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By J. F. Myers, F. M. Lewis

The selection of the proper type of flotation machine involves the consideration of a wide variety of factors. Under any condition, all types of machines will promote some kind of separation. Obviously, the correct way of deciding which type of machine is best suited for a particular problem would be to set up all types of machines and test them out in a competitive manner, but the vast number of small concentrating plants are unable to make such complete and exhaustive tests. The experience of the authors of this paper indicates that if all the factors involved in any particular problem can be determined, and if all the flotation-machine characteristics are understood, some basis for selection could be arrived at other than actual comparison. This paper is presented to show how the process factors and machine characteristics have been combined at the mills of the Tennessee Copper Co. from studies of several types of flotation machines. At the two mills of the Tennessee Copper Co. in the Ducktown Basin of Tennessee, four distinct flotation separations are made on the complex sulphide ore. Three different concentrates are produced from the ore—in the order of their importance: iron concentrate, copper concentrate, and zinc concentrate. Four different types of flotation machines are used. The selection of these four machines, for the plant operation, was based upon the study and operating experience of the machine units shown in the following list: Fagergren machine; square cell, size 56 inches Fagergren machine; level type, size 56 inches Denver machine; conical disk impeller, size 24 inches Denver machine; receded disk impeller, size 24 inches Minerals Separation Sub-A, size 24 inches Munro-Pearse deep cell, pneumatic Southwestern air machine, Hunt principle To date the study of flotation machines has been confined almost entirely to the rougher circuits. The various cleaning operations, being relatively a much simpler matter, have not been investigated so thoroughly. Table I shows a typical analysis of the two ores as well as of the mineral content.

Jan 1, 1947

By D. K. Crampton

THE study of copper alloys of the age-hardening type has received considerable attention, and, among the alloys which the authors have considered, those containing small amounts of nickel and phosphorus as essential constituents seem especially interesting. Such alloys have attractively great capacity for being hardened and also have relatively high electrical and thermal conductivity in the hardened state. In addition, it has been found that the increase in hardness and strength imparted by aging can be greatly augmented by cold-working, so that axcellent combinations of conductivity and strength are obtainable. In view of the possible importance of the alloys, it was considered desirable to investigate the solubility relationships in the copper-rich portion of the copper-nickel-phosphorus system. This paper presents some of the results obtained in this investigation to date and also gives properties of typical alloys that appear to be of commercial interest.

Jan 1, 1940

By G. L. Oldright

THE development of the reverberatory furnace for smelting copper ores up to 1912 was described by E. P. Mathewson1 with details concerning the great changes in dimensions of the furnace. Hayward2 tabulated similar data, giving developments up to about 1924, in his revision of Hofman's Metallurgy of Copper. DEVELOPMENT OF PRESENT SMELTING PRACTICE Dimensions of Furnace Very great changes were made in the dimensions of the smelting hearths of the furnaces in the period from about 1800 to 1906, the length increasing from about 11 to 116 ft., and the width from 8 to 19 ft. During this time the tonnage smelted increased from about 9 to 250 tons per 24 hr., and the tons of charge smelted per ton of coal increased from 0.77 to 4.3. Dr. Mathewson3 noted no great difference in the "fuel ratio" (i. e., the amount of charge smelted per ton of coal) as the furnace at Anaconda was increased in length by stages from 85 to 116 ft. (The percentage of copper in the slag, however, was lowered from 0.42 to 0.36 per cent. The other components of the slag were not given.) Lump coal fired on grates was the fuel used during this period. The practice in operating the furnaces over such a length of time naturally varied considerably, and there were differences in composition and nature of the charge, yet it may be considered that the improvements made were due largely to increases in the size of the furnace used. Doubt-less some credit should be given to improvements in operating technique, like changes in the methods of firing the lump coal. However, the greater part of the advance was probably due to factors influencing the

Jan 1, 1928

By Melvin H. Podwysocki

Lineament and fracture analysis have enjoyed a resurgence of interest over the last several years, particularly since the advent of the Landsat series of Earth resources satellites. Some applications for lineament analysis include mineral, petroleum and ground- water exploration, engineering studies such as highway routing, mine roof stability, dam and power plant siting and general tectonic studies. The needs of each study may be different, but the general problem of large masses of data is common to all. Methods for efficient handling of the information and some statistical methods for its evaluation are discussed. These include comparing the lengths of the fracture population against known distributions, trend surface analysis of fracture lengths and number per unit area and multivariate analysis of rose diagrams. Examples are shown in an experimental program for predicting the presence of reef structures, areas of potential petroleum production.

