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Geostatistics originated as an application of a classical statistical concept, multivariate linear regression, to the solution of a practical problem, estimation of reserves in the South African gold mines. In this respect, geostatistics should only be considered as one statistical method among many that can be used to evaluate mineral deposits. R.F. Shurtz has studied possible applications of power spectrum analysis to the same problem, and these studies may result in future improvements over the presently accepted geostatistical methodology. The intention of R.F. Shurtz's paper, as stated by the author, is to "relate geostatistical doctrine to classical statistical and mathematical concepts." However, in this comparison the "geostatistical doctrine" appears to include only the simplest among the geostatistical concepts advocated by G. Matheron, while "classical statistical and mathematical concepts" are limited nearly exclusively to power spectrum analysis. The author attempts to compare the two methods, and to prove the theoretical superiority of power spectrum analysis. Unfortunately, a number of errors and incorrect statements are made concerning both the theory and application of geostatistics, which invalidate the comparison and the conclusions drawn from it. The errors made in this comparison are understandable since few scientists can claim to have expertise in two theories as diverse as those compared here. In many respects, this paper is reminiscent of polemics which occurred 15 to 20 years ago when geostatistics and trend surface analysis were compared. Each method has its own merit and limitations, and none can claim absolute superiority. The most misleading statements found in R.F. Shurtz's paper are: The definition of the semivariogram given on page 1923 is incorrect. If the maximum difference between two assays is 1, the maximum value of the semivariogram is not 1, as stated, but 0.5. The comparison of geostatistics and linear regression made in the section entitled "Insufficiency of Classical Statistics?" is not valid. The semivariogram of the sample values given in Table 1 (page 1919) has a parabolic shape indicative of a linear drift. When such a semivariogram is observed, the simplest method of geostatistical estimation (linear kriging with unknown mean) is not applicable. Universal kriging must be used that takes trends into account. On page 1921 it is stated that the use of trends "is officially disparaged in geostatistics." Again on page 1924 mention is made to "Matheron's commitment to random process (intrinsic) models and his present categorical rejection of deterministic (trend) models for mineral deposit evaluation." Indeed, from articles published by geostatisticians in the 1960s one could infer that geostatistical methods are not compatible with the presence of trends. However, even the simplest

Jan 1, 1984

By F. R. Cattoir, R. W. Kimball, C. T. Anderson, V. V. Donaldson

THIS paper is the second of a series on the effect of various elements on hot-working characteristics of Fe-C alloys to be issued by this laboratory. The investigations being conducted at the Ferroalloy Research Branch of the U.S. Bureau of Mines, Redding, Calif., involve fundamental research on the effects of various alloying materials and impurities on the physical properties of high purity Fe-C alloys. This paper deals with the determination of the limit of forgeability of steels containing varying amounts of manganese and sulphur. A paper discussing the hot-working characteristics and the physical properties of the forgeable alloys is being prepared. One of the principal impurities in all steels is sulphur.. The phenomenon, hot-shortness, commonly attributed to sulphur, has long been a source of expense and inconvenience to both the maker and user of steels. In steelmaking practice, this effect of sulphur has been overcome by the addition of manganese which, apparently, acts as a desulphurizer. Manganese is also used as a deoxidizer and alloying material. The critical and strategic position of man- ganese gives added importance to research which may contribute to its conservation and more effective utilization. It is not the purpose or intention in the present paper to give any explanation of the mechanism of either hot-shortness or its prevention but rather to report the results of forging high purity Fe-C alloys of the range of compositions near the limit of hot-forgeability. Temperatures for each phase of reduction were duplicated within 20" to 30°F for all tests. The starting material was sponge iron, which, after melting and purification, gave a high purity iron containing about 0.001 pct each of silicon and phosphorus. Scrap iron was not considered suitable because of its high percentage of contaminants and wide variation in analyses. The sponge iron was melted and refined for melting stock in a three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating as described in the preceding paper. Additives were carefully selected to avoid addition of contaminants. The sulphur was added as resublimed flowers of sulphur or purified roll sulphur of analytical grade. The manganese used was dehydrogenated high purity electrolytic material produced by the Bureau of Mines plant at Boulder City, Nev. High purity aluminum in the form of wire was used for deoxidation. The limestone was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2,3.0; and P2O5, 0.014.

