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By J. O. Brittain, N. R. Adsit

A number of zinc bicrystal specimens with the grain boundary loaded in simple shear were plustically deformed in creep in a vacuum at 200°C and under an argon atmosphere at 350°C. The results indicated that the amount of grain boundary sliding at a given time was controlled by the slip in the grains and was proportional to the resolved shear stress on the slip plane. Curves of grain boundary sliding vs time were found to be cyclic with no regular periodicity. ALTHOUGH grain boundary sliding (G.B.S.) has been investigated in a number of different types of tests on various materials there is substantial disagreement on the interpretation of the various observations. Gifkins1 has presented a comprehensive review of the subject of G.B.S. and fracture. He reports that the activation energy for high-temperature creep is equal to that for volume self-diffusion and that pure metals show less tendency towards intercrystalline fracture than alloys. Pure metals show appreciably greater grain boundary migration than alloys, and both grain boundary migration and grain boundary sliding follow the same general trend in time as plastic deformation during creep.' While there have been a number of different mechanisms proposed to account for G.B.S., none of the models explains all the results. Since zinc has only one prominent slip system, it was hoped that experiments on G.B.S. in zinc bicrystals might enable us to separate the effect of grain boundary angle and the effect of matrix slip and thereby resolve at least one part of this complex phenomenon. EXPERIMENTAL PROCEDURE Bicrystals of pure zinc (99.99 pct) were grown by a Bridgeman technique in a furnace having a gradient of 20°C per in. The bicrystals were seeded to a desired orientation and grown in a split graphite mold which was 3/4 by 5/8 by 8 in. The mold was enclosed in a Pyrex tube and the tube was evacuated and then filled with a small amount of argon before it was placed in the furnace. The growth rates were 1/2 to I in. per hr for the bicrystals and 1/2 to 3 in. per hr for the single-crystal seeds. The longitudinal V notches served to hold the grain boundary in position during the growth process. A schematic rep- resentation of a specimen which had been cut with a jewelers saw from the bicrystals is shown in Fig. 1. All specimens of a series were cut from the same crystal, some of which were 7 in. in length. After specimen preparation the boundary was approximately 5/16 in. long and the V notches had a radius of 1/16 in. The boundaries were straight at a magnification of X100 with the exception of a few which had a gradual radius of curvature of greater than 3.2 in.-1. Laue back-reflection photograms were taken on the specimens to check the orientation of grains in the bicrystals. The method of relating the orientation of the two lattices is shown in Fig. 1, where 0 is the angle between normal to the boundary and the trace of the basal plane, is the angle in the boundary between the trace of the basal plane and a line parallel to the V notch, and x is the angle in the basal plane between the Burgers vector and the perpendicular to the grain boundary. After mechanical polishing the specimens were chemically polished.2 Subsequent to the polishing operation the specimens were encapsuled under a vacuum of better than 25 annealed at 340°C for 1 hr to remove the effects of this handling, and again chemically polished. Finally, fiduciary marks were scribed on the specimen using a micromanipulator. Creep tests, which were conducted in a modified Bausch apparatusS with the boundary loaded in simple shear, were run at a constant load (since the boundary area remained essentially constant this is approximately constant grain boundary stress). The temperature was controlled to ±1/4°C as measured on a semiprecision potentiometer with a calibrated thermocouple. The specimens were tested in a vacuum of better than 0.5 at 200°C and in purified argon at a pressure of 1/2 atm at 350°C. The op-

