Search Documents

By G. L. Oldright

NEARLY all of the present schemes for treating complex (i. e. lead¬silver-zinc-copper) ores are based on the idea that lead holds, and will hold for some time, the strongest economic place from the viewpoint of supply and demand of all the non-ferrous metals. Copper, it is thought, will come back to its own when European affairs are stabilized, although at that time competition from Chile, Peru, and Katanga, in particular, will be more severe than in pre-war days. The future for silver and for zinc is uncertain. New uses are developing for zinc, and the market has remained better than many expected, but the stabilization of world markets will bring in foreign competition instead of relief. The cost of producing zinc from simple zinc ores, by the retort process, will, from the nature of the labor required and the increasing cost of fuel, increase steadily. As a result, the small producers of purely zinc ores around Joplin are shutting down their mines, even with a good market price for zinc; on the other hand, the producer of lead from complex ores, in the Rocky Mountain states, is confident of a profit from the sale of his lead, and is seeking means to make the zinc in his ore pay some part of the cost of treatment. However, the tonnage costs for mining and ore dressing are much higher in the Rocky Mountain states, as may be seen by comparing tax-return statements from the various states. Even before the recent drop in the price of silver, many mines were operating on a very slender margin of profit; labor and supplies cost more. Mining at greater depth has shown most orebodies to grow increasingly more complex, so that improvements in mining and ore-dressing practice have not been sufficient too compensate for the additional expense involved in beneficiating these ores. The smelters have had to meet the same general economic situation, so they can only give

Jan 3, 1924

By V. F. Zackay, J. F. Carlson

CURRENT experimental work on the development of gas turbine engines in the automobile industry has emphasized the need for a relatively low cost nonstrategic castable alloy for service in the 1200" to 1400°F temperature range. Ferritic steels

Jan 1, 1956

In the examination of an undeveloped prospect a decision must be arrived at from an inspection of the outcrops and the exposures in a few shallow pits. Prospects that are offered for sale rarely expose any important quantity of good ore, work having usually been stopped when the immediate exploration no longer yielded favorable results. It should be borne in mind, furthermore, that a great majority of prospects have been examined many times, and if of conspicuous promise, would have been acquired-for development. In most cases the problem for the engineer, therefore, is to discover the traces of a valuable mineralization that has disappeared through solution, or the conditions that indicate the possibility, or probability, of underlying secondary enrichments. The available data being meager, every feature should be the subject of careful study-the condition of the outcrop, the structural relationships, the associations of minerals, the alterations of wall rocks, the chances for underlying enrichments, and so forth, as well as the actual assay value of the material exposed. It is frequently advisable to spend the time and money necessary to have trenches dug at various significant points along a promising outcrop; such exposures, even if the depth attained is slight, often disclose conditions that are not apparent at the actual surface, as for example, the existence of soft minerals and the distribution of the various minerals through the mass of the deposit. Trenches also permit samples to be taken from points that were not accessible during former examinations. Strong, persistent outcrops of uniform width may be taken to indicate the probable size and character of the underlying vein,

Jan 1, 1932

By J. Weertman

High-temperature creep experiments were carried out on indium, lead, and on binary substitutional alloys of In-Pb, In-Sn, In-TI, In-Cd, In-Hg, Pb-Bi, Pb-Sn, Pb-In, and Pb-Cd. The stress at which the power law creep equution breaks down was found to be much smaller for indium and lead than for metals with larger elastic moduli. The exponent over the stress in the power law creep equation was found to decrease upon alloying from values close to 4.5 to values near 3. THIS paper describes a set of high-temperature creep experiments made on high-purity lead and indium and on lead-rich and indium-rich single-phase binary alloys of various metals. These ex- periments were carried out to check two predictions of some creep equations derived by us"2 from a dislocation creep model due essentially to Mott. This model is shown in Fig. 1. Here dislocation loops are emitted from sources, not shown, situated on different slip planes. As the loops expand they come into each others' stress fields and are stopped. However, at high temperatures, as Mott has pointed out.

Jan 1, 1961

By Robert A. Haney, Stephen J. Gigliotti, James L. Banfield

A series of investigations were made by the Mine Safety and Health Administration to evaluate the performance of various face ventilation systems as part of a program to reduce frictional ignitions of methane and to develop face ventilation systems that could be used with the line brattice more than 10 feet from the face. Tests were conducted in a full-scale laboratory model of a face area. Systems tested included unassisted blowing and exhaust line brattice, diffuser fan and spray fan systems. Systems were evaluated at air quantities ranging from 1.4 to 7.0 m3/s (3,000 to 15,000 cfm), and brattice-to-face distances from 1.5 to 9 meters (5 to 30 feet.). Tests were designed so that systems could be evaluated for the location of the high-point methane concentration in the face area, methane dilution capacity, and face ventilation index. The methane dilution capacity is the total amount of methane a system can dilute to 1.0 volume-percent. The face ventilation index is the efficiency at which the available face air volume is being used.