Jan 1, 1955

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neill1 observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in intergranular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle' in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. [ ] In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1941

By R. V. Norris

IRving Ariel Stearns died at his home, 60 South River St., Wilkes-Barre, Pa., on Tuesday morning, Oct. 5, 1920, of pneumonia, after an illness of about a month. In his death, the Wyoming Valley loses one oflits most eminent and best loved citizens, and the loss of so strong a participant in the activities of the Valley will leave a gap most difficult to fill. Despite his more than three score and fifteen years, Mr. Stearns, at the time of his death, was president of the Wilkes-Barre City Hospital, Wyoming National Bank, and the Wyoming Historical and Geological Society, chairman of the Board of the Vulcan Iron Works, and a director of the Spring Brook Water Supply Co., and of the Wilkes-Barre Lace Manufacturing Co. Mr. Stearns came of New England stock, a descendant in the eighth generation of Charles Stearns who was admitted freeman in Watertown in 1646. Irving Ariel Stearns was born Sept. 12, 1845, in Rushville, N. Y., a son of George W. and Miranda (Tufts) Stearns. He was graduated from the Rensselaer Polytechnic Institute of Troy, N. Y., in the celebrated Class of 1868. After graduation, he was assistant professor of chemistry in charge of the analytical laboratory for a year, then went to Wilkes-Barre in 1869, as engineer in the office of R. P. Rothwell, at that time the leading mining engineer of the region. From 1871 to 1872, he was superintendent of the McNeal Coal & Iron Co. of Schuylkill County, Pa. and in 1872 succeeded to Mr. Rothwell's business when the latter became editor of the Engineering & Mining Journal of New York. From 1872 to 1885, Mr. stearns was in private practice as a mining engineer, handling a great amount of business in the anthracite region, including the building of the bridges at Shickshinny and Pittston, and the surveying and mapping of many of the individually operated mines. His practice extended throughout the country, with numerous examinations and reports upon mining properties in Pennsylvania, Virginia, West Virginia, Arkansas, Colorado, California, Wyoming, Idaho and Utah; he was responsible for the design and execution of the Lehigh Valley Railroad Co.'s great Tifft Farm improvements at Buffalo, N. Y. including canals, docks, coal stocking plant, etc. He was commissioned Quartermaster of the Ninth Regiment, N. G. P., March 29, 1880, was promoted to Major on May 15, 1884, and resigned Apr. 1, 1885. He always retained his interest in the National Guard and was trustee and president of the Ninth Regiment Armory Association.

Jan 1, 1922

By Charles R. L. Oder, Howard W. Miller

Approximately 5000 tons of zinc ore a day was mined during 1943 in the Mascot-Jefferson City district in East Tennessee. This ore came from the Kingsport formation, a part of the Knox dolomite, of Ordovician age. The Kings-port is composed of 350 to 400 ft. of limestone and dolomite. Thin cherts, sandy layers and shales are numerous. Frequently, the limestones are altered to crystalline dolomite. The Kingsport is divisible into four main lithologic zones. These divisions are illustrated in an accompanying table, which gives detailed sections of the ore-bearing beds as found in the mines and shows the exact positions of the various ore zones within the formation. Key beds are described and the practical applications of stratigraphy in mapping, prospecting and mining are discussed. Introduction The Mascot-Jefferson City zinc district is in Knox and Jefferson Counties, in the Great Valley of East Tennessee. It extends from Mascot, I3 miles northeast of Knoxville, to Jefferson City, about 30 miles northeast of that city. The American Zinc Company of Tennessee is producing from five mines in the district, in which it has operated for more than 30 years. The only other important producer is the Universal Exploration Co. The approximate daily production of the district in 1943 was 5000 tons of sulphide ore, grading from 2.5 to 6 per cent zinc. Small amounts of oxidized ore are mined intermittently. The Knox dolomite has been described by various geologists,'-' but no detailed descriptions of the rock sections revealed by mining have been published. Rock units are not conspicuously different and careful study is required to distinguish them. Nevertheless, familiarity with the stratigraphy of the mineralized zones is essential to successful exploration and extraction of the ores; therefore the purpose of this paper is to give detailed stratigraphic sections as measured in the mines, to discuss their important features and to show their relationship to the stratigraphy of the district. Generalized Section Table I gives the most characteristic general features of the major stratigraphic units. The formation names given in parenthesis are locally and widely used terms, the correlations of which are not necessarily established. For this reason they are put in quotation marks and are replaced by more restricted terms. The names "Mascot" and "Kingsport" were adopted from local towns. They were chosen jointly by Josiah Bridge, of the Federal Geological Survey, and the senior author for use in their separate unpublished manuscripts describing the Knox dolomite in East Tennessee. Descriptions of the type sections may soon be published. The name "Longview" was first applied by Butts6 in Alabama.

