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By R. C. Ku, A. J. McEvily, T. L. Johnston

The microplastic response of a series ofas-quenched Fe-Ni-C martensites has been measured at 77°K. At strains less than JO'3 the flow stress is governed primarily by the transformation-induced dislocation structure of the martensite. Only at strains in excess of 10-3 is the influence of carbon manifested in the flow stress. At these macroscopic strains, typically 10-2, the solid-solution hardening is proportional to (wt pct C)1/3, and, in an alloy containing 0.39 wt pct C, amounts to 50 pct of the flow stress. THE technological significance of high-strength ferrous martensite has stimulated many investigations of its structure and properties. Although our knowledge of the characteristics of martensite has increased immensely, especially with the advent of high-resolution techniques, an understanding of the basic strengthening mechanism still remains elusive. The purpose of the present paper is to consider certain aspects of micro-plastic behavior of Fe-Ni-C martensite which we feel can help to resolve this important problem. Such alloys are particularly suitable for experimental investigation because their compositions can be adjusted to reduce the M, to a temperature low enough essentially to eliminate the diffusion of carbon in the freshly formed martensite.1 The mechanical properties in this condition are of interest inasmuch as they reflect a state that is free of the important but complicating influence of precipitation processes. In this virgin martensite the carbon is distributed as it was inherited from the parent austenite; i.e., it is present interstitially, and gives rise to tetragonality through strain-induced ordering.' In order to determine the source of strength of such alloys, Winchell and Cohen1 investigated the low-temperature macroscopic stress-strain behavior of a series of virgin martensites of increasing carbon content but of common M, temperature (-35°C). They found that the flow stress increased rapidly with carbon content up to 0.4 wt pct; beyond this point the flow stress increased at a much slower rate. It was concluded that martensite is inherently strong. To account quantitatively for the strength of virgin or as- quenched martensite in terms of the role of carbon, Winchell and cohen3 suggested that the carbon atoms, trapped in their original positions by the diffusionless martensite transformation, interfere with dislocation motion according to a model akin to that of Mott and Nabarro. 4 In this treatment, individual carbon atoms are considered to constitute centers of elastic strain and thereby generate an average stress resisting the motion of dislocations throughout the lattice. The additional stress necessary to move dislocations, over and above that necessary for motion in a carbon-free martensite, is given by where L is an effective length of dislocation capable of motion. L was assumed to be limited to the spacing between the twins that are an essential structural element of Fe-Ni-C martensites. They assumtd the spacing to be invariant and of the order of 100A. However, recent work5 has shown that L is variable and can be in excess of 1000Å, so that the assignment of an appropriate value of L is not straightforward. In contrast to the above conclusion that there is an intrinsically high resistance to plastic flow, it has been suggested by Polakowski6 that freshly quenched martensite is in fact "soft" in the sense that dislocations are initially free to move upon application of stress. The high indentation hardness and macroscopic yield stress of ferrous martensites are then a consequence of rapid strain hardening that depends upon carbon in solution. Consistent with this point of view are the results of Beau lieu and Dubé who measured the rate of recovery of internal friction as a function of aging (tempering) temperature in a freshly quenched steel containing 0.90 wt pct C, 0.37 wt pct Mn, 0.1 wt pct Cr, and 0.07 wt pct Ni. The kinetics were clearly consistent with the idea that many dislocations are unpinned in the as-quenched state and that during aging they become progressively pinned by carbon at a rate controlled by carbon diffusion in the body-centered martensite lattice. In order to provide a basis upon which to distinguish between the "hard" and "soft" interpretations indicated above, we have made studies of the initial stages of plastic deformation in Fe-Ni-C martensites similar to those'used by Winchell and Cohen. It will be shown that the results support the contention that dislocation segments in as-quenched material are indeed

Jan 1, 1967

By W. E. Remmers

The defect in wire known as "cuppiness" has appeared and disappeared from time to time but the exact cause of its appearance or disappearance has not heretofore been known definitely. This defect is not limited to one particular metal or alloy but seems to be found at various times in all of the materials that are drawn into wire. Fig. 1 represents cuppy wire made from an aluminum alloy and Fig. 2 illustrates copper wire that became cuppy in drawing without intermediate annealing. Differences of opinion are current among the manufacturers of wire and in the literature (see bibliography at end of paper), some believing that the source of the trouble lies in segregation in the wire rod, oxides, sulfides, slag, etc.; others that the trouble is created by an unevenness of stress distribution across the section of the wire, usually thought of as being a function of die shape. All of the published work is of a qualitative rather than a quantitative nature. With this in mind, it was deemed advisable to make a study of the shape of the wire-drawing dies, as well as the oxygen content of the copper to be drawn. Experimental After several methods were tried, it was found that by studying the contour of the butt-end of the rod after drawing a measure of the "working" across the section of the wire could be made. The butt-end of the annealed rod was not sheared but was sawed off. The end was then smoothed with a fine file so that the plane of filing was perpendicular to the drawing axis. It is to be noted that this method is not an absolute measure of the distribution of cold working but is a very good indicative means of studying comparative values. The method of examining a tension break in wire was found to be the most sensitive in detecting cuppiness. Other methods, such as microscopic examination of longitudinal sections, X-ray radiographic studies, etching away of outer layers with nitric acid, and fracture by bending, can all be used to identify cuppy wire but the tension break will give the fracture characteristic of cuppiness before any of the other methods can