Jan 1, 1965

By Alan Morris

Season cracking of brass has received wide attention and there is a wealth of technical literature on the subject. Its causes arc fairly well understood and means for its prevention are inexpensive and effective, so that the frequency of failures from this source has diminished of recent years. But its sister phenomenon, the failure of annealed brass by reason of applied tensile stress plus a certain type of corrosion, has received less attention, though it has been responsible for occasional more or less troublesome cases of cracking of brass in service. The work described in the following pages was undertaken about two years ago to determine the relative resistance of various commercial brass mixtures to stress-corrosion cracking, and to learn something of the controlling factors. By stress-corrosion cracking we mean the cracking of brass free from internal stresses by reason of applied tensile stress and simultaneous attack by certain corrosive agents. Rogers,' in discussing a paper by Hatfield and Thirkell, says: " He had also applied a solution of mercuric salt to tensile test pieces of brass whilst they were under stress in the testing machine. At very moderate stresses such test pieces cracked, and very readily broke." Moore, Beckinsale and Mallinson2 subjected test pieces to simultaneous corrosion and tensile stress. In order to determine the minimum stress detectable in brass by the mercurous nitrate test, tensile samples were placed under stress and treated with mercurous nitrate solution. They found that brass stressed below a minimum did not crack. Dr. McAdam3 has investigated the effect of corrosion on the fatigue limit of brasses, among other materials. He directed a stream of either fresh or salt water against the specimen while it was undergoing fatigue test. The corrosion-fatigue limits thus determined may be considerably lower than the endurance limit without coincident corrosion. The exact

Jan 1, 1930

By J. O. Glanville, L. H. Haley

Ice frozen from a dilute chemical solution is mechanically weaker than ice frozen from pure water. This phenomenon is the basis of a practical method for reducing the strength of a mass of frozen coal. If a chemical additive is applied to moist coal prior to its shipment during freezing weather, the resulting frozen coal can be more easily broken than in the absence of the chemical additive. This greatly expedites the unloading and handling of coal during winter. There has been considerable research into the nature and mechanical strength of ice frozen from various solutions. In this paper, literature relating to this process as well as literature relating to the chemical treatment of coal and mineral particulates is reviewed. Some important articles are discussed and speculations made about the nature of the ice-weakening process. A laboratory evaluation of the effects of chemical additives on the mechanical strength of ice and frozen coal has been made. An apparatus designed for this purpose is described, and some results obtained with it are discussed.

Jan 1, 1983

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 3/16 or 1/4 in. The equipment, methods used, and accomplishments have been described in previous reports.1-7 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. 1. 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

Jan 1, 1941

By George L. Heath

It may at first appear doubtful that any further ideas can now come from such a well-trodden soil, when we consider that the ground of the subject has been so thoroughly gone over in many of its phases and that observations have been recorded in technical journals, ever since the days when Luckow and his cotemporaries brought the electrolytic deposition of pure copper to the position of an exact scientific method. Certain facts, however, which seem worthy of note, have come under the writer's observation during an extended use of the method in a large refinery, involving frequent tests of refined Lake and electrolytic copper, and thousands of assays of native copper concentrates and tailings. This work has required a careful study of the conditions suited to the assay of refined copper, and of ores and tailings— conditions which must be varied for each particular case to secure the best results. Especially is this true when we come to the exact determination of pure copper in the high-grade refined metal of the present day. Very slight traces of impurities (especially tellurium, selenium, bismuth, tin, arsenic and antimony) seriously injure the properties of copper, notably its electrical conductivity. The increasing demands of electrical science and construction lead to the conclusion that the analysis of all high-grade American coppers, at least, has become, and must be in future (in or-

Jan 1, 1898

By J. E. Russell

A brief review of the role of laboratory testing for characterization of host rocks for nuclear waste repositories is presented. Micro-and macro-scopic deformation mechanisms are discussed and constitutive laws being considered are reviewed. More information is available for rocksalt under expected repository conditions and, consequently, it receives more attention in our review. A brief comparison is made between the creep and constant strain-rate tests leading to a hypothesis that there may be systematic differences between steady-state conditions developed by the two test types. This difference is explained by considering specific power dissipated and work done on the sample. The hypothesis is tested against data for wet Westerly granite. In conclusion, progress has been made during the past five years but research and development should continue.