Jan 1, 1977

By L. W. Casteel

This is a story of progress through research, invention and innovation-progress that made a small mine in Missouri into a large and prosperous corporation. The St. Joseph Lead Co. was founded in Borne Terre, Missouri, in 1864. At that time, the mine consisted of a narrow trench eight feet deep; the mill was a hand-operated jig; and the smelter, a charcoal oven with a sloping hearth. During the first year, production was suspended for two months because of an invasion by the Confederate army. There have been few interruptions since that time.

Jan 7, 1964

Jan 1, 1927

By N. Arbiter, J. Steininger, C. C. Harris

Power consumption and operating variables in air-liquid systems for a wide range of operating conditions in the turbulent region have been correlated by two dimensionless groups involving the power ratio and the flow number. The form of the correlation was developed by considering flow balances related to the air-liquid composite density in the impeller zone. Data for two phase air-liquid systems, both from literature and from the present investigation, has been correlated with high statistical significance. Two phase solid-liquid and three phase gas-liquid-solid systems have also been correlated. The quantification of power requirements in the agitation of liquids is well established.1 Rushton, Costich and Everett have shown that, for mixers operating in the fully turbulent region with no vortex, the power number

Jan 1, 1964

By Yinchang Wang

1. INTRODUCTION 1. Subject, and Scope The formation of the oxidized ores of zinc has been recognized as a subject of great importance in economic geology. For many years these ores have been much sought, partly because they are more desirable for metallurgical treatment and partly because they are apt to be freer from gangue than is the sulphide of zinc. Up to very recent years the oxidized ores were the principal source of the metal and at present they still furnish a large portion of the commercial production. . The oxidized ores of zinc include six minerals, as shown in the-following table

Jan 9, 1915

By A. M. Gow

The trend in ball milling has been toward mills of larger diameter, but without fundamental laws as a guide. The speeds at which mills are run have been a matter of cut-and-try. This paper deals with both diameter and speed and proposes to show the laws which apply to some laboratory ball mills, ranging in diameter from 18 to 42 in., run at various speeds. The correlation of power, speed and grinding rate of the respective mills will be shown by curves of markedly significant similarity. Before presenting the results some consideration will be given to the mechanics of ball milling. Mechanics and Theory of Ball Milling As early as 1904, Herman Fischerl reported observations on specially constructed ball mills which allowed the paths of balls to be studied. The following conclusions were drawn: 1. Balls do not grind the ore, but crush it by impact. 2. At slow speeds the balls roll down the inclined heap, but at higher speeds the balls close to the wall adhere to it until they reach a certain height, whence they are thrown through an arc to the bottom. 3. The falling balls do not come down in clusters, but in series, the balls of each row keeping to their own line of flight according to their distances from the wall while ascending. 4. A further increase in speed results in the balls adhering during the whole of the circuit to the side of the drum. (This centrifuging speed may be called the "critical" speed and may be taken as a reference basis, since it is a constant function of the diameter.)2