Jan 1, 1930

By Wm. I. Weisman, Sid McIlveen

Sodium sulfate is an important industrial chemical, being one of perhaps a dozen or so chemical commodities produced and consumed in the United States in quantities exceeding 1 Mt/a. In recent years approximately half that production has come from natural sources, whereas 27 years ago only 25% was derived from these sources. Table 1 illustrates the history of production of natural sodium sulfate in the United States. Production of natural sodium sulfate from various types of deposits is the main source of this chemical in Canada and Mexico, and probably in Argentina, Chile, Spain, and the USSR. Mineralogy and Physical Properties Sodium sulfate is widespread in occurrence and is a common constituent of many mineral waters, as well as seawater. Atmospheric precipitation contains sulfate; it is one of the major dissolved constituents of rain and snow (Davis and DeWiest, 1966). Many of the saline lakes throughout the world contain varying amounts of sodium sulfate. Because sodium is usually the dominant cation, some workers make an anionic distinction, referring to lakes containing predominately sulfate as bitter lakes and those containing predominately carbonate as alkali, or soda lakes (Bateman, 1950). Sodium sulfate in its natural form is found as the hydrous salt mirabilite (commonly called Glauber's salt), and as thenardite, the anhydrous variety. The largest quantities occur in the form of mirabilite. Sodium sulfate is found in varying degrees of purity, from theoretically pure efflorescent crystals of mirabilite to combinations and admixtures of other salts and impurities. It is a common constituent of some brines; from this source much is extracted commercially. [ ]

Jan 1, 1983

By C. Hays, R. E. Swift, E. G. Kendall

Investigations of the Zr-Pt system, by metallography, incipient melting, and X-ray diffraction, determined the phase relationshifis from 0 to 50 at. pct Pt. Phase fields in the Pt-~ich region were outlined, and three intermetallics (ZrPt, Zr2Pt, and ZrPtd were located. A eutectic between Zr and Zr2Pt, and a eutectoid veaction between Zr and a Zr + Zr2Pt, were established. The maximum solubility of Pt in P Zr was approximately 13.5 wt pct, as opposed to less than 1 wt pct solubility in a Zr. EARLIER work on the Zr-Pt system was limited to an X-ray study on the intermetallic compound, ZrPt3, by H. J. Wallbaum,1 It was reported that ZrPt3 existed at 86.52 wt pct Pt, and had a hexagonal structure, isomorphous with TiNi3. Wallbaum's data revealed the following structural particulars: a = 5.633A, c = 9.21A, and c/a = 1.635A. Other studies allied to Zr-Pt alloys concerned only 1) Pt-rich alloys (0.05 to 5.0 pct Zr) for corrosion resistance,2 2) a Zr-base alloy with 5 pct Pt and 0.124 pct C for oxidation resistance,3 and 3) electroclad-ding of Zr with Pt for in-pile corrosion resistance of Zr to uranyl sulphate. 4 Metallographic, incipient melting, and X-ray diffraction techniques were applied to accurately resolve the phase relationships in the 0 to 50 at. pct (68.2 wt pct) Pt region, and to outline the phase fields in the Pt-rich area. Three intermediate phases: Zr2Pt, ZrPt, and ZrPt3, were also established by the same methods. PROCEDURE Melting stock for this program was of the highest purity obtainable. The Zr was iodide crystal bar with a low hafnium content of about 0.05 wt pct (Westinghouse "Grade 3"). The as-received Zr was treated to remove the surface film of corrosion product that resulted from a standard autoclave grade designation test. Next, the bars were processed to yield material suitable for arc melting and free of contaminants. Sheet platinum metal (Baker and Co. "Grade 2") was used for alloying additions. This material con-