Jan 1, 1984

By R. S. Cartwright

TWO types of automatic drilling controls, the Halliburton and the Hild, are now available and are coming into more or less general use in deep drilling. The primary function of both is to maintain a safe limit of torque on the drill pipe, this being accomplished by automatically controlling the weight or pressure on the cutting tool. Neither type will necessarily increase drilling speed, but by permitting advantage to be taken of "breaks" in the hole higher average cutting speed may be maintained. The control is essentially a safety device, and should be considered as such. It is not the purpose of this paper to discuss the merits of drilling controls, although the advantages over manual feed at the brake drum are obvious, but rather to point out some of the limitations. The Halliburton Control The Halliburton control is designed to operate during drilling through the agency of the draw works. Automatic and constant control of the torque on the bit is governed by clutches on the control itself, and the line shaft to drum shaft drives on the draw works. In operations other than drilling the control is simply a jackshaft between prime mover and draw works. It is, of course, adaptable to any type of power. Because control of the torque on the bit is dependent on the various ratios or clutch combinations available on the Halliburton control and the draw works, it follows that there are certain limitations in points of control. Table 1 shows the possible ratios which can be obtained with the control and a popular type of three-speed draw works, it being assumed that the highest possible gear combination—the combination which when engaged will suspend the least amount of weight—has a value of 1.00. According to the table there are "blind spots" in the series. This is true particularly among the lowest ratios, which are most used to suspend the major part of the weight when great depths are reached. It will be noted that there is a difference of nearly three units in the value of the

Jan 1, 1929

By J. F. Radavich

Many heats of steel of low carbon value have been known to produce brittle pieces of steel. The brittleness is believed to be due to the impurities located within the grain boundaries. Such brittle steels have been examined with an optical microscope to ascertain the nature and the amount of the impurities present at the grain boundaries. Due to the relatively low resolving power of the optical microscope, the impurities are not visible in fine detail. The writer obtained some sheet steel and proceeded to determine the location of the impurities and to show the application of the electron microscope to the study of grain boundaries. One sample was known to be capable of becoming embrittled, whereas another sample was believed to be much less susceptible to embrittlement. Treatment of Specimens The specimens were embrittled by annealing above the A3 point under mildly oxidizing conditions. One piece of ingot iron could not withstand a 90" bend, whereas another piece of ingot iron was not affected and could withstand a 90" bend. The brittle piece was then annealed at a high temperature in a hydrogen atmosphere. The annealed ingot iron was termed cured and could withstand a 90" bend very easily. The three specimens examined will be designated as brittle, good. and cured in the discussion that follows. Procedure The sizes of the specimens were as follows: one piece of brittle ingot iron-3/8 by 35 in.; one piece of good ingot iron-96 by 1/8 in.; one piece of cured ingot iron-36 by 54 in. The specimens were too small to be polished by hand and therefore were mounted in bakelite. The polishing procedure was carried out in the conventional manner with the use of 1/0 through 3/0 papers, and the final polish was done with alumina on a billiard cloth. The specimens were then etched in a 4 pct solution of picral in alcohol, and then they were examined through an optical microscope. An area was chosen that showed distinct grain boundaries, and an effort was made to keep near this area when pulling the replicas REPLICA TECHNIQIJE The replica technique used in the preparation of the replicas for examination under the electron microscope is described in Electron Metallography.' It consists essentially of the following steps: 1. Obtaining a suitably etched specimen. 2. Applying a swab of ethylene di-chloride on the surface. 3. Applying a formvar solution on the surface. 4. Placing a screen on any desired spot. 5. Breathing on the fornivar layer. 6. Applying scotch tape on the screen and film. 7. Pulling the film and the screen up with the Scotch tape. 8. Separating the screen from the Scotch tape. This replica technique is very similar to the one described by Harker and Shaefer. However, with the added step, the percentage of replicas removed is very much higher regardless of the length of the time from the etching of the specimen to the actual pulling of the replica. The replicas were then shadow cast with manganese at a filament height to replica distance ratio of 1 1/2:7. This produced a very high contrast replica for use in the electron microscope. One of the dificulties encountered with this study was the restricted area of the specimen. The width of the specimens was the same as that of the 200 mesh nickel supporting screen. In order to increase the effective area, the screens were cut down as shown in Fig 1. The arrow indicates the direction in which the replica was pulled. This operation made it possible to obtain a large percentage of good replicas. Fig 3 shows an electron micrograph of a brittle piece of ingot iron and a grain boundary that was polished mechanically. The surface is very rough probably due to the incomplete removal of the flowed layer by the picral etchant. The grain boundary does show evidence of impurities. It was decided to electropolish the specimens to obtain a much smoother surface than the one obtained by mechanical polishing. ELECTROPOLISHING The specimens were cut in half to expose the metal on the back side. The exposed metal had sufficient area to make good electrical contact and electropolishing was carried out easily. The conditions for electropolishing were 0.9 amp, 35 volts, and 25 sec. in an electrolyte composed of 850 cc of ethyl alcohol, 100 cc distilled water, and 50 cc of perchloric acid. The polished specimens were then etched in the 4 pct picral solution for a shorter time than was necessary for

