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By P. de Vitry, Oliver Bowles

The conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 93/16 or 54 in. The equipment, methods used, and accomplishments have been described in previous reports.'-I Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible to maintain in stock marbles of the color, size, and thickness called for, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill such orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By P. de Vitry, Oliver Bowles

The conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 93/16 or 54 in. The equipment, methods used, and accomplishments have been described in previous reports.'-I Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible to maintain in stock marbles of the color, size, and thickness called for, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill such orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By R. H. Frazier, C. H. Lorig, F. W. Boulger

This investigation establishes the effect of ferrite grain size resulting from various heat treatments on the transition temperature of a semikilled steel plate. Different austenitizing temperatures and various cooling rates were used. The ductile-brittle transition temperatures were determined by the Navy tear test and the keyhole Charpy test. THE data presented in this paper deal with quality characteristics of ship-plate material which were investigated in a research project sponsored at Battelle by the Bureau of Ships, Dept. of the Navy. Specifically, the object of this investigation was to establish the effect of ferritic grain size (resulting from various heat treatments) on the so-called transition temperature of ship-plate steel. Transition temperature is not a fixed property of steel. It is derived from a series of static or dynamic tests made at various temperatures and is qualified by specifying the type of test employed as well as the testing criteria. Because in earlier investigations of ship-plate quality1,2 the so-called Navy tear test and standard notched-bar tests (keyhole Charpy) proved to be useful in interpreting instances of brittle behavior of ship plate in service, these tests were used in the investigation reported in this paper. By definition,' in the Navy tear tests the highest temperature at which one or more of four specimens breaks with a brittle fracture (that is, when less than 50 pct of the fracture area has a dull fibrous texture) is termed "transition" temperature. In the Charpy tests, the 12 ft-lb level of energy absorption was used as a criterion indicating the "transition" temperature, although other levels of energy absorption were also used for comparison. Earlier work" on ship-plate steels indicated that the temperature at which ship plate is finished has a very significant effect on its notched-bar properties. Plates rolled in the laboratory, where the finishing temperature can be carefully controlled, showed a 16°F decrease in tear test transition temperature when the finishing temperature was lowered 200°F (from X" to Y°F). The same plates showed a drop of 10°F in the keyhole Charpy transition temperature from the same decrease in finishing temperature. Commercially finished plates' exhibit a similar trend. When the ferrite grain size of the hot-rolled laboratory plates was determined, a close relationship was found between the ferrite grain size and the notched-bar transition temperature." " he indicated relationship between grain size and transition temperature was in agreement with the findings on low carbon steels of Hodge, Manning, and Reichhold' despite the differences in composition of the steels. The cooling rate after rolling varies from one steel plant to another. This variation changes the micro-structure" and appears very likely to affect the notched-bar properties of the steel plates. In the investigation summarized in the present paper, heat treatments simulating finishing practices in the hot rolling of ship plate were used in order to vary the ferritic grain size. It is believed that the indicated relationship between grain size and transition temperatures of the ship-plate material will prove useful in estimating the effect of rolling temperature and of cooling rates from rolling temperatures on the notched-bar properties of semikilled steel plate. Material The semikilled steel plate used in this investigation was a ¾ in. hot-rolled plate from an open hearth heat. Other plates from this heat have been used on many other studies performed for the Ship Structure Committee," "," and the heat has been identified as project steel "A". The chemical composition of the plate1 was 0.25 pct C, 0.49 pct Mn, 0.011 pct P, 0.045 pct S, 0.04 pct Si, and 0.004 pct N.

Jan 1, 1956

By Samuel H. Dolbear

THE value of a mine is basically dependent on its capacity to yield profits. Since the ore must be mined, treated, and sold, some of it in various future years. there is a risk involved as to future costs, selling price, and working conditions. It cannot be expected that the economic condition existing at the time of valuation will continue unchanged for long periods in the future. During the past 20 years, mineral production in the United States has been conducted under a changing economy in many respects more exacting than that applied to other businesses. There have been increased production incentives, technical aid, exploration of privately owned mineral deposits by government at federal expense, and liberal loans for development and equipment, with risk partially assumed by government.. Some of these benefits have been counterbalanced by price ceilings, consumption controls, and stimulation of competition from foreign producers who have been offered the same advantages extended to American operators. For the present, mines will operate under a government policy directed toward reducing federal aid and control. The tenure of this change will depend upon future elections and the status of foreign relations. War and threat of war are now of the most vital significance to the mineral industries. Other factors which influence cost of production, markets, and price of mine output might be classified as Acts of God or Acts of Government. In some countries expropriation and the difficulty of exporting earnings or investment returns are risks that must be considered by foreign capital. Recognizing that this retards American investment in foreign countries, the Mutual Security Agency offers insurance against such expropriation and guarantees the convertibility of capital and profits. Since it is impossible to predict with certainty either cost of production or selling prices of metals for long periods, some assumptions must be made as to profits in the future. The basic assumption must be that the price of the company's product will vary in proportion to changes in operating cost. There is often a lag in this reaction, however, for prices of minerals are generally more sensitive to declines and less sensitive to increases than are costs. This reflects in part the resistance of labor to downward wage revision and a corresponding alertness in realizing its share of price advances. Some labor contracts include automatic adjustments to metal prices. Notwithstanding the complexity of the, problems involved and the difficulty of weighing their effect on value, such risks may be appraised with reasonable accuracy and a rate of earnings adopted that is compatible with the risk. It is, of course, possible to revert to a yardstick of value such as the commodity dollar, which has been advocated from time to time, but while revaluation in 1933 disturbed public confidence, the theoretical gold dollar continues to be the standard of greatest stability. Its gain or loss in purchasing power is reflected ultimately in cost of production and selling price of the mine product. At present 35 dollars are allocated to one ounce of gold. Measurement of Risk In the application of the Hoskold and most other formulae, a yearly dividend rate commensurate with the risk involved is set aside out of annual earnings. If the risk is great, this rate may be 15 to 25 pct of the amount invested. The remainder is placed in a sinking fund invested in safe securities such as high grade bonds or conservative equities, and the interest or dividends from these securities are added to the sinking fund. The sum of these sinking fund payments and the compounded interest at the end of the mine life is taken as the value of the mine. Admittedly the decision as to the size of the risk rate is the most difficult element in valuation and one requiring the most exacting consideration. It is necessary to look years ahead in an effort to determine future costs, market prices, demand, competition which may develop, including that of substitutes, and other influences common to the mine and to the region in which it is situated. Another phase of risk is the enactment of unfavorable legislation, taxes, and what appears to be an alarming spread of nationalization and expropriation. Capital is sometimes borrowed from the government to finance strategic production. Such loans may be collectable only out of production and involve no liability otherwise. Valuation in these cases must recognize the effect of such a reduction in liability. Offsetting some of these risks are the possibilities of mechanization and other cost-reducing discoveries, improvements in mining and treatment methods, new uses for minerals and metals, and normal growth of markets. In this paper, the terms risk rate, dividend rate, and speculative rate are synonymous. Safe rate and redemption rate are also used interchangeably. These alternatives are used here because they are commonly found in the literature on mine valuation. In Michigan, the State Tax Commission has long employed a risk rate of 6 pct in its valuation of iron mines. There the outline of reserves is well established and operating costs and conditions are based on adequate experience. The following comment on rates appears in the report of the Minnesota Interior commission on Iron Ore Taxation submitted to the Minnesota Legislature of 1941.1 Most engineers agree that 7 percent for the specu-lative rate is "an absolute minimum". C. K. Leith in