Jan 1, 1962

By Narendrakumar A. Chevli

Exploratory work was conducted in the fabrication of integrated circuitry, specifically linear amplifier circuits, by three general methods: 1) monolithic diffused silicon; 2) a combination of metal thin-film and monolithic diffused silicon; and 3) a hybrid of metal films and diffused silicon on an alunina substrate. In these linear amplifier integrated circuits the followzng conditions were desired: very high-frequency response, high voltage gain, and good thermal tracking stability of electrical characteristics. The resulting circuit designs imposed problems of isolation between elements, layout and smallness of size of active elements, and close tolerances on electrzcal characteristics of the passive elements. Interconnection problems for specific designs resulted from the small dimensions involved and the topography of the hybrid fabrication techniques. The desired integrated-circuit characteristics were achieved with the technologies of categories 2 and 3 above. Solutions to the problems imposed by these characteristics lay in the ability to isolate czrcuit elements of small size while providing a layout designed to minimize element-to-element variations. Sufficient freedom in the formation of passive elements was achieved by uniting the metal film and the monolithic silicon technologies. The most satisfactory designs were based on the beam-lead interconnection and isolation technique. SINCE the advent of integrated circuits, major emphasis has been on fabricating digital integrated circuits. Linear circuits require high performance, high voltage, and tighter tolerance components which are not always compatible with the capability of process technology available for fabrication of these circuits into integrated form. Fortunately the growth of newer and improved processes and materials for fabricating integrated circuits has been an accelerated one. This has now made possible the translation of stringent performance requirements of the linear circuits into microminiature integrated circuits of the same performance. In the exploratory work of fabricating high-performance Linear Integrated Circuits—LIC, the following objectives were formulated: i) fabrication of high-frequency transistors such as the type 2N918 isolated on a single silicon substrate; ii) fabrication of medium-frequency transistors having a very high gain at low collector currents such as the types 2N930/2N2484 isolated on a single substrate ; iii) fabrication of tight-tolerance, high-valued resistors having low temperature coefficients of resistance and stable thermal tracking characteristics, these resistors to be fabricated on an active or passive substrate; iv) simultaneous fabrication of complementary transistors—pn and pnp-on the same silicon substrate; v) fabrication of newer active elements such as MOS, FET transistors along with the conventional active and passive elements on the same silicon substrate. State-of-the-art assessment f all the available processes, materials, and technology to meet above objectives indicated that economic fabrication of LIC cannot be achieved by a single technology for all types of linear circuits. Where design and performance of a given linear circuit can be modified and tolerated to the extent of a particular technology, then alone is it possible to fabricate a LIC using a single process technology such as all diffused, planar technology. In order to evaluate this economic breakpoint with design and performance compromise in fabricating LIC, it is essential that a thorough understanding be obtained of techniques, potentials, and limitations of all the various process technology and materials

Jan 1, 1967

By Edwin B. Wilson, Joseph W. Leonard, Richard W. Borio

preparation of specification coals for the utility industry is approached from the standpoint of a cooperative effort with the power company to assure that the shipped product will be a noncorrosive coal. Selective mining, coal preparation, the use of additives, and coal blending are mine-site techniques proposed as means for upgrading corrosion-retarding constituents of utility coals (CaO and MgO) while, at the same time, reducing the concentration of those constituents of coal (Na20 and K,O) which cause corrosion. Data obtained from large-scale boiler testing in combination with bench-scale physical and chemical tests are used as a basis for the formulation of mine-site procedures to improve coal combustion utilization. Electric power generation remains the greatest market for coal in the United States. A major reason for this strong market has been the ability of the coal industry to supply a superior product for combustion while maintaining competitive prices. Now that the coal industry is engaged in intensive competition with nuclear power for future energy demand, it becomes ever more imperative that superior coal products are produced. One important problem when burning some coals is a liquid phase corrosive attack on boiler tube metal in the superheater and reheater areas of the furnace where steam temperatures may exceed 1050°F. In addition to causing power outages and high maintenance costs, corrosion is a continuing barrier to the future development of more efficient steam cycles which permit lower generation costs when using coal. Research methods of the past which have been directed at finding solutions which could be applied at the power plant site have been only partially successful and are generally costly. This paper contains a suggested --method of corrosion control through investigation of the problem at the source of the trouble—the coal supplier facility. It is proposed that mine-site pre-ventative procedures be considered as an effective means of cooperative corrosion control between the power company and the coal supplier. Economic justification must be applied to the individual situation. This paper is based on recent work by Combustion Engineering, Inc. and the Coal Research Bureau of West Virginia University under a contract from the Department of the Interior Office of Coal Research.',' Results which are of importance to this discussion may be summarized as follows: 1) The alkali minerals of coal (Na2O and K2O), as measured by an acid leaching process, can be related to corrosion rate in utility boilers. As these constituents increase in a coal product, its corrosiveness can be expected to worsen. 2) The alkaline-earth minerals contained in coal, reported as total CaO and MgO reduce corrosiveness 2s their concentration increases. 3) Naturally occuring, alkaline-earth-bearing materials, such as limestone and dolomite, may be added to a coal to reduce its corrosiveness. 4) Coals with very low iron contents tend to be less corrosive. These results provide the groundwork for examination of the system of operations which occur at the supplier facility from the seam face where mining is begun to the point of loading for shipment. The Mining System Fig. 1 is a cross section of one of the typical coal seams (designated coal A) that was boiler tested during this research program. This seam is overlain by material which consists primarily of a gray-black shale. In the lower third of this seam, there exists a thin rock parting of less than 4 in. in thickness which is consistent throughout the seam. The floor material is fireclay. In order to examine mineral distribution throughout this particular seam, the Coal Research Bureau collected a