Jan 1, 1930

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942

By Frank Reiber

The study of earthquakes long ago developed the fact that by study-ing the travel .times of the various groups of waves from the same earthquake, as received on seismographs :it varying distances, major discont'inuities in the earth's crust, could be reasonably well defined. Using this original discovery, and adapting the mathematical methods originally devised in seismology for determining the depth below the surface at which such discontinuities occur, other investigators were able to develop a new branch of seismology which promises to be extremely useful in extending the boundaries of our information on local conditions Below the earth's surface. As an outstanding example of the applications of this work, we have the so-called " seismograph " exploration of the Gulf Coastal region, which has resulted in the discovery of a large number of salt domes, from many of which oil fields may be developed. The original seismological investigations, from which different major discontinuities in the earth's crust were deduced, as well as these later successful experiments in locating salt-dome structures, involve relatively simple problems. In each case we arc dealing with surface materials in which elastic waves will be propagated with a fairly definite velocity. Under this material we have something quite different', in which the elastic waves will be propagated with a much higher velocity. The transition from one medium to the other is likewise relativtly abrupt. For example, in the Gulf Coastal region the sedimentary formations have a velocity of 6000 or 7000 ft. per sec., while the velocity of elastic waves in the cap rock of a salt dome may exceed 15,000 ft. per sec. Under such conditions, delineation of the formation is a relatively simple matter, and, furthermore, there is very little opportunity for ambiguous results. Development of Elastic-wave Method The success of this Gulf Coast work immediately suggested the advisability of attempting to extend elastic-wave methods to a point

Jan 1, 1929

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By Oscar Weiss

STILFONTEIN and surrounding areas gave negative results in all prospecting attempts since about 1904 when Goerz and Co., a forerunner of Union Corporation Ltd., first drilled in the region and on the farm Stilfontein. Subsequent efforts by African and European Investments Co. and Anglo American Corp. from 1934-37 were completely unsuccessful. Holes drilled by these companies on the farms Rietfontein, Hessie, and Palmietfontein were stopped in the Lower Witwatersrand system without finding payable reefs.

Jan 10, 1951

By R. W. Raymond

In a paper on the Divining-Rod (Transactions, xi., 411), presented at the Boston meting, in February, 1883,I suggested, among other signs of which the skilled prospector might consciously or unconsciously avail himself in the search for springs of water or mineral deposits, the presence of particular grasses or shrubs, and the general appearance of the flora. There are not wanting, in the literature of our art, indications that greater attention was paid to such signs in ancient days than at present. It is the tendency of a scientific age to ignore, or regard as superstitious, what cannot be classified or explained. But the acute though unscientific observation of earlier times often, doubtless, accumulated facts which it would be worth our while to re-examine. It is highly probable that the mining prospectors of the sixteenth and seventeenth centuries, to go no further back, were close students of nature, and knew, though they could not explain, and, for reasons of private gain, would not communicate, many curious and significant facts. We can generalize better than they could; but for that very reason we are, perhaps, their inferiors in observation. They let nothing pass, because all things were equally significant to them. We take wider views, and miss more. And, no doubt, there still exists among practical millers, prospectors,, hunters, Indians, etc., an unwritten.

Jan 1, 1887

By Benjamin C. Greene, H. Beecher Charmbury

Water is a most remarkable substance, essential for life of all kinds. As well as needing water to survive, man has always used it for agriculture, transportation, recreation, and many other things. When our country was young and inhabited by few people, the streams, rivers, and lakes were able to provide all the clean water needed by man and take away all the wastes created. However, with our growing population and an ever-increasing demand for goods and services, the public, industry, and government at all levels have become acutely aware of the need to manage the nation's water resources more efficiently. Abundant energy from many sources has helped this nation to become the greatest industrial nation in the world. Coal has contributed a major portion of this energy, generating electricity, running railroads, and maintaining national security during wartime. The result has been the highest standard of living in the world and a time of widespread economic prosperity. The use of water in coal mining is somewhat different from its use in most industries. With the exception of water used in cleaning plants, for underground dust control, and for fire protection, most of the water en- countered in coal mining operations serves no useful purpose. In other words, it is an undesirable element and must be removed, otherwise it will interfere with operations, cause potential water quality problems, and may even stop operations by flooding. In the past, removing water from working areas of most mines was usually a fairly simple matter. Pumps with piping were installed at sumps or low spots in the mine and the water was pumped to the surface or to drainage control facilities constructed for the operation. Ditches were often used to collect and drain the water by gravity to the outside or to main sumps for pump discharge. In either case, the water was allowed to flow into the nearest stream or river. The concept of "water is water" was generally accepted without too much concern for what was in