Jan 1, 1954

By J. J. Forbes

'"THE Federal Coal Mine Safety Act (public Law T. 552. 82nd Congress) was approved oil July 16, 1952. It incorporates, as Title I, the Coal Mine Inspectio1.1 and Investigation Act of May 7. 1941 (Public Law 49, 77th Congress), which gave Federal inspectors only the right to enter. coal mines for inspection and investigation purposes but no power to require compliance with their recommendations. Title 11 contains the enforcement provisions of the act; its purpose is to prevent major disasters in coal mines from explosions, fires. inundations. and man-trip 01. man-hoist accidents. At this point a brief account of events that preceded the enactment of the Federal Coal Mine Safety Act seems appropriate. The hazardous nature of coal mining was recognized by the Federal Govermment as long ago as 1865, when a bill to create a Federal Mining Bureau was introduced in Congress. Little was done, however, until a series of appalling coalmine disasters during the first decade of this century provoked a demand for Federal action. As a result an act of Congress established a Bureau of Mines in the Department of the Interior on July 1, 1910. The act made it clear that one of the foremost activities of the Bureau should be to improve health and safety in the mineral industries. One of the first projects selected by the small folce of engineers and technicians then employed was to determine the causes of coal-mine explosions and the means to prevent them. By investigations aftel mine disasters the fundamental causes and means of prevention were soon discovered, and the coal mining industry was informed accordingly. However, despite this knowledge and the enactment of State laws and the Federal Coal Mine Inspection and Investigation Act of 1941, mine disasters continued to occur with disheartening frequency and staggering loss of life. The devastating explosion at the Orient No. 2 mine on December 21, 1951, resulted in the death of 119 men. The Orient disaster rekindled the memory of the Centralia. Ill., disaster of March 25. 1947, which caused the death of 111 coal miners. These two tragedies ultimately brought about enactment of the Federal Coal Mine Safety Act. The act is a compromise measure. Senator Matthew M. Neely of West Virginia and Congressman Melvin Priec of Illinois introduced almost identical versions in the 82nd Congress, but they were considered too drastic. The final version was introduced by Congressman Samuel K. McConnel, Jr., of Pennsylvania, after considerable discussion and amendment in committee hearings. It was passed by the Congress and became effective when signed by the President on July 16, 1952. The act is somewhat limited in scope because it applies only to approximately 2000 coal mines in the United States and Alaska that employ regularly 15 or more individuals underground. It exempts approximately 5300 mines employing regularly fewer than 15 individuals underground and all strip mines, of which there are about 800. Moreover, it covers only conditions and practices that may lead to major disasters from explosion, fire, inundation, or man-trip or man-hoist accidents. According to Bureau records, such accidents have resulted in less than 10 pct of all the fatalities in coal mines. It is important to mention that the law is not designed to prevent the day-to-day type of accidents that have caused the remaining 90 pct or more of the fatalities, because it was the specific intention of the Congress to reserve the hazards which caused them to the jurisdiction of the coal-producing states. Many who opposed any Federal legislation that would give the Federal inspectors authority to require compliance with mine safety regulations claimed that such legislation would usurp or infringe upon States' rights. To assure that the principle of States' rights would be preserved, the act provides for joint Federal-State inspections when a state desires to cooperate in such activities. The Director of the Bureau of Mines is required by the act to cooperate with the official mine-inspection or safety agencies of the coal-producing states. The act provides further that any state desiring to cooperate in making joint inspections may submit a State plan for carrying out the purposes of this part of the act. Certain requirements are listed: these must be met by a state before the plan can be accepted. The Director of the Bureau of Mines, however, is required to approve any State plan which complies with the specified provisions. The Director may withdraw his approval and declare such a plan inoperative if he finds that the State agency is not complying with the spirit and intent of any provision of the State plan. When this paper was prepared, agreements for joint Federal-State inspections had been entered into with Wyoming and Washington. A few other states have indicated their desire to submit a State plan and negotiations toward that end are now under way. Reluctance to enter into such agreements may be due to the mine operators' knowledge that in the states that adopt a cooperative plan they are prohibited from applying to the Director of the Bureau of Mines for annulment or revision of an order issued by a Federal inspector and must appeal directly to the Federal Coal Mine Safety Board of Review for such action. Experience has proved that review by the Director as provided in the act is a less expensive and time-consuming procedure to all concerned than applying to the Board. Reluctance also may stem from the fact that joint Federal-State inspections somewhat restrict the movements of the State mine inspectors and tend to reduce the number of inspections of mines. Where a State plan is not adopted, the Federal coal mine inspector is responsible under the law to take one of two courses of action if he finds certain hazardous conditions during his inspections. The first action involves imminent danger. If a Federal inspector finds danger that a mine explosion, mine fire, mine inundation, or man-trip or man-hoist accident will occur in a mine immediately or before the imminence of such danger can be elim-