Jan 1, 1971

By Herbert Haas

ChEap power is essential to large-scale mining and metallurgical operations, particularly where fine grinding of large tonnages has to be resorted to, as is the case with an increasing number of mines treating disseminated copper ores, or low-grade gold ores, in the grinding of which considerable power is consumed. A comparison of the cost of generating power with Diesel engines and steam turbines and a brief discussion of the different factors governing the profitable use of either type of prime mover may be timely in view of the importance of a cheap supply of power to the mining industry, and the prominence that has lately been given to Diesel engines in America. As many of our most important mines and largest producers of metals are located in sections where neither cheap coal nor water power is available, and the price of oil fuel is increased by long hauls, the Diesel engine will become a prime mover of increasing importance. This applies particularly to the Southwestern States, where an ample supply of cold water for condensing purposes is unusual and local climatological conditions interfere in securing the high vacua essential to high turbine efficiency. About 12 times as much water will be required for condensing purposes with steam turbines under general conditions as is needed for jacket-cooling of two-stroke cycle Diesel engines; four-stroke cycle Diesel engines require only one-twentieth of the cooling water. Another condition favoring the use of Diesel engines is the high load factor at which most mine power plants operate. The influence of load factor on the cost of generating power is shown in Tables 1. and 2 and in Fig. 1. The higher the cost of fuel and the load factor, the greater will be the proportion of the fuel to the other costs making up the total cost of generating power. Capital charges (interest and redemption), maintenance, operating labor, and lubrication are practically constant amounts regardless of the load-output of the station; the fuel consumption and its cost are practically the only variables with the load. The costs here given are based on conditions as generally found in the Southwestern States, and on Diesel engine operating experience in European countries, where this type of prime mover has reached a high state of perfection, units upward of 4,000 hp. having proved entirely successful in operation.

Jan 1, 1917

THIS chapter and Chapter 19 deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the first two laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only: 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the heat balance of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced. The cause probably lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities in flow distribution and air leakage present in any real open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot- metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million Btu per net ton of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million Btu and the sensible heat in the preheated air at the port ends is 117 million Btu, so that the total heat input at the ports is 477 million Btu. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million Btu, but 120 million of this is supplied by the heat in the hot metal and by various heat-evolving reactions in the bath,

Jan 1, 1964

By John Garcia

THE presence of carbon de terre along the banks of the Illinois river was noted by the members of the Joliet and Marquette expeditions in 1673, and that may be referred to as the birthday of coal in the Middle West. The march of progress in the majority of indus-tries radiating from Chicago-one of the phenomena of history-is due in no small measure to this same carbon de terre and to the development and exploita-tion of the vast coal resources, which nature in a generous mood spread so lavishly over almost the en-tire state. The geological records indicate that coal-bearing rocks underlie three-quarters of Illinois, in-cluding 85 of the 102 counties and the entire area is estimated at from 36,000 to 42,000 square miles. Not all of the coal in this great area may be mined under the conditions existing today; producers are now taking the "cream" since industry demands the best quality and the lowest cost, thereby forcing competition among operators, which, in turn, com-pels the development of mines in those areas where the coal may be most readily .won, leaving the coal that is more difficult and expensive to mine to pos-terity. This is not such a bad arrangement, since the engineers of succeeding generations will enjoy the advantage of the experience of their ancestors, where-by they should profit and know how to mine a 2-ft. seam with as much economy and dispatch as we today work coal of thrice that thickness. During the period between 1830 and 1850, Illinois coal-mining progressed from the art of scratching along the outcrop to the development of small mines, mostly slopes, drifts and shallow shafts, but the real progress in the industry was coincident with the con-struction of railroads.

Jan 2, 1927

By J. T. Ryan

SiR Humphry Davy's epoch-making treatise delivered on Nov. 9, 1815, before the Philosophical Society of London, first announced and demonstrated a flame safety lamp for detecting methane in mine air. Coal mining was known in England as early as 1180, more than 600 years before the advent of a safe lighting and gas-detecting appliance. Mining, no doubt, took place first in outcrop coal, and danger from gas did not become apparent until the workings became deeper and more extensive. Davy's lamp did much to increase the safety of miners, and a modified Davy lamp is still widely used for detecting the presence and approximate amount of combustible gas in mine air. No factor in coal mining has improved more rapidly during the past 15 years than safety measures. This progress came about not only as a result of the workmen's compensation laws now in force in most of the states of the Union, but because the research work of the U. S. Bureau of Mines had demonstrated some dangers incident to coal mining which were not considered to be serious matters prior to that time. Electric power and explosives are necessary but potential hazards in American coal mines. A general mechanization program is now under way, while the mines are growing deeper and more extensive. Consequently ventilation problems are more complex and a demand has been created for positive detecting devices for carbon monoxide as well as methane. Scientists and manufacturers, working hand in hand during the past 10 years, have invented and developed appliances which make systematic and effective examination of mine air possible. The object of this paper is to describe briefly the approved testing devices in use today, with the hope that they may lead to the saving of life. Two Groups of Dangerous Coal Mine Gases Dangerous coal mine gases may be placed in two groups: (I) those that are dangerous because of their explosive properties, and (2) those that are dangerous because of their toxic properties. Methane (CH4) is the important gas of the first group, and in so-called gaseous mines constantly exudes from the coal and rock; it may accumulate and form an explosive mixture. The explosive range of methane-air mixtures is well defined. The low limit is 5 per cent., the high limit 15 per cent., and the most explosive