Jan 1, 1982

By Robert E. Green, Edmund G. Henneke

The velocities of the three possible modes of elastic wave propagation have been calculated for single-crystal copper at 1-deg intervals throughout the standard stereographic triangle. The results are presented as isospeed contours. The deviations between the direction of maximum energy flux and specimen axes are presented as arrows drawn on stereographic projections. The orientation factors associated with dislocation motion on the primary slip system only and also on all twelve slip systems have been calculated for all three elastic waves. The orientation factors associated with a longitudinal standing wave resonant specimen have also been calculated. The results of these calculatians are compared with earlier calculations on aluminum crystals and the relevance of these results to ultrasonic attenuation measurements is discussed. GREEN and inton' have recently outlined a procedure for determining the orientation factors for dislocation damping in single crystals. The stress field associated with a given mode of elastic wave propagation is resolved on the slip systems in which it is assumed the dislocations are vibrating due to this stress field. Since, at room temperature, slip has been observed on a limited number of systems in fcc and hcp metal crystals, it is assumed that these systems are the appropriate ones to use for the resolving process. This procedure has been applied to aluminum crystals by Hinton and hreen' and to zinc crystals by Henneke and Green.3 In the present paper the modes of elastic wave propagation have been calculated for copper crystals possessing orientations at 1-deg intervals throughout the standard stereographic triangle. The deviation of the energy flux vectors from the specimen axis have been calculated for each mode. The stress field associated with each mode has been resolved on the (111)(110) slip systems in order to determine the orientation factors for dislocation damping. MODES OF ELASTIC WAVE PROPAGATION For any direction in a linear homogeneous aniso-tropic material three elastic modes can be propagated. In general, each of these modes has both longitudinal and transverse particle displacements associated with it and thus are not "pure" modes. However, there is always one component which is greatest in either a longitudinal or transverse direction and hence the mode may be referred to as quasi-longitudinal or quasi-transverse, accordingly. For certain axes of high symmetry pure modes may be propagated. The phenomenon of refraction of the energy flux vector is also exhibited by elastic wave propagation in ani-

Jan 1, 1969

By M. Gensamer

ALTHOUGH a large number of X-ray photograms of cold-rolled steel have been published, two circumstances have led to the experimental work reported in this paper. The first is that no complete study, making use of the pole-figure method of Wever1, has been made of cold-rolled low-carbon steel. Wever has published pole figures of mild steel sub-jected to plane parallel deformation1,2 and undoubtedly he has applied the method to cold-rolled mild steel, but the authors have not found these data published. Kurdjumow and Sachs3 have applied the method to the study of rolling and recrystallization textures in electrolytic iron; their results will be referred to later. The reason for this dearth of papers using the pole-figure method is obvious; a greater number of photograms and more analytical work (although this work is quite simple and straight-forward) are required to construct a pole figure than most investigators have felt worth while, despite the fact that no other method of which the authors are aware will satisfactorily depict the orientations of the crystal-lites in a polycrystalline aggregate. The second circumstance that led to the work reported in this paper was the appearance of a paper by Wayne A. Sisson4 on the same subject. In his valuable study of the factors influencing the development of pre-ferred orientations in cold-rolled mild steel, Sisson made one observation that required confirmation; that is, that at some stage of the rolling proc-ess the type of preferred orientation changed from the type that gives a photogram characterized as a "six-point" X-ray pattern to that known as a "four-point" pattern. A similar observation had been made by Tam-mann and Heinzel5, who studied the orientations developed in the rolling of steel by the specular reflection of light from the etched surface of rolled samples. These workers also found that the type of preferred orientation

Jan 1, 1936

By Daniel M. MacNeil, Carle R. Hayward, Raymond L. Presbrey

At the February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500" it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence was presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. coöperated by furnishing the steel and turning the tensile specimens. The steel used in this investigation came in three bars 3/4 in. in diameter; analyses are as follows: Carbon. MaNGanese, Phosphorus, Sulfur Bar NUmber PeR Cent. Per Cent. Per Cent. Per Cent. 1 0.46 0.56 0.010 0.055 2 0.44 0.58 0.007 0.042 3 0.48 0.58 0.007 0.048