Jan 1, 1950

By Franz R. Dykstra, R. F. Tatnall

A ferroalloy is defined as: "An alloy of iron with some element other than carbon used as a vehicle for introducing such an element into the manufacture of steel. The element may alloy with the steel by solution or, as the carbide, -neutralize the harmful impurities, by combining with them and separating from the steel as flux or slag before solidification."a The most commonly used ferroalloys are: ferromanganese, ferrochrome, ferrosilicon, ferrovanadium, ferromolybdenum, ferronickel, ferrotungsten, ferrocolumbium, and ferrophosphorus. Concern here is with the sources and markets of the major metallic alloying elements. The discussion is further restricted to those - ferroalloy ores, the principal use of which is in the production of steel. Phosphorus, silicon, and tungsten, for example, are ferroalloys of some economic significance, but other uses dwarf their alloying applications. Thus, this discussion will deal with the ores of managanese, chromium, nickel, molybdenum, vanadium, and columbium. As shown in Table 14.1B.1 ferroalloys serve to- facilitate processing and impart to the finished steel such characteristics as tensile strength, ductility, low-temperature impact, hardenability, high-temperature strength, corrosion resistance, toughness, and abrasion resistance. In the steel-making process, ferroalloys may be added in the charge, in the molten bath near the end of the finishing period, in the ladle, or in the molds. Timing of the addition depends on the effect of the addition on the temperature of the molten metal, the formation and elimination of reaction products, and the protection of subsequent additions from oxidation. MANGANESE General Approximately 95% of the manganese ore sold is consumed by the steel industry, either as ferromanganese or as manganese metal. Manganese is the universal alloy, without which good steel cannot be made. It serves as a scavenger, removing phosphorus, sulfur and, to a degree, oxygen from the melt. As an alloying material it makes steel hard, tough, and resistant to wear. Approximately 6 kg of manganese is required for every ton of common steel produced by United States steelmaking practice. The remaining 5 % of the manganese ore consumed consists of special or so-called "chemical" ores, including high-grade pyrolusite ores, electrochemically reactive "battery ores," and a number of special varieties, as well as those otherwise regarded as "metallurgical ores."

Jan 1, 1976

By H. R. Deeth

NEPHELINE syenite is a sodium, potassium, aluminum silicate rock occurring in many countries. Large deposits have been investigated in Russia, India, and Norway and in the U. S., where it is known to occur in Arkansas, New Jersey, and Wisconsin. There are extensive areas containing nepheline syenite in south-central Ontario, a region surveyed in 1905 by Adams and Barlow. By 1925 considerable interest had developed in searching for aluminous raw materials that could be used by the glass industry. This finally focused attention on the nepheline syenite described by Adams and Barlow in 1910.1

Jan 11, 1957

The high-grade orebody at Miami was mined successively by top-slicing, shrinkage, stoping and under caving. The method described in this paper was developed to enable the low-grade orebody (36,000,000 tons assaying 1.06 per cent copper) to be mined at a low cost without further dilution of the grade. The method is clearly described and illustrated by drawings and photographs, and the original paper should be consulted as it is impracticable to abstract it, beyond noting that the mining cost is just under 40 cents per ton and the average grade of ore now being produced yields less copper than the mill tailing of 1915, the tons mined per day having increased from 4000 to 18,000 in the same period. Vertical and Incline Shaft Sinking at North Star Mine By Arthur B. Foote, Grass Valley, Calif. (Tech. Pub. No. 324: Class A. Metal Mining, No. 36) THE main shaft of the North Star mine is an inclined one following the main vein at an average dip of 26 deg., a vertical shaft intersects it at the 4000-ft. (incline) level, the incline continuing to the 6300-ft. level. At this point the vein was found to give out and a new vein, called the No. 1, was found to dip in exactly the opposite direction.