Jan 1, 1949

By C. E. Berry

NATURAL stone or manufactured porcelain pebbles are used as the grinding elements in pebble mills and the mills are lined with stone or porcelain blocks. Steel balls usually form the grinding medium in ball mills, and the mills may he lined with steel. Pebble mills are used to avoid contamination by metal of the material being ground, to avoid rapid wear due to corrosion, and for other specialized reasons. Belgian silex (silica) blocks formerly were used widely for lining pebble mills, because of their good resistance to wear, light color, and low cost, but the importation of these blocks was suspended early in the war. The stocks of Belgian silex diminished so rapidly that it was found desirable to compare the properties of a number of domestic substitutes for use in critical operations. Accordingly, a study was made to determine the best substitutes for fine grinding of white pigment and for certain heavy-chemical process work such as the disintegration of phosphate rock in weak phosphoric acid solution. A comprehensive survey of substitute lining materials was not contemplated. It was stipulated at the beginning of the investigation that only materials on the market, available in large quantities, would be tested and that these should be reasonable substitutes from a wear-resistance viewpoint as determined from known physical characteristics. Marble and limestone, for example, could be eliminated immediately. Quartzite, granite and porcelain were selected as likely substitutes for Belgian silex and were subjected to quality tests. MATERIALS TESTED I. Belgian Silex.-Sample blocks of a standard grade were taken from crates in which they had been imported. The stone was light gray in color and contained inclusions of small clusters of quartz crystals as well as light colored portions that might be calcite. This was a siliceous rock which appeared to be of igneous origin. 2. Quartzite.-Samples of quartzite were obtained from a quarry in Minnesota. The blocks exhibited a crystalline fracture. The stone was pink in color and composed of fine quartz crystals bound together with a siliceous cement. 3. Granite A was a fine-grained granite quarried in South Carolina. 4. Granite B was coarse-grained granite quarried in South Carolina. 5. Granite C was a coarse-grained granite quarried in North Carolina. 6. Porcelain A.-Sample blocks of the pebble-mill lining material were obtained direct from the manufacturer. It was white in color and of lower specific gravity than the natural materials. It did not have a crystalline structure. 7. Porcelain B.-Sample pebble-mill lining blocks of the porcelain were received direct from the manufacturer. It was white

Jan 1, 1946

By E. S. Wheeler

The conversion plant of the Clirnax Molybdenum Co. is at Langeloth, Washington . County, Pennsylvania, approximately 30 miles west of Pittsburgh. The molybdenite concentrates converted originate in the company's mine and mill at Climax, Co1orado.l They are delivered to the Langeloth plant by rail packed in 175-lb. bags. War production of concentrates at the mill started in 1918 but it was not until about 1920 that any peacetime uses of the metal began to develop. Early conversion of Climax concentrates was mainly into ferromolybden um, produced for the company by a custom smelter. Chronology of Plant Development In 1924 a small hand-rabbled roaster was built at Langeloth, the roasted concentrates being used principally in the production of calcium molybdate by a conventional wet method. The size of the original plant is indicated by the fact that during 1925 about 400,000 lb. of molybdenum was converted. In 1925-1926, a multiple-hearth roaster was erected (12-ft. 0.d. 8-hearth Nichols-Herreshoff); also the first experimental ferromolybdenum was produced at Langeloth. At this time sa.1cium molybdate was produced in the furnace by a process to be described. With continued interest in and increased use of molybdenum, it was necessary to arrange for enlargement of plant facilities. Although only one 12-hearth 16-ft. 0.d. roaster was erected at this time (1929), plans were prepared for a duplicate unit, which was completed in 193 5, giving a potential roasting capacity of some 16,000 lb. Mo per day under the then prevailing roasting practice. Shortly after this second unit had gone into production, increased demand overtaxed the plant, and as a result two 12-hearth 18-ft. 0.d. roasters were placed in operation in 1936 and 1937. This gave the plant a potential roasting capacity of 40,000 to 50,000 lb. Mo per day, and necessitated major changes in auxiliary handling equipment as well as improved facilities for producing ferromolybdenum. Following the introduction (1938) of a new product—molybdic oxide briquets— and because of the constantly growing demand for molybdenum, plant facilities were again enlarged in 1940 and 1941 by the erection of two 16-hearth 18-ft. 0.d. roasters. These two new units, along with a change in roasting practice, brought the potential roasting capacity to 150,ooo to 190,000 Ib. Mo per day, based on about 15 lb. per sq. ft. of hearth area. Other departments of the plant have necessarily grown, until today the plant is modern throughout and completely mechanized, with equipment geared to produce marketable products as follows:

Jan 1, 1944

By Howard W. Miller, Charles R. L. Oder

Approximately 5000 tons of zinc ore a day was mined during 1943 in the Mascot-Jefferson City district in East Tennessee. This ore came from the Kingsport formation, a part of the Knox dolomite, of Ordovician age. The Kings-port is composed of 350 to 400 ft. of limestone and dolomite. Thin cherts, sandy layers and shales are numerous. Frequently, the limestones are altered to crystalline dolomite. The Kingsport is divisible into four main lithologic zones. These divisions are illustrated in an accompanying table, which gives detailed sections of the ore-bearing beds as found in the mines and shows the exact positions of the various ore zones within the formation. Key beds are described and the practical applications of stratigraphy in mapping, prospecting and mining are discussed. Introduction The Mascot-Jefferson City zinc district is in Knox and Jefferson Counties, in the Great Valley of East Tennessee. It extends from Mascot, I3 miles northeast of Knoxville, to Jefferson City, about 30 miles northeast of that city. The American Zinc Company of Tennessee is producing from five mines in the district, in which it has operated for more than 30 years. The only other important producer is the Universal Exploration Co. The approximate daily production of the district in 1943 was 5000 tons of sulphide ore, grading from 2.5 to 6 per cent zinc. Small amounts of oxidized ore are mined intermittently. The Knox dolomite has been described by various geologists,'-' but no detailed descriptions of the rock sections revealed by mining have been published. Rock units are not conspicuously different and careful study is required to distinguish them. Nevertheless, familiarity with the stratigraphy of the mineralized zones is essential to successful exploration and extraction of the ores; therefore the purpose of this paper is to give detailed stratigraphic sections as measured in the mines, to discuss their important features and to show their relationship to the stratigraphy of the district. Generalized Section Table I gives the most characteristic general features of the major stratigraphic units. The formation names given in parenthesis are locally and widely used terms, the correlations of which are not necessarily established. For this reason they are put in quotation marks and are replaced by more restricted terms. The names "Mascot" and "Kingsport" were adopted from local towns. They were chosen jointly by Josiah Bridge, of the Federal Geological Survey, and the senior author for use in their separate unpublished manuscripts describing the Knox dolomite in East Tennessee. Descriptions of the type sections may soon be published. The name "Longview" was first applied by Butts6 in Alabama.