Jan 1, 1927

By B. H. Dunshee

This paper is not intended to be a technical discussion of square-set framing as used in mines, but merely a short description of the different kinds of framing that have been used in the Butte mines, and what has been decided upon, after years of practical experience, as being the best, taking into consideration the physical condition of the veins and country rock, and also the supply of timber available for mining purposes. Butte is, essentially, a square-set district. Virginia City, Nev., was the first mining camp to use this method of timbering, and to Philip Deidesheimer, who went to the Ophir mine in 1860, is given the credit of solving the problem of square-set framing, where large bodies of ore were stoped and the timbers were supposed to hold the ground from caving without any filling. That he did his work well is shown by the fact that the main features of his framing are in use to-day. In the Butte mines the conditions are such that this method of timbering is generally used. We do not, of course, depend upon the timbers any more than is necessary. The worked-out stopes are filled with waste rock as close behind the miners as possible and not interfere with mining operations. The waste rock is obtained from development work on the different levels or from the surface. In the earlier days of mining in Butte there were numerous independent companies and naturally there were different ideas as to the best way to frame the square sets, although the general features were the same. Timber was abundant for mining purposes and the common practice was to use sawed lumber, generally 10 by 10 in. or 12 by 12 in. square. Some of the mines used for girts 6 by 10 in. or 8 by 12 in. timber, depending upon whether they used 10-in. square or 12-in. square timber for posts and caps. This avoided the necessity of framiug the ends of the girts, and also required less timber for the

Jan 1, 1914

By T. A. Wright

THE SAMPLING of waste materials containing copper, lead and tin has taken on a new significance within recent years, and is of increasing importance, on account of the entry of some of the copper refineries into this field and the tendency towards consolidations among the smelters. In the past, such material was sold on the basis either of a rough or grab sample or of casual inspection of the lot. The two principal sources of this waste are the processes of fabrication and the scrapping of automobile, electrical, plumbing, railroad and other equipment. In both cases much material can be sorted, salvaged and sold by classification and grade to be melted "as is" or with the addition of new or virgin metal. The increasing care in classifying exercised in the large manufacturing plants tends to increase the proportion of this usable scrap; on the contrary, the increasing use of more complex and special non-ferrous alloys tends to make sorting and grading more difficult in turnings, borings, clippings, etc., and consequently is making sampling of more moment. In tin, lead, aluminum, and zinc furnace by-products such as ashes, drosses, skimmings, etc., the trade practice of evaluation has not varied much. For instance, tin drosses, battery lead, and aluminum skimmings are ordinarily sold on what is called' "metallic button" or "metallic recovery" or "metallic yield." Copper and lead waste, however, is being sold more and more on actual copper and lead contents based on sample and chemical analyses. This paper will be devoted chiefly to the sampling of materials suitable only for refining and recovery of one or more of the metals present. The methods described are often based on the fact that but one metal, such as copper, is to be paid for. The loss of volatile constituents in melting does not appreciably affect the final copper result, as the "after-melting" assay can be readily calculated to the "before-melting" basis, but if smelter efficiency continues to increase, so that in time zinc, for instance, may be recovered on a paying basis, the method of sampling dirty brass, for example, will have to be changed also.

