause no change in the deformation twins in vanadium,16 columbium, 17, 18 tantalum,19 tungsten,'' and zinc.7 The purpose of this investigation was to note the effects of annealing on the coherent and noncoherent boundaries of deformation twins in columbium and to locate the nucleating sites for recrystallization. The orientation relationships, which the new recrystallized grains have with the parent crystal and the deformation twins, were also determined. EXPERIMENTAL PROCEDURE Single crystals of columbium were obtained by cutting large grains from electron-beam-melted buttons which contained 10 to 50 ppm C, 10 to 100 ppm O,, 1 to 10 ppm H2, and 10 to 15 ppm N2. The crystals were hand-ground and chemically polished until all grain boundaries were removed. The specimens were mounted in an epoxy resin and a face of each crystal was mechanically polished on a Syntron polisher using Linde A and then Linde B polishing compounds. After all faces were mechanically polished, the crystal was electrolytically polished to remove all distortion due to cutting and grinding. Laue photographs were taken of all faces of the crystals to determine the quality and orientation of each crystal. The crystals were compressed about 10 pct at -196 C in a specially constructed compression cage with an Instron tensile machine. Each crystal was separated from the top and bottom anvils by teflon films which acted as a lubricant. With the specimen crystal in position, the entire cage was cooled to -196°C by being submerged in a Dewar containing liquid nitrogen. The crystals were compressed at a rate of 0.02 in. per min and the load was recorded on a strip-chart recorder. After deformation the crystals were mechanically polished on 600-grit paper and Pellon cloth with Linde A and Linde B polishing compounds. The crystal faces were chemically polished and then etched. The twin planes were identified metallographically from an analysis of the twin traces on two surfaces. Annealing was carried out by placing each crystal in a columbium bucket made from the same electron-beam-melted material as the crystal itself and suspending the bucket by a tantalum wire in a quartz tube. After a vacuum of 10-7 Torr was attained, a furnace at 1000" or 1600 C was raised into position and the crystals held for various lengths of time. The crystals were repolished and etched after annealing to remove any surface contamination. Approximately 0.010 in. was removed during this process. The resulting surface was examined metallographically for microstructural changes due to annealing. A microbeam Laue camera mounted on a Hilger Micro-focus X-ray unit was used to determine the Orientstions of the recrystallized grains. This X-ray micro-beam camera had a 0.002-in.-diam collimator and incorporated the ideas of both and and chisWik21 and Cahn.22

Jan 1, 1967

By R. J. Brison, O. F. Tangel

The development of a new method of mineral separation was sponsored by the International Salt Company, which requested Battelle Institute to investigate means for improving the quality and appearance of rock salt from the Company's Detroit mine. Although developed specifically for removing impurities from rock salt, the general method may be applicable to other separation problems. The principal impurities in rock salt from the Detroit mine are dolomite and anhydrite which represent 2 to 5 pct of the weight of the mined salt. In the size range from 1/4 to M in. (the range of primary interest in this project) the impurities are only partially liberated from the halite in normal production. Further size reduction to improve the liberation of impurities is not practicable in view of the market requirements for the coarse grades of rock salt. Laboratory separations in heavy liquids showed that, to improve the quality and appearance of the rock salt substantially, it would be necessary to remove not only free gangue particles but also a large proportion of the locked-in particles. Because rock salt is an inexpensive commodity, a low-cost process was required. Gravity methods were, of course, considered. The heavy-liquid separations indicated that a split at an effective specific gravity of 2.2 to 2.3 would be required. (The specific gravity of pure halite is 2.16.) Heavy-media separation was investigated but had the disadvantages that it was necessary both to operate with saturated brine and to dry the cleaned salt, and that the cleaned salt was darkened by the magnetite medium. Air tabling was tried but did not give the desired separation. It soon became apparent that established methods would not provide a satisfactory solution and work was undertaken on the development of a new process to solve the problem. PROCESS DEVELOPMENT Preliminary Experiments: At the start of the investigation, an analysis of the problem indicated that the diathermacy of rock salt—that is, its ability to transmit radiant heat—might form the basis for an efficient separation process. Under this theory, the impurities might be selectively heated by radiant heat. The particles could then be fed over a belt coated with a heat-sensitive substance so that the warm impure particles would adhere preferentially to the coating. After the initial experiments, made by heating the rock salt with an infrared lamp and separating the product on small sheets of resin-coated rubber, proved encouraging, a small continuous separation unit was set up. This comprised 1) a simple heating unit consisting of a vibrating feeder covered with aluminum foil and an infrared lamp mounted above the feeder and 2) a separation belt 6 in. wide and 36 in. long. A sketch of the device is shown in Fig. 1. Results with this apparatus confirmed the fact that a good separation was possible. It was apparent, however, that a considerable amount of experimental work would be needed to develop the scheme to a practical and economical process. The Process: Basically, the process consists of two main steps: 1) selective heating by radiation and 2) separation of the heated particles on a heat-sensitive surface. Because neither of these steps had previously been utilized commercially in mineral processing, it was necessary to do basic research on both aspects. Factors studied in the investigation included type of heat source, design of heating unit, design of separation belt, selection of heat-sensitive coating, removal of heated particles from the belt, contact between particles and coating, and maintenance of the heat-sensitive surface. Part of the experimental work was carried out on a small-scale unit consisting of the 36x6 in. belt and auxiliary apparatus, and part on a larger unit. For simplicity, discussion of work on both of these units is grouped together. SELECTIVE HEATING Radiant-Heat Source: The essential requirements for a radiant-heat source were 1) that the radiant heat be in a wave length range which is effectively absorbed by the impurities but not absorbed appreciably by the rock salt and 2) that it be dependable, practical, and economical. Selection of a heat source of suitable wave length range was one of the first considerations. It is well known that pure halite is highly transparent to radiant energy in wave lengths from 0.3 to 13 microns. However, the available data on infrared transmission by dolomite and anhydrite, particularly in the range below two microns, were not complete enough to serve as a reliable basis for selection of a heat source. Although it may have been possible to obtain sufficient data on infrared transmission and absorption to enable one to select the best heat source, a more direct procedure was used. This consisted simply of exposing the crude rock salt to each of several types of radiant-heat source on the small continuous separation device. The heat sources investigated, approximate source temperature used, and calculated wave length of maximum radiation are tabulated in Table I. Of the two types of tungsten-filament lamps investigated, both the short wave length photoflood lamps and the longer wave length infrared lamps were satisfactory from the standpoint of selectivity