Jan 1, 1949

By R. D. Barer, M. B. Bever

Age hardening alloys are quenched from the solution treatment to room temperature in order to retain a supersaturated solid solution. Some alloys age "naturally" in this condition but in most alloys aging is induced "artificially" by heating to intermediate temperatures. Cold working of the supersaturated solid solution accelerates the aging process and quenching strains have the same effect. The investigation reported here is a study of the progress of aging in specimens quenched directly from the solution treatment to various aging temperatures. This procedure reduces the temperature interval of quenching and the resulting quenching stresses. It also eliminates any changes which would take place in the undercooled sample at room temperature prior to aging at an elevated temperature. Isothermal aging is thus approached and its kinetics may be studied. An aluminum-copper and an aluminum-silicon alloy were chosen for this investigation. The aging mechanism of aluminum-copper alloys is complex while the aging of aluminum-silicon alloys is nearly ideal. As standards of comparison for the samples directly quenched to the aging temperature, specimens were also age hardened by the usual procedure in which solution treated samples are first quenched to room temperature and then reheated to the aging temperature. Review of Previous Work The mechanism of age hardening has been the subject of a controversy which has ranged from the theory of outright precipitation of an equilibrium phase to theories based on subtle changes occurring in the matrix prior to precipitation. A detailed critical review of the literature up to 1939 is available1 and contributions to the general theory of age hardening continue to be made.2,3 Age hardening, whatever its mechanism, involves the nucleation of a second phase within a supersaturated solid solution. Theoretical considerations4,5 indicate that the rate of nucleation reaches a maximum at an intermediate temperature below the temperature at which supersaturation sets in. Studies of precipitation at various subcritical temperatures have demonstrated that the largest property changes in a given time occur at such intermediate temperatures.6,7,8 The precipitation of a phase from supersaturated solid solution is accelerated by strains which may result from quenching or cold work. Phillips and Brick9 established that quenching strains are an essential condition for the age hardening of aluminum-copper alloys at room temperature, at least for aging periods of less than 30 days. They also found that on aging at 300°C the hardness increased faster and reached a higher maximum after quenching into water than after quenching directly to the aging temperatures. Fink and Smith10 observed preferential precipitation on slip bands and grain boundaries in aluminum-

Jan 1, 1950

By Charles C. Hawes

DETERMINATION OF SILICA OXIDE iron ores usually are found in intimate association with silica and phosphorus compounds. Their quantitative separation and purification sometimes present difficult problems to the chemist. Silicic acids may represent various degrees of dehydration. They are exceedingly weak, but combine with metallic acids and form some of the most stable oxides in nature, the silicates. When iron ores are treated with hydrochloric acid, they yield practically all their iron. However, apart from rare exceptions, varying amounts of insoluble residues of silica, alumina, lime, magnesia and compounds of phosphorus, sulphur, titanium, chromium and others will be left. If the oxides of silicon, aluminum and titanium are present in small quantities, the insoluble residue is generally very small, but the presence of these oxides more usual in larger quantities. Therefore, only a special treatment can break the bond between these elements. Ore Residues Acids remove the soluble constituent of the ore, leaving the insoluble residue, which chemically is rock or gangue and must be treated accordingly. Alkali carbonates are used frequently to break up the residue, but other fluxes have also been recommended, such as a number of lead and boron salts. The introduction of these salts, which offers certain advantages, requires, however, their removal before the other constituents can be analyzed, and this elimination is sometimes difficult. Usually in quantitative analysis silicates are dissociated by fusing them in a platinum crucible with sodium carbonate, thereby forming sodium silicate, Na2SiO3, sodium aluminate, Na2A1204, sodium titanate, Na2TiOs, and carbonates of other elements. All the carbonates are soluble in hydrochloric acid, but also some silicic acid is formed that must be rendered insoluble. To this end the solution is evaporated several times, as the first evaporation still leaves as much as 5 per cent of the silica soluble. Even after a number of evaporations, minute quantities of silica may be found with the iron and alumina present. Perchloric Acid as an Agent for Dehydrating Silicic Acid Perchloric acid, HCI04, (60 per cent), has been used for years as a solvent, but few chemists have used it to dehydrate silica. It is derived from anhydrous perchloric C1207, which is most unstable and dangerous. Perchloric acid is a strong oxidizing agent, which boils at 203°C. It is more effective in rendering silica insoluble than any other known agent, and most rapid in action. After perchloric acid is added to a mixture containing silicic acid, the resultant solution is