Jan 1, 1928

By H. Biloni, B. Chalmers

Metallographic studies of the segregation of solute in and near the surfaces of chill-cast alloys have shown that, under sufficiently severe conditions, nucleation on the cold mold surface is followed by the formation of a disc of solid of the same composition as the liquid. This disc is surrounded by two concentric rings in which the concentration first decreases and then increases. The discs and rings are surrounded by a region in which arms of low solute concentration separate regions of high concentration. These arms start at the periphery of the outer ring and are initially radial; they make a gradual curved transition from the radial direction to a crystallographic direction. A normal dendritic substrcture is established beyond the position at which the arms have become crystallographically aligned. When the cooling is less severe, the disc becomes less irregular in shape and has a concentration minimum at the center. The term "Predendritic" is proposed for these transitions. A qualitative explanation is outlined for the phenomena observed at the surface and in the equiaxed region of the ingots. It is well-established1-' that the normal mode of solidification for alloys under most conditions is dendritic. A characteristic of dendritic solidification is the growth of rods or plates in specific crys-tallographic directions. The remaining liquid solidifies later, usually with a higher concentration of solute than the original liquid. Very little is known, however, about the transition from a crystal nucleus until the dendritic pattern is established. It is clear that there must be a transition because the nucleus is much smaller than the characteristic spacings found in the "steady-state" structure. And it also seems clear that the initial conditions must be important since the undercooling existing during the nucleation of the grains has a remarkable influence upon the grain size4 and the segregation pattern. The present paper reports a study of the micro-segregation in regions where crystals have nucleated, and the conclusions that can be drawn regarding the early stages of growth, in connection with the details of the solidification process. Aluminum of 99.993 purity, A1-Cu alloys containing 0.5 to 20 wt pct Cu, and Pb-Sn alloys with 5 wt pct Sn were cast and examined metallographically at the as-cast surface, close to the surface, and in the interior after casting. The alloys were cast from controlled temperatures against surfaces at different temperatures ranging from room temperature to approximately the liquidus temperature of the alloy. The surfaces were, in various experiments, graphite, stainless steel, copper, and aluminum. The methods used for metallographic examination were as follows. 1) The Nomarski phase contrast interferometer6 was used to obtain information on the topography of the as-cast surface. 2) The distribution of any solute present in A1 99.993 pct and copper in the A1-Cu alloys was studied by the anodic film technique originated by Lacombe and Mouflard7 and previously applied in the study of the solidification of aluminum by Biloni.8 The electropolished surface of the specimen is anodized under controlled conditions so that the thickness of the oxide film and therefore the interference colors under white light are sensitive to the local composition. This technique was applied to the as-cast surfaces and to metallographically prepared surfaces from the interior. 3) If in Al-Cu alloys, the surface is anodically oxidized for several minutes, instead of seconds as in the color-film technique, the copper segregation is outlined by a different level with respect to the matrix. This method is less sensitive but complementary to that for the color films. 4) The distribution of copper revealed and mapped by the metallographic techniques was confirmed by electron probe. 5) In samples with high concentration of copper, evidence for the copper distribution could be seen optically after electropolishing.

Jan 1, 1965

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

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

Jan 1, 1961

By O. W. Ellis

THE question of the influence of gases upon the properties of copper has received the attention of a number of investigators, among whom Sieverts,1 Iwasé,2 Lobley and Jepson3 stand preeminent. SOLUBILITY OF . GASES IN. COPPER Sieverts and Iwasé concerned themselves with the solubility of a variety of gases in the metal in the solid and liquid states. They determined the absorption coefficients of these gases and in all cases found a sharp change in solubility at the melting point of the metal. In this respect they disagree with Lobley and Jepson, who have based their opinions upon the appearance of small ingots of the metal which had been fused in an atmosphere of one or other of three gases and had then been rapidly cooled, while surrounded by gas, to the freezing point (rate-possibly 30° to 60° C. per sec.). The ingots that had been fused and cooled under nitrogen and carbon monoxide were free from blowholes and it was assumed that these gases were not absorbed in amounts much in excess of those which would dissolve in the solid metal; the ingots similarly treated under hydrogen were full of blowholes and it was assumed in this case that gas was ejected on solidification of the copper. The effect of varying the rate of freezing upon the character of the test ingots was not examined by these investigators; otherwise, it is felt, their views might have been subject to modification. Sieverts' most important contribution is that the solubility of a gas in any metal is proportional to the square root of its pressure or concentration. Knowing then the absorption coefficients of the various gases in copper, it should be possible to determine the analysis of the

Jan 1, 1928

By L. L. Wyman

Previous studies1 by the writer dealing with the embrittlement of copper have been concerned with the behavior of various pure and deoxidized coppers when exposed to an oxidation-reduction cycle, and the consequent evaluation of these materials on the basis of their resistance to this action. No attention was devoted to the variations in penetration of embrittlement with time, when these copper materials are exposed to a strong reducing gas, such as hydrogen, nor to the variations in oxygen penetration, with time and temperature, into the "pure" coppers. The cause of the embrittlement is the reduction of the oxygen in the copper by the hot reducing gas, so that a consideration of time, temperature, the occurrence of hydrogen and oxygen must be given. For the purpose of differentiating some of the involved factors, the present work may be divided into two separate series of experiments. The first of these deals with the oxidation of purified coppers under various conditions and then the subjection of these to a standard hydrogen treatment. The second series concerns the reduction, under different conditions, of tough-pitch coppers of several oxygen contents. The resulting data will give the rates of oxidation, and of reduction, for the materials involved. The first series of experiments will reveal how rapidly copper may become oxidized, while the second series will indicate how rapidly embrittlement will penetrate into an oxygen-containing copper when it is exposed to hydrogen at different temperatures. Materials For the purpose of determining these variables, three types of material were selected, to cover the extremes in the ranges of materials commercially obtainable. The first class of materials is represented by an oxygen-free copper, as well as the high-purity vacuum-melted copper2 used in previous work. These materials were selected to determine the variation of oxidation with time and temperature, by oxidizing these coppers under various combinations of these factors, and noting the effect as indicated by a