Jan 1, 1922

By Daniel M. MacNeil, Raymond L. Presbrey, Carle R. Hayward

At the February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500" it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence was presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. coöperated by furnishing the steel and turning the tensile specimens. The steel used in this investigation came in three bars 3/4 in. in diameter; analyses are as follows: Carbon. MaNGanese, Phosphorus, Sulfur Bar NUmber PeR Cent. Per Cent. Per Cent. Per Cent. 1 0.46 0.56 0.010 0.055 2 0.44 0.58 0.007 0.042 3 0.48 0.58 0.007 0.048

Jan 1, 1922

By J. Gordon Parr, A. J. Goldak

OgdEN et al.1 and Bumps et al.2 suggested that the solubility of aluminum in a titanium extended to 30 pct.* Sagcl,3 Clark and Terry,4 Anderko et al.,5 Ence and Margolin6 and Saulnier and croutzelles,7 subsequently proposed the existence of an intermetallic compound in the region of 25 pct Al. Although Anderko et al.5 suggested that the structure of this phase, Ti3Al, was of the DO,, (Ni3Sn) type, their conclusion was based only upon the results of a powder photograph that included reflections from ? = 0 to ?= 27° (CuK),some of which were reported to be indistinct. Ence and Margolin,6 referring to a 25 pct alloy (but without indicating whether the figure referred to weight or atomic pct) stated: "The structure of Ti2Al is isomorphous with Ti3Sn DO19, as pointed out by Pietrokowsky". But the point was not proven, because Ence and Margolin did not report values of calculated intensities of Ti2Al with the DO,, structure. In fact, the observed intensities they reported are in poor agreement with the values we calculate for DO19 (see Table I). Saulnier and croutzelle7 concluded, on the basis of electron micrography and microdiffraction studies, that the structure of the 25 pct A1 alloy was ordered hexagonal. Our purpose has been to unequivocally determine the Ti3Al structure. Alloys containing 25 pct Al were prepared from iodide titanium and spectrographic standard aluminum by levitation melting. The levitation chamber was evacuated to 10-6 mm Hg before filling with 99.999 + pct A. After casting, the alloy was chilled to liquid air temperature and crushed to -200 mesh in a percussion mortar. The powder, wrapped in molybdenum foil, was annealed (by induction heating) at 1000 "C for 2 hr in the argon atmosphere of the levitation chamber. No sublimate was seen on the foil or elsewhere, and therefore the assumption is

Jan 1, 1962

By Y. C. Liu, R. H. Richman

The effects of gel,manium and tin on the deformation and 9-e-crystallization textures of copper have been explored in detail with in the copper-rich terminal solid solutions. Addition of solute to copper produces a change in deformation texture from the copper type to the 70 :30 brass type. This transition has been measured quantitatively The types mid proportions of recrystal-lization components have been determined as a function of com-position, and correlation of recrystallization components with specific deformation components is discussed. On the basis of information available in the literature, it has been suggested that the effect of solute elements on the recrystallization texture of copper

Jan 1, 1961

By Sherwin F. Kelly

THIS is intended as a simple review of the principles and practice of geophysics, so will not be of interest to the geophysicist, who is hereby warned of its elementary character. The engineers for whom it is written are those who, having glimpsed the formidable formulas and discussions of the geophysicists, give all publications on the subject a wide berth. For a few years now the geo-physicists have had a tendency to be ingrowing at their meetings, going deeper and deeper into theory and instrument construction, and forgetting to present the topics that would interest the practicing engineer who desires merely to know how geophysics can help him, not why.

Jan 1, 1934

By D. K. Crampton

INTERNAL stress and season cracking in brass have been studied for many years and the technical literature contains many data on various phases of the subject. A résumé of the literature shows certain fairly well established points upon which various authors are mostly agreed: 1. Season cracking is primarily caused by the presence of relatively high internal stresses, or possibly in some cases by external stresses, or both. 2. A specific corrosion is also essential to season cracking: Certain agents, particularly mercurous salts, mercuric salts and ammonia salts; have such a specific corrosive effect. 3. The tendency to season crack under given conditions increases with increasing zinc content, brass containing less than 20 per cent zinc being relatively immune. 4. In alpha brass the season cracks are intercrystalline; in alphabeta brass they lie between the two constituents; and in beta brass they are transcrystalline. 5. The ordinary impurities or added elements in special brasses have little or no effect on the tendency to season crack. 6. Internal stresses can be eliminated, or at least reduced to a safe 'limit by annealing treatments at temperatures that do not produce visible microstructural changes or appreciable softening of the worked brasses. There are, however, some points in connection with the phenomenon of season cracking which have not been thoroughly investigated, or wherein different authors and investigators are not entirely in agreement. The investigations described in this paper were undertaken to determine: 1. The correlation between mercurous nitrate tests and actual season cracking on long-time atmospheric exposure. 2. The quantitative effect of type and degree of drawing operations on the intensity of internal stress and on the tendency to season crack in brass tubes. 3. The possibility of drawing high-brass tubes in such a manner as to prevent the occurrence of harmful stresses rather than to find a remedy for such stresses once having obtained them.