Jan 1, 1955

By J. P. Timmons, J. H. Moran, G. K. Miller, M. A. Coufleau

A prototype equipment has been designed and built for the digital recording of well logs on magnetic tape at the same time that the regular film recording is made. The format of the digital tape produced is such that it can be used directly at the input of the ZBM 704, 7090 or other models of ZBM computers which accept digital magnetic tape. This apparatus has been used for the experimental field recording of dipmeter tape logs which were subsequently computed by means of an ZBM 704 or 7090. In this paper the equipment and the digital tape are described briefly, and their application to the computer-interpretation of dipmeter data is discussed. A principal element in the interpretation of the dipmeter log is the correlation of the three microresirtivity dipmeter curves to determine the depth displacements between them. Several correlation methods for computer use are considered, with particular attention to their sensitivity to error and their consumption of computer time. The tape data were used to compute information content of the dipmeter microresistivity curves in terms of their frequency spectra. The results show that the sampling rate used in recording the digital information is quite adequate and illustrate a use of the digital tape in evaluating the characteristics of new tools. Some examples of field results are shown. It can be foreseen that, when digital tape recording becomes available for general field use, a whole new realm of possibilities will be opened up for the processing of other well logs through computations, which hitherto were not feasible because they were too laborious and time-con.sunzing. INTRODUCTION The last few years have seen a revolution in the design and production of data-processing equipment. Stored-pro-gram digital computers have progressed from a research curiosity to the basis of a major industry. There are now hundreds of such machines in daily use in the United States. With the acceptance of a technique that was, in fact, already clearly described by John von Neumann in 1945, the last decade has seen great strides in the development'of components, reliability, programming systems and, most spectacularly, in the sheer number of machines built and in use. In 1957 there were enough digital computers available to the oil industry to justify the suggestion that it would be worthwhile to investigate the possibility of using these machines in processing well log data.' The first result of this investigation was the appearance of what may be referred to as the input-output bottleneck. Well logs are customarily recorded on film. To get these data into a machine required then (and still does): a time-consuming semi-automatic reading of the film; conversion of the log data to digital form; and recording these digital data in some medium acceptable for computer input, such as cards, magnetic tape, or punched paper tape. However, the recording, reading, and re-recording could only result in deterioration of the data. Therefore, it was concluded that the fist step should be the development of a new, more direct recording technique supplemental to the film recording, which would provide easy access to the digital computer. There are many solutions to the problem of recording log data in an easily recoverable form. After careful consideration it was decided to adopt the boldest solution which, it was felt, was also the most elegant. It was decided to record well logs directly, in the field, on magnetic tape in such a way that this tape could be used without further modification as an input to the IBM 704 or 7090 computer. To realize practical field recording of magnetic tape logs, it became necessary to develop in a rather small package, an analog-to-digital converter, a tape recorder, and the necessary multiplexing and control circuits to allow the simultaneous recording of a multiplicity of logging signals. The magnetic tape recording was to be made simultaneously with the conventional logging operation in such a way as not to interfere with it. Along with the development of hardware, it was necessary to begin development of interpretation techniques and machine programs that would exploit the power of the digital computer. Here, again, there is a long list of possible applications. After much consideration it was decided to concentrate on the interpretation of the dipmeter log as a first application. It is the object of this paper to describe in some detail the developments sketched in the last three paragraphs.

By D. E. Thomas, C. E. Birchenall

ALTHOUGH Eoltzmann gave a mathematical solution for the diffusion equation (for planar diffusion in infinite 01. semi-infinite systems only) in 1894 allowing for variation of the diffusion coefficient with a change in concentration, it was not until 1933 that this solution was applied to an experimentally investigated metallic system. The calculation was carried out by Matano' on the data obtained by Grube and Jedele3 for the Cu-Ni system. Since that time concentration dependence of the diffusion coefficient has been demonstrated for many pairs of metals. However, the nature of this dependence has never been fully elucidated. Many investigators have suspected that these variations could be related to the thermodynamic properties of the solutions, one of the earliest explicit statements being contained in a discussion of irreversible transport processes by Onsager' in 1931. Development along these lines has been greatly retarded by the lack of reliable data on the variation of tliffusivity with concentration, the paucity of the thermodynamic data for the same systems at the same temperatures and compositions, and an incomplete understanding of the relation of the thermodynamic properties of the activated state for diffusion to the bulk thermodynamic properties. The last factor has been discussed by Fisher, Hollomon, and Turnbull.5 In many instances where data exist, it is difficult to know which are acceptable. This problem probably applies more strongly to diffusion data than to activity measurements. For instance, four sets of observers"-" have reported self-diffusion coefficients for copper. The average spread between extreme results is a factor of about four, though the individual sets of data are self-consistent to about 20 pct. Thus one or more factors are out of control, at least in these experiments, making estimates of internal error unreliable. The most reliable diffusion data in most systems have resulted from the use of welded couples with a plane interface from which layers for analysis are machined parallel to the interface after diffusion. The layers are analyzed, and the result is a graphical relation between distance and concentration, usually called the penetration curve. Given the same set of analytical data and distances and following the same procedure in computation, different observers will generally produce diffusion coefficients which vary appreciably, especially at the extremes of the concentration range. Experiments must be carefully designed so that the precision is good enough to answer a particular question unequivocally. In the first calculation of the dependence of the diffusion coefficient on concentration in the metallic solid solution Cu-Ni, Matano found that the coefficient was insensitive to concentration from 0 to 70 pct Cu, after which it rose more and more steeply to some undetermined value as pure copper was approached.' The same behavior was reported for Au-Ni, Au-Pd, and Au-Pt.* The data used were those of Grube and Jedele which were very good at the time, but are not considered particularly good by present standards. Furthermore, the method of calculation makes the ends of the diffusion coefficient-concentration curve unreliable. For better reliability, the high copper end of the curve has been checked by incremental couples, where the concentration spread is 67.7 to 100 atomic pct Cu. The implication of the curves calculated by Matano was that diffusion is very concentration sensitive in one dilute range of this completely isomorphous system and hardly at all in the other. Matano's result is confirmed. Later Wells and Mehll0 published data on diffusion in Fe-Ni at 1300°C, which represent a thorough test of the shape of the concentration dependence curve. They ran couples with the following ranges of nickel concentration: 0-25 pct, 1.9-20.1 pct, 0-20.1 pct, 20.1-41.8 pct, 0-99.4 pct, and 79.3-99.4 pct. Although the trend of the data indicates an S-shaped concentration dependence, their curve was drawn to the pattern set by Matano. Their original data have been recalculated for the 0-99.4 and 79.3-99.4 pct couples. Wells and Mehl's points and two independent recalculations from the raw data are plotted in Fig. 1. What appears to be the best curve is drawn through them. This curve shows little sensitivity to composition in both dilute ranges with a strong dependence at intermediate composi-tions.? Similar experiments on the Cu-Pd system are reported here at temperatures where solubility is unlimited. These lead to the same type of concentration dependence for the diffusion coefficients as was found upon recalculation of the data for the Fe-Ni system. Experimental Procedure Cu-Pd: The concentration dependence of the diffusion coefficient may be determined by the use of