Jan 1, 1934

By Charles Will Wright

Brief descriptions of the occurrence of the various deposits of strategic minerals then known in South America are published in "The Mineral Deposits of South America," by B. L. Miller and J. T. Singewald, 1919; in "Ores and Industry in South America," by H. F. Bain and T. T. Read, 1934; and in many publications on the individual countries. To give a gen.era1 idea of the situation today and possibilities for future output of strategic minerals in several of the countries, the following notes are offered. All tonnages are in metric units.

Jan 1, 1940

By N. Mungan, J. L. Thompson

Laboratory displacement tests were performed to study oil recovery elficiency by gravity drainage in fractured systems under miscible conditions. The porous media used were cylindrical Berea and Blue Jacket sandstone cores containing a number of well-defined, artificially formed, vertical and subvertical fractures. Butane and Soltrol 130 were the two miscible fluids used. The purpose of the study was to examine the influences of the displacement rate, fracture density, fracture orientation, fracture permeability, matrix permeability, crossflow, core length and connate water on the oil recovery. It was found that displacement rate, matrix permeability and the subvertical fractures affected oil recovery most. The critical flow rate, based on the matrix permeability, was found to be a significant factor in the process. For displacement rates below the critical flow rate, the oil recovery efficiency appeared to be unaffected by the density of the subvertical fractures. At the high displacement rates, the fracture density becomes important, with the recovery being the most efficient in the core having the greatest number of the subvertical fractures. The magnitude of the fracture permeability, the fracture orientation, the core length and the connate water have little effect on the oil recovery efficiency. INTRODUCTION Gravity drainage under miscible conditions from relatively thick reservoirs can be a very efficient recovery process, especially at low flow rates where the gravity forces are dominant and, consequently, the adverse viscous fingers associated with the unfavorable viscosity ratio are minimized or eliminated. Such a process might involve injection of an LPG or some solvent bank at the crest and then driving the bank with dry gas. For some favorable combination of reservoir temperature, pressure and oil composition, there may be no need to inject any solvent bank, since enrichment of the dry gas by the light ends of the crude creates an in-situ solvent bank. Slobod and Howlett2 have studied the effects of gravity segregation in vertical unconsolidated porous media under miscible conditions in the laboratory. The main variables in their study were the viscosity ratio, the density differences and the rate of flow. In this study, the objective was to find the influence of fractures on gravity drainage under miscible conditions. A greater number of related variables were also studied. LABORATORY STUDY CORE DESCRIPTION Displacement tests were performed mostly in cylindrical Berea sandstone cores. In a few cases in which a much lower matrix permeability was desired, Blue Jacket sandstone cores were used. The vertical fractures were formed by cutting the cores with a thin circular blade or by parting them along a bedding plane. The vertical fracture plane always contained the axis of the cylindrical core. The subvertical fractures, cut with a saw, were inclined 45' from the horizontal. The line of intersection between the planes of the vertical and subvertical fractures was parallel to the circular faces of the cores in all cases except one, as depicted by VF3HF-2 in Fig. 1. Fracture geometry of the other cores is also given in Fig. 1. Tables 1 and 2 give the physical properties of the solid and fractured cores, respectively. The suffixes and prefixes shown for each core have been used throughout the paper so that the reader may discern the fracture geometry from the core numbers.