Jan 1, 1930

By Peter J. Lean

The introduction oE computer control in the grinding circuit of the New Broken Hill Consolidated Limited concentrator in the early 1970's gave smoother operation at optimum performance. The ore feedrate and water additions to the grinding circuit were controlled to operate each of the ball mill/ rake classifier grinding units at the upper limit of the circulating load while classifier overflow density was maintained to give a product size and pulp density suitable for flotation. An incremental expansion of the concentrator in 1981-82 included the installation of hydrocyclones in closed circuit with three of the four ball mills. Without the rake classifiers in circuit the previous control strategy could not be used and the complex interaction of hydrocyclone performance characteristics when classifying coarse grained sulphide ore resulted in the over-grinding of the lead mineral galena. Testwork aimed at optimising grinding circuit performance recognised the enhanced tendency of higher specific gravity minerals to report to the cyclone underflow. The data has been evaluated on an individual mineral basis and then used to develop a model For grinding circuit control. The development of the model which uses inputs of ore feedrate, metal content of the Feed and slurry density of the cyclone overflow to predict the size of the minerals in the grinding circuit product is described and model predictions are compared with plant performance.

Jan 1, 1984

By Joseph A. Holmes, Henry Kreisinger

At the Mining Experiment Station of the U. S. Geological Survey, in Pittsburg, an investigation of the process of combustion is being carried on in a specially-designed furnace having an unusually long combustion-chamber. This work is conducted by a con~mittee consisti~lg of 11. Kreisinger, mechanical engineer; Dr. J. C. W. Frazer, chemist; and Dr..J. K. Clement, physicist. The problem, essentially one of physical chemistry, is estremely interesting to all who are concerned in the burning of coal or the construction of furnaces. The main object of these experiments is to ascertain the relation between the amount of' the volatile combustible driven from the coal and the combustion-spaces necessary to burn it completely. Our best steam-coals vary from 15 to 45 per cent. in volatile matter and from 40 to 75 per cent. of fixed combtistible. The greater part of the latter is burned on the grate: but the volatile combustible leaves the freshly-charsed coal and must be burned in the combustion-space. If this space is not large enough, the volatile combustible mill leave the furnace only partly burnecl, and the result will be a considerable heat-loss and a smoky stack. Strictly speaking, the factor which determines the completeness of combustion of the volatile matter, after it has been mixed with a certain amount of air, is the length of time the mixture is allowed to remain in the combustion-space; but this length of time depends on the extent of the space itself. Let us suppose, for instance, that, when a given coal is burned at a certain standard rate, the volume of the volatile combustible driven oft' per second is 10 cu. ft. Adding, say, 10 cu. ft. of air, the volume of the resulting burning mixture is increased to 20 cu. ft. If the combustion-space is 30 cu. ft., the burning mixture will stay in it,

Jan 1, 1911

By Carl Thieme

INDUSTRIAL specialization has rapidly created a demand for new and better alloys. A more thorough understanding of the requirements of specific industries and the discovery of processes by which it has been made possible to utilize certain metallic elements in larger quantities, together with greater purity in most virgin metals, has resulted in a great increase in the number and variety of alloys. This increase in the number of elements entering into non-ferrous alloy manufacture has increased the contamination in secondary metals, as received by the smelter. In order to successfully refine scrap of a much more complex nature it has been necessary for the smelter to install new equipment and to constantly search for new methods of refining as well as to improve the methods already in use. In some instances it is largely responsible for specialization in the secondary metal industry. It is usually necessary to remove the contaminating impurities in scrap or eliminate to a degree not objectionable, no matter how introduced. In order to know what metals or elements are of an objectionable nature, the smelter must make a study of the effect of single elements and combinations of elements on many of the physical and mechanical properties, such as strength, ductility, color, hardness, casting soundness, etc. The smelter of secondary metals must be able to utilize scrap materials of all kinds, for, sooner or later, most fabricated metal parts and the waste products formed during the process of manufacture find their way to the smelter. In addition, the smelter, in contracting for salvaged material from the producer, gets some undesirable and unusual materials. The value of secondary metals and the importance of their recovery has increased in recent years and it is no longer sufficient to recover the base metal only, such as copper from copper-bearing material, but it inessential that other elements present be recovered and converted into useful form.