Jan 1, 1961

By Samuel Doak

THE utilization of rotary kilns, of the well-known cement type, for the preparation of iron ores, for the blast furnace, has become of considerable economic importance within the past 10 years in certain localities, notably those where the native ores are lean. Such kilns may be used simply for the agglomeration of ores too fine to be charged into the blast furnace (i.e., ores whose loss in the dust catchers is excessive, and whose fineness is detrimental to the working of the furnace), or for the desulphurization of lump and fine ores the sulphur content of which does not exceed 6 or 7 per cent. The desulphurizing action can be combined with that of agglomeration provided the kiln is sufficiently large. Other processes have been developed for the same purpose, but while I am not able to draw a comparison between them by reason of lack of sufficient data, it is safe to say that the kiln, if properly dimensioned for the character of ore to be treated, will compare favorably in its results, both as to economy and quality of product, with any other process. It is not, however, as well adapted for the treatment of flue dust, as is a sintering operation, on account of the large percentage of fine coke contained therein. Any combustible entering the kiln at its feed end renders the process very much more expensive and unsatisfactory on account of the difficulty of controlling the temperature, also because of the rapidity with which long "rings" form, due to the increased heat at the cooler end of the kiln. The greatest value of the kiln at present is in the treatment of pyrites cinder; that is, the residue from pyrites ore after the extraction of the greater part of the sulphur. This cinder, while high in iron content, has too much sulphur remaining in it to be allowed to form a large part of the blast-furnace burden, without further treatment. It will range in metallic iron from 42 per cent., representing a very low-grade cinder, from a domestic pyrites, to 64 per cent. of the residue from the best Spanish ore, and the corresponding silica content will vary from the maximum of about 25 per cent. to 1 ½ per cent. The residual sulphur depends largely on the type of burner used in the original desulphurization. In general, the leanest original ores retain the greatest amounts of sulphur. In

Jan 9, 1915

By E. G. Dean

A method of top slicing has been devised at the Miami Copper Co.'s mine at Miami, Aria., which differs radically in some ways from the customary methods of top slicing. The area of that section of the orebody in which top slicing is used is about 800 ft. square. The ore, while for the most part soft, is, nevertheless, considerably harder than the capping. The latter is siliceous, seldom containing any clay or other binding material, and breaks into fine particles so that it runs like sand if given the opportunity. Because of these facts, and because the ore is above the average grade of the mine ore, it has been mined by top slicing. Haulage levels are opened up 150 ft. apart, vertically, with two sub-levels between at 50-ft. intervals, to facilitate the putting up of ore chutes. These sublevels are used during slicing for distributing air in the ventilation system. On the haulage level the drifts are spaced on 50-ft. centers, and raises along these drifts are also spaced on 50-ft. centers, except the incline raises as hereafter noted. The raises are cribbed where necessary. Where the wear will be excessive, 1/4-in. iron plates are spiked to the top of every third set of cribbing, for its protection. When top slicing was first used, an attempt was made to carry a slicing face from fifty to several hundred feet long. Timber and other supplies were brought in through long drifts from an auxiliary shaft. Great difficulty was experienced in keeping these drifts open, the side pressure breaking the posts and the top weight breaking both caps and posts. Furthermore, the men could not work efficiently while these drifts were being repaired. The slicing faces advanced irregularly, due to varying conditions, and in many ways the results were not all that could be desired. It was then decided to divide the slicing area into blocks 200 ft. square and this was later changed to 250 ft. square. At the center of each block a two-compartment raise is put up as a supply raise, the compartments being 2 ft. 6 in. and 4 ft. by 4 ft. 4 in., the smaller being used as a manway. Station sets of 12 by 12 timber with