Jan 1, 1953

By Hollis L. Caswell

The present status of integrated circuits utilizing. superconductive switching. elements is reviewed with special attention given to fabrication techniques, methods for interconnecting completed circuits, and refrigeration requirements. Cryoelectronics has been largely an "inte- grated-circuit" technology since its conception because the switching speed of superconductive devices is attractive only when these devices are fabricated with thin-film techniques. It is true that cryotron circuits can be constructed from wires of appropriate materials (as indeed was done by Dudley Buck 1 in his early investigations) but these circuits will switch in times characteristic of milliseconds whereas similar circuits fabricated by thin-film methods have potential switching times of nanoseconds. Furthermore, cryo-electronic devices such as the cryotron lend themselves readily to fabrication by thin-film techniques since these components may be made from polycrys-talline thin films and are relatively insensitive to the presence of impurities (as measured by semiconductor standards). Therefore, during the past decade considerable effort has been devoted to developing techniques for batch fabricating circuit arrays containing superconductive switching elements. Technology had developed to the point several years ago that fabrication of cryoelectronic arrays containing up to one hundred devices was rather straightforward. However, larger arrays containing between lo4 and 106 components which are required for commercial development of cryoelectronics still pose very severe yield problems. Thus in a sense cryoelectronics found itself in 1962 at the point semiconductor technology finds itself today; namely, individual devices and small groups of integrated devices could be fabricated with acceptable yield and the outlook for building larger integrated-circuit arrays was bright. Unfortunately, problems associated largely with yield have made fabrication of these larger arrays difficult. Unlike semiconductor technology, cryoelectronics had to solve the problems of large-scale integration before it could become economically attractive. This has proven to be a sizable burden to bear. Since several reviews exist on superconductivity,2 superconductive devices,3 and cryoelectronic technology, no attempt will be made in this paper to summarize these areas. Instead a few specific topics will be dealt with in more detail. First, a brief description is given of selected superconducting switching and storage devices with special attention to several metallurgical techniques which improve the performance of these devices. Second, techniques used to fabricate cryoelectronic devices are described with emphasis on problems affecting yield. Third, techniques for interconnecting a number of cryoelectronic planes are described. And last, refrigeration of cryoelectronic components is discussed briefly since the low operating temperature of superconductive devices is an important consideration in this technology. SUPERCONDUCTING STORAGE AND SWITCHING DEVICES The basic superconductive switching device is the thin-film cryotron. The geometry of this device is attractively simple, since it involves only the intersection of two lines that are electrically insulated from each other. The switching element (gate) and control element (control) of a crossed-film cryotron are arranged as illustrated in Fig. 1. The material for the gate is selected to permit the gate to be switched from the superconducting to the normal (resistive) state by the application of a control current. Tin, which has a critical temperature (T,) of 3.7°K, is commonly used for the gate and the cryotron is operated at a temperature just below T, (for example, 3.5°K). The control material (normally lead, with T, = 7.2°K) is chosen so that the control is never driven normal during circuit operation. To improve cryotron operation, a ground plane, also of lead, is placed under all of the circuitry to act as a diamagnetic shield and improve the current-density uniformity across the width of various thin-film elements. Normally, line widths vary from 0.005 to ^ 0.020 in. and film thicknesses from 300 to 10,000A, although new fabrication techniques make narrower lines feasible. In fabricating cryotrons it is important that the edges of the gate elements be geometrically sharp to avoid undesirable switching characteristics associated with a thinner edge region, Fig. 2. One technique which has been used extensively to form patterns consists of placing a physical mask containing the film pattern between the evaporation source and the substrate and depositing through the mask. Film strips formed in this manner possess a penumbra at the film edges due to shadowing of the evapor-ant under the mask. Several techniques have been proposed for minimizing effects due to this penumbra. One of the more promising metallurgical techniques

Jan 1, 1967

By D. W. Frommer

Processing nonmagnetic taconites by selective flocculation-desliming and flotation requires large volumes of water. If impounded without treatment, these off-process waters require excessively large areas for containment. To discharge the waste water into natural waterways would contribute to stream pollution and likely would not be permitted. In U.S. Bureau of Mines experiments conducted in the Twin Cities Metallurgy Research Center's 900-lb per hr pilot plant, approximately 85% of water requirements for the flotation-based treatment of a Michigan nonmagnetic taconite were met by reclaimed water. Water reclamation of the off-process streams from flotation was accomplished by controlled additions of lime, sodium carbonate, and a synthetic flocculant to reduce turbidities to 51000 ppm equivalent SiO*, while maintaining a Ca(II) content of =16 ppm in the finished effluent. Flotation concentrates of good quality were obtained using the reclaimed water. The cost of chemicals used in water reclamation was approximately equal to the savings in flotation reagents attributed to recycling of the water. Water quality is perhaps as important to flotation as are the reagents used. The character of water is extremely variable, depending on whether the source is a well, lake, or stream, upon the season and temperature, upon prior use, and upon the character of the watershed. All of these factors influence the water hardness and the quantity of other dissolved inorganic salts, turbidity, dissolved and suspended organic matter, dissolved gases, and pH. Frequently, the differences in water quality can measurably influence flotation selectivity, often to the point of spelling success or failure. Water hardness is particularly troublesome in flotation systems employing fatty acids, but other unrecognized constituents may also contribute to peculiarities in flotation behavior. Furthermore, a given water source may be entirely satisfactory in one flotation system, but entirely inappropriate in another. In recent years, society has given more attention than formerly to water use, even in areas where water is plentiful. However, both the demands of a growing population, with increased per capita needs, and also those of industry must be met. As a result, riparian rights must be negotiated with the appropriate government agency or agencies so that consumption of water is often allocated or otherwise controlled. Furthermore, the disposal of off-process industrial and domestic water is coming under the increasing scrutiny of these same governmental units. In these respects, the mineral industry is no exception, so that conservation, water reclamation, and reuse may be expected to assume increasing importance. In 1932, it was stated that, "water reclamation is generally more expensive than the economy in water and reagents resulting from its use. It is employed only if it is urgent to save water."' The economic aspects of this statement may still be true, but the unrestricted use of water is becoming less and less an option of the user. The purpose of this paper is to discuss an investigation conducted by the U.S. Bureau of Mines (USBM), in which water reclamation and treatment were undertaken to develop procedures for, and to assess the effects of, water reuse on the flotation treatment of nonmagnetic taconites. This investigation is a logical extension of previous work described by the author and associates at the Twin Cities Metallurgy Research Center employing selective flocculation-desliming and anionic flotation of silica from low-grade, nonmagnetic iron ores2,8 The requirements for the selective flocculation-de-sliming and the anionic flotation of silica processes determined the direction of the investigation. Previous studies had indicated that pH levels of about 11.0 and 11.8 were required for selective flocculation and flota-tlon, respectively. The calcium content of the water was believed to be of importance in both of these operations, and since Minneapolis tap water with a Ca(I1) content of about 16 ppm had been successfully used, an attempt was made to reclaim the process water at an equal level of dissolved calcium. Additionally, the objective was to nullify or effectively limit the effects of dispersants and fatty acid residuals from prior stages of processing. Last but not least, the system of water treatment had to have the capability of reducing turbidities to workable levels. With about half of the effluent being derived from the selective flocculation-desliming step and carrying about 25,000 ppm of highly dispersed, suspended fines, this last objective appeared formidable at the outset. Procedures for water reclamation were derived, in part, from well-known mineral dressing practices, from past observations and investigations, and from concepts contained in various pertinent publications on water treatment."c These procedures involved: 1) flocculation with lime and poly electrolyte-type flocculants, 2) lime-soda-ash softening, 3) chemical precipitation, and 4) mineral surface adsorption. Control was exercised at various stages of water reclamation by frequent measurements of Ca(11), pH, and turbidity.