Jan 1, 1928

Minerals: When man first picked up an appropriately shaped stone and fastened it to a stick of wood to create a primitive axe or hammer he started down the long road of mineral dependency that has continued until today (Fig. 2). Though he did not realize it, that man and his stone axe created an extremely simple form of mineral economy. The struggle against extinction from that day has been fought with minerals. In addition to providing himself with a means to fight for survival, he also exhibited an increase in intelligence. As his curiosity was stimulated, his ability increased to provide himself with better mineral and metal weapons and tools. Today, when we examine the artifacts of past civilizations, we measure the degree of development that had been attained by the variety of metals and minerals possessed and how they were used. The metals employed are so characteristic of the level of intelligence that we have named the various stages of human progress by the metals that were most commonly utilized. Thus, mall went through the Stone Age, the 13ronze Age, the Iron Age and now has reached the Steel Age. The first period of mineral development, the Stone 4ge, began during late Pliocene time. In this first mineral age, prehistoric man began to shape stones by chip- ping off small pieces until the stone assumed the crude form he wanted. As his intelligence increased, he progressed to finer workmanship and turned out finished spear heads and barbed arrows. Throughout this very

Jan 1, 1950

By B. Wilshire, W. J. Evans

The high-temperature creep properties of nickel, zinc, and iron have been determined over a range of stresses. The creep strain, E, was found to vary with time, t, as: where e0 is the instantaneous strain on loading, ET the total transient creep strain, $ the steady creep rate, and m is a constant relating to the rate of exhaustion of transient creep. Deviations from this relationship occurred during the initial 10 to 15 pct of the transient stage. These deviations result in the initial creep rate, go, calculated as (m . ET + es), being considerably lower than those obtained by measurements on the creep curve. For all materials, the initial creep rate, the constant m, and the duration of transient creep are all related to the steady creep rate. These relationships suggest that transient and steady-state creep should not be regarded as distinct stages.

Jan 1, 1969

By R. B. Snow

Inclusions revealed by the ultrasonic inspection of forgings, slabs, and blooms cause costly diversion or rejection of the product. Most of those inclusions are so large that they should have floated out of the liquid steel soon after teeming and been removed when the top discard was taken from the ingot. To investigate the source of the relatively large inclusions found in the body portions of ingots, a large forging ingot was examined from top to bottom along the centerline, and special studies were made of open-hearth and BOP ingots. A study of the inclusion distribution in the as-cast 134-inch-diameter forging ingot revealed only a few inclusions larger than 15 microns in the body of the ingot. Larger inclusions may be formed by entrapment of rising inclusions in large falling dendrites rather than by the precipitation and agglomeration of oxides from the liquid steel-dendrite interface during solidification. The original top crust of the ingot investigated broke away from the hot top and sank to the bottom during the solidification process, as indicated by entrapped inclusions found in a band 12-1/2 inches above the stool. A change in the hot-top insulation practice on subsequent ingots to insure the integrity of the top crust has produced clean ingots. A ZrO2 tracer was added to the hot-topping compound and to the top surface of open-hearth and BOP ingots after teeming. The tracer was found in large inclusions in slabs and blooms from these ingots. Large inclusions in the body of ingots appear to be related to disturbances of the natural freezing and shrinkage processes in the hot- top region of the ingot.