Jan 1, 1981

By H. Bartholomew, L. Bernstein

Experirmental bonds of Ag-In SLID to gold, copper, nickel, Kovar, Dumet, nickel-plated molybdenum, ALL-Pt vrzetallizing on ceramic, and nickel-plated Mo-Ti metallizing on Al2O3 ceramic have been made and exalnined. Metallographic taper sections were made of all bonds for Phase identification. In addition, failuve temperatltres were determined for bonds heated undev shear load. Sowe bonds were subjected to electvon-probe microanalysis. The ternary SLID system Ag-In-Sn was similarly evaluated. Plwtonticrogaphs and electron-probe data are discussed and related to over-all phase diagrams , diffusion effects, and wetting properties of the liquid. The rates of diffusion andor compound formation of gold, silver, and copper in indium and In-Sn liquids are found to descend in that order, as measured by the relatzve thickness of phase layers in the interfaces of bonds made at 200to 400°C. It is concluded that the SLID process enables one to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures, and meet most requirements for application in interconnection, silicon bonding, or hermetic sealing of electronic devices. In a previous publication by one of the authors, the theory and principle of SLID bonding in simple binary systems was discussed. SLID bonding can be defined as a joining process using a preform with a laminated structure: a low-melting material clad on a high-melting core. During the bonding cycle a metallurgical transformation occurs such that the resultant structure can withstand, without reliquefying, temperatures higher than those at which the bond was made. The phases present in the joint interface region are high-melting compounds or, if equilibrium is reached, solid solution. Properties will depend on the phases present, ultimately approaching those of the solid substrate core of the SLID preform. The high-temperature strength of bonds made in these systems was correlated to phase identification in the interfacial bond regions from metallographic cross sections and electron-probe X-ray microanalysis data. When complex electronic components are assembled, multiphase systems result at the interfaces of bond regions. In these ternary and higher-order systems very little diffusion and phase-diagram data is available with which to predict the nature of the interfacia1 region that will result from conventional fabrication processes and subsequent field use of the component. Clarke and Rhines did early work in the field using the Al-Mg-Zn system as a vehicle. Guy and co-workers studied a portion of the Cu-Zn-Ni system and some mathematical4 and general5 aspects of multiphase diffusion. irkald' and coworkerse recently studied diffusion in the Cu-Zn-Sn system. No diffusion studies have been made on ternary systems directly applicable to this investigation but some phase diagrams are available: g-u-n, u-i-n, and CU-i-n. I) DESCRIPTION AND EXPERIMENTAL PROCEDURE The elements Au, Ag, Cu, Ni, In, and Sn are found in alloy systems commonly used in fabricating and assembling electronic components. Reference to the appropriate phase diagrams9 and the previous publication will indicate that the binary systems of any of the two low-melting elements, indium and tin, with any one of the other four higher-melting elements are capable of producing SLID bonds. It is not unreasonable to assume that any ternary or higher-order alloy system containing at least one of the elements gold, silver, copper, or nickel and one or both of the elements indium and tin could be used to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures. Indeed, the liquidus contours and isothermal sections of those phase diagrams available7 do so indicate. The parameters affecting the bond and the equipment used in evaluating the bond were described in an earlier paper.' The current investigation used the