Jan 1, 1971

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By M. R. J. Wyllie, H. W. Patnode

In the quantitative interpretation of electric log data it is essential to know the formation factor, defined as the ratio of the resistivity of the formation 100 per cent saturated with brine to the resistivity of the brine.' This concept implies that the formation factor for any given rock is constant irrespective of the resistivity of the brine or solution with which it is saturated. It is apparent that this can be true only when the rock matrix is wholly non-conductive. As reservoir rocks may contain clay or shale having an appreciable conductance one may expect these constituents to influence the determination of true formation factor. The formation factor may be theoretically derived from log data by dividing the resistivity of the mud filtrate invaded formation by the resistivity of the mud filtrate. Such a method of calculntion has implicit in it the assumption that the fluids in the invaded formation are wholly replaced by mud filtrate. that the solid matrix is non-conducting, and that the formation factor of the invaded zone is identical with the formation factor of the uninvaded zone. Since the validity of the first two basic assumptions regarding the insulating character of porous matrices and the displacement of the interstitial fluids in porous media do not appear to be fully established, the formation factors of a number of cores and clay slurries have been measured under conditions suitable for verifying the assumptions and the extent of any errors inherent in them. CORE STUDIES Apparatus and Procedure Resistivity measurements were made on short cylindrical permeable cores which had been previously mounted in lucite.2 The cores were clamped by means of insulated bolts between brass plates about 5 cm square and 1 cm in thickness. The plates were provided with a ring seal to prevent leakage between them and the core mount, and had a centrally located orifice so that fluids could be flowed through the mounted core. The brass mounting plates were used as electrodes and any current flow between them necessarily passed only through the constituents of the intervening core. Fluid saturation of the core, and fluid flow through the core, were effected by a centrifugal pump connected to the outflow end of the core, thus providing a differential pressure across the core of approximately one atmosphere. The procedure used was first to evacuate each core by means of the pump and then to saturate the core with an aqueous sodium chloride solution of known resistivity. The resistance of the core was measured and flow of the solution through the core continued for sufficient time to establish a constant resistance reading. After equilibrium had been reached with one solution, another sodium chloride solution of a different resistivity was flowed through the core and the flow continued until a constant resistance reading was again obtained. This procedure was continued until resistance measurements of the core had been made with a series of solutions within a salinity range from 1.0N NaCl to distilled water. The data obtained enabled the apparent formation factor of given porous rocks when saturated with fluids of different resistivity to be computed and also provided information regarding the ability of an invading fluid to displace interstitial water from a core. Results Berea Sandstone — The first core examined was a specimen of Berea sandstone." This core had been cut essentially parallel to the bedding for permeability studies. The core was clamped in the core holder and saturated with 1.0N NaCl solution and the resistance determined. It was subsequently flushed and the resistance measured when saturated in turn with 0.1N, 0.025N, 0.01N, .005N sodium chloride solutions and finally with distilled water. In flushing the core with each

Jan 1, 1950

By W. C. Knopf, G. Samsel

For several years International Minerals & Chem-ical Corp. has used a radiation method to assay potassium content of products from potash and feldspar beneficiation. The procedure is rapid, accurate, and inexpensive and is easily handled, if necessary, by nontechnical personnel. Data are presented to show the accuracies that may be expected if the technique is used for control of pilot plants or large-scale plants. Natural potassium is composed of three isotopes —K, K and K. Five other isotopes, artificially produced, have been detected. In natural potassium only the K isotope, with a half life of 1.4x10 years, is radioactive. Its modes of decay are beta and gamma rays, positrons, and x-rays. Only the more abundant beta rays, however, are important in radiation measurements using geiger tubes. Barnes and Salley' measured radiation of potassium salts in solution in 1943. Gaudin and Parnell2 first reported the use of solid salts arranged in a vessel surrounding the ß counter in 1948. Later, Scheel used the method to assay potassium content of various crude and finished potash salts. Experimental: Dip-type Geiger-Muller tubes (TGC-5) supplied by Tracerlab Co. were used in all radiation counting measurements. The tube was encompassed by a glass container about M in. larger in diameter than the tube. This container, which served as a sample holder, was closed at the bottom with a rubber stopper to facilitate removing the samples. Samples were not weighed, but about 40 g of sample were needed for each test. Electrical impulses from the tube were counted on either a Tracerlab scaler or a rate meter. To obviate the need for constant attendance, preset features were incorporated into the scalers, so that at a predetermined time or count the units were automatically deactivated. When rate meters were used, counting rates were read directly from instrument or from a recorder used in conjunction with the rate meter. Each tube was calibrated, according to the manufacturer's instructions, to determine the correct operating voltage to insure reproducible results. A linear calibration plot of percent K2O vs counting rate was also obtained for each tube by recording the counting rate plus background count of several standards of different K2O content chemically analyzed by the chloroplatinate method.' These standards were of approximately the same particle size distribution as samples to be assayed. Specific background count caused by cosmic rays and other surrounding radiation was checked periodically by counting a sample of pure NaCl. Fig. 1 is a representative calibration plot. Assays were determined directly from the standard plot or calculated by subtracting the background count from the counting rate, then multiplying by the slope of the line. Chemical assays of the test samples were made by the Sherril method," a flame photometric technique, or the chloroplatinate method. Data: The radiation assay method has been used for three years by International Minerals & Chemical Corp. in the laboratory and in pilot plants processing ores containing potassium. These dry concentration plants process sylvinite and langbeinite ores at Carlsbad, N. M., and feldspar ores at Top-sham, Maine. Sylvinite ore is predominantly a mixture of syl-vite (impure KCl) and halite (impure NaCl). Contaminants include sulfates, such as langbeinite (2MgSO - K2SO4), kieserite (MgSO H2O), poly-halite (MgSO4.K2SO, 2CaSO, . 2H2O), and slimes. Langbeinite ore is predominantly langbeinite and halite with small amounts of sylvite, sulfates other than langbeinite, and slimes. Several variables, in addition to correct calibration and standardization of tubes, were found to be important in obtaining reproducible results. Particle size distribution of standard samples should be