Jan 1, 1970

By T. E. Leontis

Data are presented in this paper to show that addition of zirconium to sand-cast Mg-Th alloys effects a marked decrease in the grain size of these alloys which is accompanied by a significant increase in the mechanical properties over the entire range of thorium content investigated. The beneficial effect of zirconium on the strength properties is maintained at elevated temperatures up to 700°F. In addition the alloys exhibit exceptionally high creep resistance at temperatures up to 600°F. Zirconium does not greatly improve the strength or creep characteristics of extruded Mg-'Th alloys. Cerium is not a desirable addition to Mg-Th-Zr alloys. IN a previous paper,' it was shown that addition of thorium to magnesium imparts exceptionally high resistance to creep at elevated temperatures both in the sand-cast and in the extruded states. The large grain size of the sand-cast alloys, however, renders them of questionable value as engineering materials. Sauerwald² showed that the grain size can be reduced effectively by the addition of zirconium. Results of a detailed study of the properties of Mg-Th-Zr alloys over a wide range of thorium content are presented in this paper. In accordance with the preliminary findings of Sauerwald,² it is shown here that Mg-Th-Zr alloys possess the unusual combination of fine grain size and a high level of strength and creep resistance at elevated temperatures. Some information on the effect of cerium on the properties of Mg-Th-Zr alloys is presented also. Effect of Th on Solubility of Zr in Molten Mg Sand-cast test bars and 3 in. diam extrusion billets of Mg-Th-Zr and Mg-Th-Ce-Zr alloys* were pre- pared according to the procedures described in the previous paper.' The zirconium was added in the form of sponge metal as supplied by the Bureau of Mines.' The maximum amount of zirconium that usually can be introduced into magnesium at the customary alloying temperature of 1350° F is about 0.7 pct. The analyses in Table I clearly show that thorium in- creases the solubility of zirconium in liquid magnesium. The tabulated zirconium contents are designated as "acid soluble;" this serves to distinguish these values from the small amount of zirconium that is not dissolved when the alloy is subjected to the action of a dilute acid solution. The "acid-insoluble" zirconium is believed to be ineffective as an alloying ingredient. The acid-insoluble zirconium contents ranged between 0.03 and 0.16 pct in the present alloys, the tendency was toward higher values in alloys with higher thorium content. In contrast to the effect of thorium, cerium decreases the solubility of zirconium in magnesium. This is shown by the three Mg-Th-Ce-Zr alloyst in- cluded in Table I and stands in agreement with the observations of Nelson and Stricter".' on Mg-misch-metal-Zr alloys. Effect of Zr on Grain Size of Mg-Th Alloys The potent effect of zirconium as a grain refiner has been demonstrated for many types of magnesium alloys.3-8 Of greatest importance to date are Mg-Zn-Zr alloys5,6,8 and Mg-mischmetal-Zr alloys.3,4,7 Zirconium has also been found to exert a marked grain-refining action on Mg-Th alloys. All the Mg-Th-Zr alloys cast in the form of ½ in. diam test bars have an exceedingly fine grain size (Table I). Reference to the previous paper' will show that binary Mg-Th alloys containing up to 6 pct Th are almost completely columnar even in the M in. diam reduced section of a test bar, and that 10 to 50 pct Th alloys have an equiaxed grain structure of 0.03 to 0.08 in. The data in Table I also show that addition of cerium to Mg-Th-Zr alloys has no effect on the grain size. In addition to increasing the strength properties, the fine grain size of Mg-Th-Zr alloys

Jan 1, 1953

By C. E. Birchenall, R. H. Condit

THREE surface activity procedures are in com--L mon use for the determination of diffusion coefficients in solids. In the oldest of these' the activity observed at the original surface is compared before and after diffusion, where all the activity is in a thin, plated layer on the surface before diffusion. Partial absorption of the radiations from active atoms which have diffused below the surface reduces the effective activity after diffusion. The formula employed to calculate the diffusion coefficient is where F, is the ratio of final to initial activity at the surface, measured with identical counting geometry; Z=u3Dt, where D is the diffusion coefficient; t is the diffusion time; and u is the absorption coefficient for the radiation in the solid as defined by Lambert's law. This absorption law implies that all the rays are parallel to each other and normal to the specimen surface. This assumption of a collimated beam used by Steigman, Shockley, and Nix has been adopted by all other investigators and, although it gives results which are approximately correct under restricted physical conditions, it does not represent many actual circumstances. It is the purpose of this paper to show the importance of the divergent rays and to indicate a procedure for taking them into account. In the residual activity method the activity is determined on a series of surfaces ground on the specimen at progressively greater depths in the diffusion layer parallel to the initial surface. Gruzin2 has de- rived a formula for this procedure, which may be put in the form where I is the ratio of the activity measured at a newly ground surface at distance k below the initial surface to the activity at the initial surface measured after diffusion, and K= k/2p Dt. A third procedure involves the autoradio-graphic determination of activity on a plane ground at a small angle to the initial interface through the penetration zone. Aut oradiography can be particularly sensitive to the oblique rays. Unlike most counters which detect essentially all ß particles or X-rays which enter the active volume as a single event, the photographic emulsion may be thin enough so that oblique rays with longer path length in the emulsion produce more darkening than rays which move normal to the film plane. Consider a plane containing a source of radiation uniformly spread over a circle and a point counter located on the perpendicular through the center of the circle. As the counter moves along this line, the total angle 6, at the counter subtended by the specimen will vary. For a fixed counter distance, let 6 be angle between the counter axis and the line connecting the counter to a point P on the active plane. If an absorber of thickness X is interposed parallel to the source between counter and source, the ray from point P to the counter will pass through an absorber thickness X secant 6. Exponential absorption is assumed to hold for all rays. If r, is the ratio of intensity at the counter with absorber to the intensity without absorber and a = pX, 1 00 The behavior of this integral, evaluated numerically,

Jan 1, 1957