Jan 1, 1967

By J. E. Dorn, L. A. Shepard

LOW and Gensamer' demonstrated a number of years ago that the yield point phenomenon in mild steels was associated with the presence of fer-rite soluble carbon or nitrogen. More recently the yield phenomenon in body-centered-cubic metals containing interstitials was rationalized by Cottrell' in terms of a simple dislocation model. Interstitial atoms interact with dislocations in two ways; they cause not only local expansions but induce local tetragonality in the lattice. Consequently, interstitial~ interact with the hydrostatic tension and shear components of the stress about dislocations. They tend to migrate toward the expanded regions of edge dislocations and to assume sites that relieve the shear stresses of screw dislocations. Thus, a dislocation saturated with solute atoms constitutes a lower free energy state than that obtained when the dislocation threads through the average composition regions of the matrix. A greater stress will be required to separate the dislocation from its atmosphere than to move the dislocation through the matrix. This factor gives rise to the upper yield stress, which is required to unleash a series of dislocations in a localized region. This local yielding is propagated across the specimen to form a thin band of plastically deformed material known as a Lueder's band, making an angle of about 45" to the stress axis. Once the band has formed, deformation continues at the lower yield stress by the spreading of the Lueder's band in the direction of the applied stress. Undoubtedly the spreading of Lueder's bands at the lower yield stress is accomplished by the high stress concentrations at the band fronts, which serve to induce continued unlocking of new dislocations in advance of the migrating band fronts. Cottrell and Bilby have shown that the dependence of the yield point on temperature can be deduced by assuming that thermal fluctuations aid the stress in unlocking small dislocation loops from their solute atmospheres. Once a loop that exceeds a critical size has been nucleated, the entire locked diqlocation is released and can migrate. Fisher4 simplified this analysis by assuming that the locking forces were short range, so that if the dislocation loop were displaced only one Burgers vector from its atmosphere, it would be unlocked. Applying his model to the special case of delayed yielding under a constant stress of the order of the upper yield strength, he demonstrated that the delay time 7 for yielding should depend on stress and temperature according to where A and B are constants, G is the shear modulus, and u and T are the resolved shear stress and absolute temperature, respectively. Cottrell and Bilby, Fisher, and Fisher and Rogers' have shown that the above deductions are at least in qualitative harmony with the experimental facts. A number of investigators5-0 have shown that the yield point phenomenon can also be induced in sub-stitutional alloys of face-centered-cubic metals. In general such yield points are not as pronounced as those encountered in body-centered-cubic metals containing interstitials. The yield point phenomenon in these materials is usually enhanced by prestrain-ing at low temperatures and aging at intermediate temperatures. Undoubtedly the yield point phenomenon induced by strain aging substitutional alloys also results from locking of dislocations. But the locking of dislocations in substitutional alloys of face-centered-cubic metals differs somewhat from interstitial locking of dislocations in body-centered-cubic metals. Substitutional elements in face-centered-cubic lattices cause only radial displacements of the adjacent lattice points. Consequently, only the edge components of dislocations can be locked by the mechanism suggested by Cottrell. Additional locking, however, can be obtained by the Suzuki mcchanism.10 In face-centered-cubic metals, dislocations exhibit lower energies when they are present in the

Jan 1, 1957

By Alexander R. Troiano, Taylor Lyman

Studies of the transformation of aus-tenite at constant subcritical temperatures have been numerous since the work of Davenport and Rain.' Considerable information has been obtained on low-alloy steels and on high-carbon alloys containing undissolved carbide or graphite at the austenitizing temperature. Little is known of the isothermal transformation of aus-tenite containing in solution large amounts of both carbon and a single alloying element. In this investigation four steels containing one per cent carbon and with chromium in the range 3 to 9 per cent have been examined with the view to establishing the fundamental character of the isothermal reactions when all carbon and chromium are initially in solution in austenite. Experimental Procedure Alloys The chemical compositions of the steels investigated are given in Table I. The 4 per cent Cr alloy is a commercial steel. The other steels were made by the Carpenter Steel Co. as 50-lb., induction-furnace heats and rolled to 5/8 -in. round bars. Bars were softened at 650' to 700°C. before the specimens were cut. Most of the lines on the transformation diagrams presented here have been placed on the basis of the microscopic examinatioll of partially reacted specimens, Thees specimens were approximately 1/2 by 1/4 by 1/8 in. ill size, specimens of the 9 per cent cr steel were held 10 to 12 hr, at 1200°to 1225°C. before quenching to the various subcritical temperatures. The other steels were held for 2 to 2 1/2 hr. at 12ooOC. before quenching. These treatments, carried out in an atmosphere of purified nitrogen, produced an austenite grain size larger than A.S.T.M. So. I, some grains being 1 to 2 mm. in diameter. There were a few undissolved carbide particles in some specimens of the 9 per cent Cr steel. It is believed, however, that any errors in the results due to incomplete solution of carbon and chromium in austenite are negligible; that is, austenite compositions may be considered as being those listed ill Table I. X-ray Methods Constituents were identified and mar-tensite axial ratios determined from Debye

Jan 1, 1945

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965