Jan 1, 1959

By R. K. Iyengar, G. C. Duderstadt

An investigation was carried out to determine the effect of Ca-Si additions on the dissolved oxygen content of liquid steel. An apparent equilibrium was reached after holding the melt for some time when the total oxygen content of the melt was identical with the dissolved oxygen. Results of the investigation show that for deoxidation with silicon and manganese the apparent equilibrium is reached after 8 to 12 min and the oxygen content of the melt is in good agreement with values reported in the literature for similar steel compositions. Ca-Si additions decrease the dissolved oxygen content appreciably below that obtained with Si-Mn deoxidation. It is postulated that some calcium dissolved in liquid steel at the time of its vaporization combines with dissolved oxygen to form CaO which then fluxes the manganese silicate, thereby lowering the activity of the deoxidation products. Slow flotation of calcium silicate inclusions is attributed to their slower growth rate. An addition of aluminum (to yield <0.005 pct Alsol) prior to introduction of Ca-Si improves the kinetics of removal of resulting deoxidation products. WITH the introduction of continuous casting of billets and blooms, application of calcium-containing alloys for deoxidation purposes has gained new interest. More so than in conventional ingot casting, the degree of control of the dissolved and total oxygen contents in steel for continuous casting can determine the success or failure of the operation because these affect both surface (pinholes) and internal quality of the billets. Of the available deoxidizers, only silicon has so far found wide application. However, in the typical range of application (0.20/0.30 pct Si), it is too weak a deoxidizer to suppress pinhole frequency to the level desirable for all but the least demanding appli-cations (approximately 10/50 pinholes per sq ft, de-pending on degree of subsequent reduction). On the other hand, Vincent&apos; has shown that it requires ap-proximately 0.007/0.008 pct A1 soluble in the steel to suppress pinhole formation to <10 pinholes per sq ft. In view of the difficulty of consistently maintaining this aluminum level and the associated problem of tundish nozzle constriction2 when aluminum is added to the ladle, steelmakers have searched for other de-oxidation alloys to circumvent the problem. Calcium-containing alloys offer such a possibility. When employed as a partial substitute for silicon, CaSi (30 pct Ca/60 pct Si) additions are reported to yield adequate pinhole contro1.3 Its use simultaneously preserves the "fluidity" of the steel and ensures good castability.4 Oxygen contents as low as 0.007 to 0.014 pct have been obtained with CaSi additions varying between 3 to 8 lb per ton.5-7 Due to the high degree of vaporization of calcium at the temperature of molten steel and the different methods used to introduce it into the liquid, the reported results show considerable scatter and lack of consistency. According to several investiga- deoxidation tors, the flotation characteristics of CaSi products are not as favorable as those found for alumi-num but are similar to those established for silicates with low alumina content.678 Thus, cleanliness ratings were improved when CaSi was replaced by a com-bination of Si + A1 followed by CaMnSi additions.5,9 In view of the lack of a comprehensive description of the deoxidation potential of CaSi alloys, a study was undertaken of the effect of CaSi additions on oxygen content in comparison to Si + Mn and Si + Mn + Al. The alloy chosen for this study contained 63 pct Si, 32 pct Ca, <3 pct Al, and 2.5 pct Fe. EXPERIMENTAL PROCEDURE The experiments were divided in three groups as shown in Table I. In each group, the CaSi addition was increased successively while maintaining the melt composition constant. The experiments in the third group were designed to determine the effect of prede-oxidation with small amounts of aluminum. Ingot iron, containing 0.02 to 0.03 pct C and 0.03 to 0.05 pct Mn, was melted in a 100-lb magnesia crucible. Pig iron was added to the melt under air in an induction furnace to attain the desired carbon content of 0.05 to 0.15 pct and thereby control the initial oxygen content of the melt between 0.04 and 0.015 pct. After removal of the slag, the furnace was sealed and argon was introduced through an opening in the graphite cover, Fig. 1. When the desired temperature was reached, electrolytic manganese was added to the melt and pin samples were taken (7 mm silica tubing) to establish initial oxygen content. To obtain maximum efficiency, CaSi and metallic silicon were introduced in a sealed steel pipe into the bath. This procedure assured minimum loss of calcium through vaporization as the deoxidants were always released at the bottom of the melt. Samples were taken at regular intervals and quenched in water. Temperature of the bath was measured with a Pt/Pt-10 pct Rh thermocouple. Portions of the pin sample were used for oxygen analysis; five determinations per sample were made to obtain average oxygen content. Oxygen analyses were made by the inert carrier gas fusion method with frequent cross checks with the vacuum fusion method.

Jan 1, 1970

By James P. Kimball

In a paper which I had the honor to present to the Institute at the Montreal meeting, September 1879,I took occasion to refer incidentally to certain practical difficulties in the sampling of coal-seams {Trans. Vol. VIII., p. 181-3). This reference was particularly to the unequal distribution of sulphur in the form of pyrite, and to the necessity of discriminating between the several members or " benches " of a coal seam as to their relative proportion of visible sulphur. What is a practically truthful estimation of the sulphur of a coal seam, is not necessarily the estimation of an average of sulphur in any given line of cross-section of the seam. Cornparatively speaking, the range of sulphur in quantity is generally so low that errors in its determination, arising from neglectful sampling or from slips in the laboratory, fall chiefly upon this single ingredient. Not so,