Jan 1, 1917

By Goro Shimaoka, Kichizo Niwa

IN the past, the crystalline states of graphite in cast iron have been studied by many investigators. Recently several authors 1-4 have published interesting information on the crystal texture of the individual graphite grain, especially spherulites in nodular cast iron. In regard to the crystal structure of graphite, Lipson and Stokes0 howed by powder X-ray analysis that most of the crystals contain about 14 pct rhombohedra1 structure (ß-form) which differs from the hexagonal structure (a-form) in the sequence of layer stacking. Hoerni6 onfirmed the existence of the ß-form in a single crystal with electron diffraction by Kossel-Moellenstedt's method. Furthermore, Hoerni and Weigle7 found extra reflections in electron diffraction patterns, which are given by a unit cell twice as large as the usual one in the basal plane. Recently, Lukeshs observed graphite twinning and satellite reflections in his X-ray work and considered them as evidence for the existence of an orthorhombic superstructure. Owen and Street" and Matuyama" studied the structures of graphite crystals in several types of cast iron, using the X-ray powder method, and they showed that the graphite crystal contains a certain amount of the ß-form, an amount which varies with the sources of the cast iron used. The present study was made in order to secure structural information on graphitization in cast iron. Electron diffraction studies on the structure of single graphite flakes segregated from molten carbon or silicon-rich iron at 1200" to 1500°C are reported. Experimental Honkeiko pig iron (4.05 pct C, 1.59 pct Si, and 0.65 pct Mn) was used as the solvent of carbon or silicon. The pig iron was melted in an open furnace and a small quantity of metallic silicon was added to the melt at 1300°C. The melt was heated to 150O°C, and then retort black carbon or metallic silicon was added little by little. The components added to the bath contained approximately 5.0 pct C and 2.0 pct Si in the carbon-rich material, and 3.8 pct C and 5.4 pct Si in the silicon-rich iron. These two types were held at 1500°C and then cooled without graphitizing by cutting the heat sup-

Jan 1, 1958

By George C. Ference

Sulfur is the 13th most common element in the earth's crust, constituting approximately 0.05% of the total. It occurs naturally in its elemental form, as metallic sulfides, nonmetallic sulfates, and as combined or free sulfur in natural gas, crude oil, and coal. COMMERCIAL SOURCES Most of the sulfur that is consumed is converted into sulfuric acid before use; therefore, it is not necessary to recover sulfur solely in its elemental form. Processes for recovery are peculiar- to the types of reserves being processed. The major commercial processes as well as the general geographic locations where the appropriate reserves occur are listed in the following. It should be noted that the sulfur values may be recovered as the primary product, as a coproduct with other materials, or as a byproduct. Elemental Sulfur 1) Frasch mining is used for subterranean deposits of elemental sulfur around the Gulf Coast areas of the United States and Mexico. Generally, but not exclusively, such deposits are located in salt dome structure. 2) Autoclaving, flotation, or solvent extraction of surface deposits of elemental sulfur is practiced throughout the world. 3) Extraction and conversion of hydrogen sulfide from sour natural gas into elemental sulfur is done principally in Canada, France, and the United States. 4) Conversion of metallic sulfides from pyrites into elemental sulfur is done via the Outokumpu process in Finland. 5) Catalytic cracking and hydrocracking of sulfur-bearing crude oils to produce elemental sulfur is done worldwide. Desulfurization of refined petroleum products also yields elemental sulfur. 6) Recovery of elemental sulfur from sulfur-bearing oil sands (Athabasca tar sands) has been initiated in Canada. 7) As of this writing (1970), a plant has been constructed for the thermal decomposition of gypsum to produce elemental sulfur in the United States. Sulfuric Acid Sulfur values in the form of sulfuric acid are recovered via: 1) Recovery from smelter gases throughout the world. 2) Roasting of pyrites throughout the world with iron sinters as a byproduct. 3) Roasting of anhydrite with cement as a coproduct, primarily in Europe. 4) Processes currently are being developed for recovery of sulfuric acid from combustion gases resulting from the burning of high-sulfur-content fuel. Other Sulfur values also are recovered from waste products which normally occur in highly industrialized areas. Some examples are: coke-oven gases, sludge sulfuric acid, and pickling liquors (ferrous sulfate).

Jan 1, 1976