Jan 1, 1972

By Don M. Jackson, Robert W. Howard

Techniques for the epilaxial growth of single -crystal silicon carbide films on silicon were developed. The vapor-phase decomposition and bydrogen reduction of silicon tetrachloride (SiC14) and Propane (C3H8) resulted in clear films of silicon carbide, lip to seveval microns in thickness. The growth took place in a horizontal . silicon epilaxial reactor at 1100°C (pyrometer) at a rate of- 3000Å per minute. Electron diffraction and X-ray diffraction studies demonstrated that the films were single-cyrstal, ß -phase, or cubic silicon carbide. SiO2 film were used to mask areas of the silicon sur-lace in order that the silicon carbide might be grown in controlled geometries. Both n- and p-type films were grown on p-type silicon waters.. Heavily doped silicon films of the same conductivity type as the silicon carbide films were deposited over the silicon carbide in order to affect better probe contact to the structures. when n-type silicon carbide mesas were grown on p-type silicon substrates the de vollage-current relationships between films and substrates were that of junction diodes. These diodes showed a sensitivity to while light ill that the incident light increased forward- and reverse-satro,ation currents, P-type silicon carbide mesas grown on p-type silicon were ohmic rather than rectifying in their voltage -current relationship. No conclusions could he reached concerning heterojunc-tiou rectification in the structure. SILICON carbide is a semiconductor with many interesting properties. It decomposes at temperatures above 2200°C.1 It occurs in two general crys-tallographic forms—hexagonal (a Sic) and cubic (ß Sic)—with the cubic form having a forbidden-gap energy of 2.32 ev and the hexagonal form (specifically the 6H polytype) a gap energy of 2.86 ev.3 It behaves as an extrinsic semiconductor at temperatures approaching 5003C. It has been shown to have a high resistance to radiation damage4 and p-n junctions formed in Sic have been shown to radiate visible light under forward- or reverse-bias conditions. Epitaxial silicon carbide on silicon carbide has been successfully grown through the use of a variety of techniques, such as gaseous cracking of SiCL4 and CC4, nearly all of which require a deposition temperature above 1500°C.6 This paper will cover very recent work on the gas-phase deposition of highly ordered films of silicon carbide on high-quality silicon single-crystal substrates. The films have been shown to ex- hibit junction-rectification properties when geometrically isolated regions are electrically biased with reference to the silicon substrate. There will be no discussion of the mechanism of heterojunction rectification, but the methods of film fabrication, geometry control, and structural evaluations will be covered in detail. Electron diffraction, X-ray diffraction, and diode electrical properties were used to characterize the films and the junctions. GAS-PHASE DEPOSITION OF Sic The techniques for the deposition of silicon carbide films were a logical outgrowth of the standard silicon epitaxial process. The major premise followed was that, for any film to nucleate in an ordered fashion where there is considerable mismatch in lattice parameters (in this case 22 pct), an extremely clean, damage-free substrate surface must be presented to the gas stream. Thus a standard gas-phase HCl etching step was used to prepare the substrates for growth. A minimum of 5 µ of substrate-surface material was removed prior to the deposition of Sic overgrowth films. The techniques used for growing silicon carbide films were those of growing silicon alone, with the added injection of a hydrocarbon gas into the hydrogen and silicon tetrachloride gas stream. The hydrocarbon gases used thus far have been research-grade (99.99 pct) methane (CH4) and propane (C3H8). Propane ultimately gave the best results. The gas flows were controlled through a panel shown schematically in Fig. 1. A hydrogen main stream of 30 liters per min passed through the horizontal quartz-tube epitaxial reactor, while SiC14, C3H8, HC1, and doping gases were injected as side streams. The

Jan 1, 1965

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965

By N. Lilienberg

During the past fen- years, the requirements for steel have been raised so high that soundness is more important than ever before. The old practice mas to make steel ingots of suffciently large sections to permit a considerable reduction of area in rolling and hammering to a given size, relying on the fact that by such rolling and hammering all cavities will be squeezed together and practically eliminated. The finished sizes, if found by inspection of the surface to be faultless, were therefore pronounced to be sound. But when such steel is " worked up," the manufacturer is surprised and disappointed to find that it splits, or that streaks and seams make the product unmarketable. Large sections, such as rails, beams or heavy forgings, may, within certain limits, be sufficiently strong, even if the sides of the cavities are only squeezed, and not welded, together. But it is well known that, in the interior of heavy articles, under certain conditions, forging may develop small streaks into large cavities. Small sections, steel for ordnauce and tubes, and numberless articles in the tool-trade, always show up the defects. It may be doubted whether cavities in steel ingots can ever be completely welded. The old theory is, that the silver-clear blow-holes, without the blue oxide, can be welded by suffcient working. They are, however, not empty, but are filled with carbonic oxide. It is admitted that the " blue " cavities, resulting from air mechanically drawn down into the mold during the casting, can never be welded, because the oxide does not melt, and there would be no escape for it if it did. The only way in which steel can be made satisfactory for the above-named particular purposes is by having it " dead molten." But then the trouble of piping is encountered. As is well known, a pipe is the result of the contraction of the liquid interior after the surface of the ingot has become solid by contact with the mold. When this contraction is partly

Jan 1, 1907