Jan 1, 1884

By P. R. Sperry, P. A. Beck, J. Towers

Dahl and Pawlek1 found that electrolytic copper develops extremely coarse grains at 1000°C after about 90 pct reduction by rolling. This coarsening occurs only under conditions of penultimate grain size, deformation, and alloying which lead to the "cube" recrystallization texture.l,2,3,5 The peculiar angular shapes and straight grain boundaries of the coarse grains were noted by several investigator.1,4,5 On the other hand, coarsening in Fe-containing aluminum or in AI-Mn alloys8 does not depend on a "cube" (or any well developed) recrystallization texture. It is true that increasing deformation by rolling, and, therefore, an increasingly well developed re-crystallization texture, are associated with decreasing incubation periods of coarsening.6-7-8 Nevertheless, coarsening readily develops in aluminum even after only 30 pct reduction by rolling, where the recrystallization texture is very weak.6,8 Also, coarsening was observed by Jeffries9 many years ago in sintered thoriated tungsten, which presumably has no preferred orientation. In all these cases coarsening is associated with grain growth inhibition by a dispersed second phase.8,9 The annealing temperature has to be suficiently high to overcome the inhibition at a few locations. But if it is too high, growth starts at many points, and the resulting grain size becomes much smaller.9 Normally, the coarse grains are more or less equiaxed, and the boundaries have a typical ragged appearance.6.8 Cook and Macquarie4 demonstrated that, in addition to the texture-dependent coarsening previously found at 1000°C,l electrolytic tough pitch copper may also coarsen at 800°C after 50 pct reduction by cross rolling. The coarse grains formed under such conditions have rounded shapes and ragged boundaries, like those in aluminum. When the annealing temperature is higher, the tendency for their formation decreases. All these observations suggest that the coarsening at 800°C is associated with inhibition by a second phase. Actually, coarsening at 800°C after 50 pct reduction by cross rolling was observed only in tough pitch copper,4 which contains Cu2O particles. On the other hand, the texture-dependent 1000°C coarsening occurs in both tough pitch and oxygen-free copper;4 it does not appear to depend on the presence of a dispersed second phase. However, the interpretation of the 800°C coarsening in Cu after 50 pct rolling as an inhibition-dependent process, similar to the coarsening in A1-Mn alloys, is somewhat weakened by the fact that this coarsening was reported4 to occur only after cross rolling, and not after straight rolling. It was, therefore, decided to re-examine this question. A 1 in. diam electrolytic tough pitch copper rod, No. 2 hard drawn, was annealed for 20 min at 700°C, rolled to 0.5 in., annealed 10 min at 700°C, and straight rolled to 0.064 in. It was then given a penultimate anneal of 20 min at 500°C and it was cut into four sections, which were given final reductions by straight rolling as follows: A 30 pct reduction of area B 50 pct reduction of area C 70 pct reduction of area D 90 pct reduction of area Specimens cut from the four sections were finally annealed at 800°C in an oxidizing atmosphere. Strip A remained fine grained up to 10 hr, but the specimen annealed 12 hr consisted of only 2 large grains. Strip B had a few scattered large (1/2 to 3/4 mm) grains after 1 min, although the balance of the specimen consisted of fine grains of about 0.02 mm. After 5 min there were several 10 to 15 mm grains present, and after 1 hr strip B was completely coarsened. The coarse grains had the same characteristics (see Fig 1) as those obtained by Cook and Macquarie at 800°C after cross rolling. Strip C had several grains of 0.05 to 1 mm after 1 min, but it was still largely fine grained after 12 hr. After 48 hr it consisted entirely of grains of about 0.5 to 4 mm, with an extraordinarily large number of twin bands. Strip D remained com- pletely fine grained after 4 hr at 800°C. These results indicate that, in the deformation range of 30 to 70 pct reduction, the incubation period for coarsening as well as the rate of growth and the final size of the coarse grains decreases with increasing deformation. Similar

Jan 1, 1950

By P. D. Merica

ALUMINUM and its alloys have been the subject of much investigation, during recent years, in the course of which the principal features of the constitution of most of the binary alloy systems with aluminum have been determined. Except in the case of a few metals-silicon, bismuth, cadmium, lead, zinc, and tin-an aluminum-rich compound is formed in each binary system, which forms a eutectic with the aluminum or its solid solution with this compound. Thus such compounds as FeAl3, CuAl2, Mg4Al3, and NiAl3 are formed, which are found in aluminum-rich alloys of their respective series as eutectics with the aluminum solid solution. These compounds are, in all cases, hard and brittle and their presence affects profoundly the physical properties of the alloys in which they occur. Within the zinc-aluminum system a compound, Al2Zn3, is formed that decomposes at lower temperatures. Silicon and tin each form a simple eutectiferous series with aluminum; bismuth, lead, and cadmium are only partly miscible in the liquid state with it. The extent of the solubility in aluminum, in solid solution, of these compounds or of the elements themselves, in the case of those series

Jan 7, 1919

By R. Steven Maxwell, Ulrich Petersen

Most minerals have experienced a slow hut perceptible decline in their annual primary production growth over the past hundred years. This decline is due to a combination of factors: (1) increased recycling; (2) exhaustion of the more accessible or higher grade ores; (3) partial substitution; (4) the more efficient use of materials; (5) progressive saturation of markets as living standards rise. Therefore, future demand for new mineral resources will probably be lower than anticipated. As the world population stabilizes, this slowdown in production growth will become even more pronounced.

Jan 1, 1979

By R. I. Jaffee, F. C. Holden, H. R. Ogden

Ti-Mn alloys were studied in order to determine the factors affecting the mechanical properties of &stabilized titanium alloys. The principal compositional factors have been found to be solid-solution strengthening, the martensitic transformation, and instability of the P phase. Structural factors, such as grain size and shape, were found to have more influence on ductility and toughness than on strength. THE alloys of titanium with the &stabilizing elements offer the chief hope for developing useful heat treatments. Conversely, the heat-treatment response possible with the p-stabilizing elements causes difficulties such as weld embrittlement and thermal instability during service at elevated temperature. Therefore, it is of considerable technical importance to understand the factors that govern the heat-treatment responses in these alloys, so as to be able to soften the alloys if they are embrittled by an adventitious heat treatment, to render them stable in service, or to harden them while maintaining adequate ductility and toughness. The Ti-Mn system is a good example with which to demonstrate the factors that govern strength and heat-treatment response in. a P-stabilized system. The region of the a-j3 transformation, after the work of Maykuth, Ogden, and Jaffee,&apos; is shown in Fig. 1. The a solubilities are low. This means that, in the two-phase a-p field, partition of manganese between the two phases occurs practically only to the P phase. The solid-solution effects are therefore chiefly the result of solution in the ,8 phase. The eutectoid occurs at 20 pct Mn and 550°C, and proceeds very sluggishly. It can be ignored in heat treatments in hypo-eutectoid alloys, except for long-time storage at low temperatures below the eutectoid temperature. Even here, there is some question that diffusion proceeds far enough to involve eutectoid decomposition. Three compositional factors bear on the mechanical properties and structure of titanium a-P alloys. These are: 1—solid-solution strengthening, 2—mar-tensite transformation, and 3—P instability. Combined with the purely structural factors of grain size and shape, these govern the properties of the alloys. Perhaps the most important factor is solid-solution strengthening. The facts that manganese dissolves in a titanium to a maximum of only 0.5 pct and most of the manganese partitions to the p phase dominate the structure and properties of the a-/3 alloys. Because of the overwhelming preference of manganese for the ,3 phase, the P phase is harder and the a phase is softer. The relative amounts of both phases may be modified by heat treatment in the a-P field as application of the lever rule in the two-phase field clearly shows. A critical temperature in the Ti-Mn diagram is 800°C. This is the P transus temperature of the 6.4 pct Mn alloy, which has the lowest manganese content which will form all retained-P phase on quenching to room temperature. Any quench performed from below 800°C will produce a structure consisting of only a, a plus retained P, or retained p, for alloys of the compositions used in this work. For alloys containing less than 6.4 pct Mn, any quench from above 800°C will always result in structures