Jan 1, 1930

Discussion -of the paper of I. N. KNAPP, presented at the New York meeting, February, 1915, and printed in Bulletin No. 96, December, 1914, pp. 2783 to 2793. A. C. LANE, Tufts College, Mass.-Is there any noticeable effect in drilling against salt water? Mr. Knapp says that the mud settles very quickly when brine is added-. What is the effect when you strike a strong salt water ill boring? I. N. KNAPP.-You are supposed to have enough mud pressure in your well to keep the saltwater out. I have drilled against what I knew to be 80 ft. head of water, and hot water too at 99.5°; this water did not show until the well was bailed and the mud pressure reduced. HENRY Louis, Newcastle-upon-Tyne, England (communication to the Secretary*).-Mr. Knapp may be interested to learn that the use of mud in drilling through porous strata is much older than lie appears to be aware of. It has been used notably by Honigmann for boring shafts in Holland and in some of the adjoining portions of Germany. At the Oranien Nassau colliery, shafts about 12 ft. in diameter and 425 ft. deep were sunk in. this way-namely, by boring with a rotary borer, a thick mud puddle being pumped into the shaft, so as to maintain a pressure in the shaft greater than the hydrostatic pressure in the surrounding loose sands and thus keeping the sides of the shaft from collapsing. He will find references to this method in Das Abbohren von Schächten; Handbuch der Ingenieurwissenshaften, p. 134, also in the Transactions of the Institution of Mining Engineers, vol. xiii (1896-97), p. 155. The process appears to have been employed even before 1895, though I cannot give the exact date when it was first used.

Jan 5, 1915

By Herbert Ives

THE incandescent gas mantle is of considerable interest from the standpoint of temperature measurement because it presents a series of apparent contradictions to the established laws of radiation on which are based some of our best methods of temperature determination. One of these contradictions is that the mantle of least brightness (of the commercial thoria-ceria group) is the one having the highest temperature; this, though explicable without any violation of radiation laws, was long a stumbling block to the understanding of the performance of the mantle. Another anomaly is that the energy radiated by the mantle decreases with the rise of temperature, thus apparently invalidating total radiation methods of pyrometry, based on the fourth-power law. The discussion of methods of measuring mantle temperature which follows, is largely taken from an extensive study of the physics of the Welsbach mantle. 1 The incandescent gas mantle consists of a skeleton of refractory oxide of very light weight and open structure, formed by the ignition of a cotton or silk "stocking" previously thoroughly impregnated with salts of certain rare earths. The mantle of commerce is a mixture of approximately 99 parts of thorium oxide with 1 part of cerium oxide. This mixture, discovered largely by accident, gives luminous radiation many times greater than that from either of the constituents taken alone. It is customary to speak of the thoria as the "base" and the ceria as the "colorant," and the commercial mantle represents one of a family in which an oxide of low emissive power is employed as a base, which will assume a high temperature, while a small amount of some other oxide of high visible emissive power is added, which will reduce the temperature of the mantle but little. This is, in general, the most efficient- way, from the standpoint of visible emission, to utilize a substance of high emissive power in the visible spectrum. But it is not necessary. that two substances should be employed to produce a radiator

Jan 9, 1919

By W. I. Duvall, L. D. Sadwin

Three explosives with different detonation characteristics were tested by studying their cratering ability in a granite-gneiss. The strain wave generating characteristics of these explosives were also studied in the same rock medium. Correlations between the relative performance of three explosives as evaluated by crater studies and other methods of evaluation are indicated. Numerous test methods have been employed to evaluate the output performance of explosives; for example, the underwater explosion method, the airblast method and the ballistic pendulum method.'*' For blasting applications, the study of explosion produced craters and explosion generated strain waves are the most meaningful. This laboratory has employed these techniques extensively for many years and has shown that the detonation properties of explosives and their ability to generate strain waves in rock are related and that the amplitude and shape of the strain wave is related to some of the crater parameters such as slab thickness and fly rock velocity.3'11 However, a good comparison between the relative performance of explosives as determined by the crater and strain wave methods had not been made. The purpose of this investigation was to determine if the relative performance of three explosives as determined by the crater method shows a correlation with the relative performance as determined by the strain wave method. If a good correlation exists between these two sets of relative performance, it should then be possible to relate the detonation properties of an explosive to its ability to break rock in a crater test. In most commercial blasting operations, the diameter of the blast hole remains constant even though the type of explosive may change. In general, it is the explosive volume rather than the weight which remains constant when two or more explosives of different density are compared. Therefore all tests in this investigation were conducted on a constant volume basis rather than on a constant weight basis. TEST SITE AND ROCK PROPERTIES The tests described in this paper were conducted at a granite quarry owned and operated by the Consolidated Quarries Div. of the Georgia Marble Co. at Lithonia, Ga. The tests were performed in an area where the exposed rock surface was nearly horizontal and where the general rock mass had few joints or faults. The rock has an apparent sp gr of 2.6 and a longitudinal propagation velocity of 18,000 fps. The characteristic impedance of Lithonia granite gneiss is 53(lb - sec/in3). EXPERIMENTAL PROCEDURE There are many parameters which must be considered in the study of explosion-produced craters. The role played by each variable in the explosive-rock-crater system can be determined by experimental techniques in which one parameter is varied while others are maintained constant. In this investigation, the crater geometry was studied as the depth was varied for each of three explosives. The explosive volume and rock-type were held constant for all crater tests. The experimental arrangement used in performing the crater tests is illustrated schematically in Fig. 1.

Jan 1, 1965

By F. C. Pittman, D. W. Harriman, J. C. St. John

This paper mentions briefly the history of hydraulic jetting as applied to perforating and fracture initiation. It points out the advantages of hydraulic perforation and undercutting as an aid for creating a fracture at the point desired rather than depending upon the weakest point in the formation for breakdown. It describes early experimental work with jet nozzles in search of better nozzle materials. The effect of splash-back damage and its subsequent influence on jet body and tool design during this work is discussed. A series of cutting-rate curves for jets cutting steel and steel-cement-formation combinations is presented to show the effect of hydrostatic head and the point of diminishing returns with respect to cutting time. There is a series of photographs showing various types of rock formation in which perforation and undercutting tests were made. These stones were drilled and the casing cemented in place as in an actual well. The casing was perforated and circularly cut as if preparing for a fracturing job. The conclusion reached in the paper is that hydraulic jetting with sand-laden fluid can be used for perforating and undercutting casing, cement and formation rock for the intended purpose of inducing the formation to fracture at a desired point. INTRODUCTION Hydraulic jetting as a means of cleaning a formation during acidizing has been used for many years. The acid-jet gun was used to clean formation and for drilling cement from casing with acid. This tool was dropped to a seating ring installed on the tubing and could be retrieved by reverse circulation or wire line. In this process, the fluids were directed against the formation to clean and penetrate beyond the mud-damaged area. After the development of the hydraulic fracturing process, interest in jetting the formation with abrasive-laden fluid was renewed. The cutting action of abrasive fluid on pumping equipment, which is a well known problem, has been utilized to perforate and undercut casing, tubing and formation. In this process, surface areas are provided in the formation on which the frac- turing pressures may work to produce a fracture at the location desired. EQUIPMENT The tools used consist of bodies containing two, three or four jets in a single horizontal plane equally spaced around the circumference. The body is threaded to the end of a string of tubing and run into the well. In addition, an expendable tool is available that may be left in the hole after perforating and produced through until necessary to remove the tubing. The bottom of each tool is equipped with a ball-type back-pressure valve. The ball can be reversed to the surface and recovered. This allows reverse circulation so that loose sand which accumulated below the tool while jetting may be removed before the fracturing job. The present jetting tools are of such length that, when screwed together, the jets fall on 12-in. spacing. ANALYSIS OF THE PROBLEM Early work with nozzles indicated that hardened steel was not a suitable material for jets and that more durable material would be required. Ceramics were tried and found to be superior to steel but still too shortlived for most applications. Tungsten carbide, which was tried and found to be the best material available, is now being used for jet nozzles. Analysis of the problems presented by this process indicated that the following information was needed. 1. The effect of submergence on a jet stream and the effect of submergence on the cutting rate of a jet stream. 2. The cutting rate and depth of a jet stream in steel. 3. The cutting rate in various formations and point of diminishing returns. 4. Size of hole or slot cut in a pipe by a given jet. 5. Fluids and sands used. 6. The flow of various weight fluids through the jet nozzle and the discharge coefficients. 7. The type cut formed in the formation by the jet stream. 8. The stretch and contraction of tubing due to temperature and pressure. The cutting effect of a jet stream on a target in the atmosphere is rapid and spectacular as most of the

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

Jan 1, 1934

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962