Jan 1, 1955

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE mechanism by which the super-saturated solid solution of 20 per cent silver in aluminum decomposes has been reported in two previous publications. 1,2 The analysis of streaks in Laue photograms showed that thin platelike particles (the so-called Guinier-Preston aggregates) form upon {111} matrix planes in the early state of decomposition.1 The size of these particles is larger, the higher the temperature at which they form in accordance with nucleation theory;3 at all temperatures they increase in size with aging.2 When they have grown thick enough to afford three-dimensional diffraction, powder X-ray photograms show that the structure is not that of the equilibrium precipitate y but that of a transition lattice ?&apos;. Since this is also platelike in shape and also lies upon the {111} matrix planes with the {110} direction in the matrix parallel to the {11.0} direction in ?&apos;, it seems likely that the original platelet particles are merely ?&apos; in an early stage of formation, and thus finely dispersed. The atomic spacing and pattern on the {00.0} plane in ?&apos; are identical with those on the {111} matrix plane to which it lies parallel, and since comparable directions in the two planes are parallel, the lattices are thus coherent at the interface; an analogous coherence has been found in aluminum-copper alloys.3 The structures ?&apos; and y are both close-packed hexagonal and are oriented alike; they differ only in interatomic distances. Consequently, ? &apos; is regarded as y strained from its ordinary dimensions by the lattice coherency between it and the matrix.2 The lattice movements that transform the matrix to the equilibrium precipitate appear to be very simple.2 The mechanism of precipitation in this system is simpler and is more precisely known than that in any other system,2,4 hence the system should be a profitable one for the difficult task of correlating property changes with structural alterations. The present report provides additional studies on powder X-ray diffraction from alloys of 10 per cent, 20 per cent and 30 per cent Ag, and presents the correlation of crystallographic changes with changes in microstructure, Brinell hardness and electrical resistivity of the three alloys. PREPARATION OF SAMPLES AND EXPERIMENTAL PROCEDURE The preparation of the 20.2 per cent Ag alloy has been described.2 Alloys containing 9.9 and 29.7 per cent Ag were prepared from 99.97 per cent Al and 99.99+ per cent Ag using a similar procedure. Rolled

Jan 1, 1943

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

The activity of Sb,03 in PbO-Sb,03 slags containing less than 50 mol pct Sb,03 was determined by the inert-gas saturation method at 700°C. In this composition range, the activity gf SbzO3 shows a strong negative deviation from ideality. The activity of PbO in these slags was calculated by application of the Gibbs-Duhem iniegration to the Sb203 activity data. The calculated activity of PbO in slags containing more than 63 mol pct PbO was found to deviate in a positive direction from ideality uthile a negative deviation was found for slags containing less PbO. The standard Gibbs free energies of formation of Sb,03 and PbO. Sb203 have been calculated and compared with existing data in the literature. The activity of Sb203 in PbO-Si0,-Sb203 (PbO/SiO, = 2) slags containing less than 25 mol pct Sb,03 was also determined by the inert-gas saturation method at 700°C. In this composition range, the activity of Sbz03 shows a very large negative deviation from ideality. VERY little experimental work has been published in the past to determine equilibrium data in the oxide systems connected with the refining of lead. These data are of value since impurities such as antimony, arsenic, and tin must be removed from lead and recovered for further treatment. Equilibrium studies on antimony and arsenic systems are also of interest for the design of new processes for lead refining and lead dross treatment. Maier and ~incke&apos; first determined the liquidus curves for the PbO-Sb203 system and identified the compound PbO . Sb203. They found the phase diagram for this system to be two simple eutectics located on either side of the congruent melting compound. They also determined a very limited amount of vapor pressure data for Sb406 abbve PbO-Sba3 melts at 697"~. A second phase diagram investigation on this system was reported by Hennig and Kohlmeyer&apos; who confirmed the existence of the compound PbO . Sb203 as well as the form of the diagram. A disagreement was noticed, however, in that their liquidus temperatures over nearly the entire composition range were higher than those reported by Maier and Hincke. Barthel~ and pelze14 redetermined the liquidus curve at the PbO-rich end of the PbO-Sb@, system and agreed very closely with the results of Maier and Hincke. None of the investigators mentioned above reported any mutual solid solubility in the PbO-SbD3 system. Zunkel and Larson5 have determined the phase diagram for the PbO-rich end of the PbO-Sb203 system by slag-metal equilibrium studies in the Pb-PbO-Sb203 system and by thermal analysis studies in the PbO-Sbz03 system. A maximum solid solubility of 5.6 mol pct Sb203 in PbO was observed at the eutectic temperature of 604°C. Their results for the phase diagram agree favorably with those of Maier and Hincke. The vapor pressure of Sb2O3 in the temperature range from 470" to 800°C has been determined by Hincke, using a modification of the transportation meth~d.~ His results for temperatures below the melting point of Sba3 are the only data reported in the published literature. The predominant vapor species has been shown to be Sb,06 by Norman and staley.? Myzenkov and Klushin,8 using the boiling-point method, have determined the pressure of Sb406 above liquid SbD3 in the temperature range from 715" to 1025°C. The agreement between these two studies is not very close. A portion of the discrepancy lies in the fact that Hincke used silica crucibles, which were attacked by the liquid Sbz03 at high temperatures. This fact does not account, however. for the large difference observed at the melting point. ~aier&apos; gives a brief summary of vapor pressure data for Sb,O, above pure liquid Sbz03 which agree quite well with the data of Myzenkov and Klushin at temperatures near the melting point. This paper describes the determination of Sb2O3 activity data in the PbO-Sb203 and Pb0-Si02-Sb203 (PbO/SiOz = 2) systems by the inert-gas saturation method. These activity data are compared with the data calculated by Zunkel and arson. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade PbO (99.8 pct PbO, 0.14 pct insoluble in CHsCOOH, 0.02 pct not precipitated by HB, 0.1 pct CaO, and 0.08 pct SiOz), Sbf13 (99.6 pct Sb203, 0.004 PC~ C1-, 0.005 PC~ SO;-, 0.15 p~t AS, 0.001 pct Fe, and 0.03 pct other heavy metals such as Pb), and SiOz (chromatographic grade). Apparatus for Vapor Pressure Determinations. The apparatus used in this investigation consisted of a transportation reaction system with two separate gas trains. The argon transporting gas was first mixed with a small amount of hydrogen, metered, and dried by passage through silica gel and anhydrone drying tubes arranged in series. After this preliminary drying, the argon was passed through copper wool at 500°C to convert the residual oxygen to water vapor which was removed by three anhydrone drying tubes. A second stream of argon was metered and dried and then passed around the outside of the alumina reaction tube to flush away the volatile species to pre-

Jan 1, 1970