Jan 1, 1945

By C. G. Dunn, J. L. Walter

The c/laracterzstics of cube-oriented nuclei ard other matrix grains that are associated with secondary, recrystallization to the cube texture in high-purity silicon iron were investigated by me-tallographic and X-ray methods. The results show that the structure consists of relatively perfect grains of average diameter between one and two times the sheet thickness ad that the texture has a moderately strong (110) [001] component and a weak (100) [001] component. The results also indicate that matrix stability results from the two-dimensional nuture of the graitzs and that cube-orzented nuclei are neither more Perfect nor larger grains than other matrix grains but have a preferred [001] direction in the rolling direction and have a more effective driving force for growth than other grains because of a low (100) surface energy. THE structures and textures of fine-grained rnatrices determine to a large extent the kinds of secondary recrystallization textures that form on annealing. The understanding of secondary recrystallization processes therefore depends on adequate information about the initial matrices. Matrices usually have three characteristics: 1) they consist of fine-grained primary recrystallization structures, 2) the fine-grained structures are stable toward normal grain growth, and 3) they contain secondary recrystallization nuclei. Stability toward normal grain growth may be due to either a strong single orientation texture (texture inhibition)' or a dispersed second phase (dispersed phase inhibition).2"4 If normal grain growth is not inhibited by either of these two factors, it nevertheless stops when the average grain size is between one and two times the sheet thick- ness.5 This thickness effect satisfies one of the characteristics of a matrix for secondary recrystallization. Its importance in the development of the cube texture in high-purity silicon iron by secondary recrystallization was pointed out by the authors in a recent paper on tertiary recrystallization7 and will be discussed further in the present paper. Assmus, Detert, and he8 have provided some information on a matrix for secondary recrystallization to the cube texture in silicon iron. They found a (110)[001] or Goss texture with enough spread about the rolling direction to include a small amount of the (100)[00l] orientation. The distribution of the [00l] directions was strongest parallel to the rolling direction for both (100) primaries and cube secondaries. These authors found no correlation between size of a matrix grain and orientation and concluded that some property other than size must be the distinguishing characteristic of the cube-oriented nucleus. No consideration was given, it

Jan 1, 1961

By A. U. Seybolt, V. A. Phillips

Binary iron alloys containing 1 pct of Al, Cr, Mn, Mo, Si, Ti, or V, and 0.4 pct C, 1 pct Cr steels with and without 1.2 pct A1 or 2.0 pct Ti additions, were ion-nilrided at 550° to 600° in N-H mixtures. Nitriding increased the inicrohardne ss of all the binary alloys except those containing manganese or molybdenutn, and also hardened the heat-treated steels if aluminum or titanium urns present. Transmission electron microscopy revealed particle formation in all casts where hardening occurred. Electron diffraction gare positive identifications for ALN, CrN, and a, Si3N4 in the binary alloys, and AlN and CrN in the aluminum- cold chromium-bearing steels, respectil&apos;uly. Cubic VN with a, = 4.13A was tentatively identified. Particles, apparently of CrN, also formed in the base steel but did not increase the hardness very much. Chromium and vanadium formed nitride platelets on {001}° matrix planes, while titanium gave clusters <15A diam. Aluminum nitride precipitated at grain and subgrain boundaries, and within the grains. Silicon gave profuse precipitates of several Morphologies at grain boundaries and cubical particles within the grains. No effect of the alloy carbides on nitride precipitation was observed in the heat-treated steels. THE nitriding of steel has been a well-established commercial process for about 40 years, but in spite of this comparatively long period of use there have been few studies aimed at understanding the process. Most studies, like the early but very competent work of Jones and organ&apos; and nones.&apos; were concerned with establishing the pertinent engineering variables of steel composition, gas composition, temperature, and time. As far as the present authors are aware, there have been no studies of the composition, size, shape, or distribution of the nitrides formed in the nitriding of steel. Noren and Kindbom3 did, however, examine a few nitrided steels by surface replica electron microscopy, and were able to show the presence of car-bonitrides and AlN and TiN nitrides. pitsch4,5 and Hrivnak6 examined nitrided pure iron by transmission electron microscopy. Baird7 found manganese nitrides in Fe-1.6 pct Mn when nitrided at 650°C, using the same technique. In the present work, emphasis was placed on transmission electron microscopy because of its inherently better resolution, using principally binary alloys of iron containing 1 pct of alloying element. In addition, a few simple 0.4 pct C steel compositions were examined to investigate possible carbonitride formation. It was not anticipated that all of the added elements would form nitrides under the conditions used, but it was considered desirable to obtain direct experimental evidence on this point. It would be considerably easier to ascertain the presence of alloy nitrides by examining appropriate binary alloys in preference to relatively complex steels. The work reported here could have been done using orthodox ammonia-nitriding procedures, but an operating ion-nitriding equipment was available, and was therefore used for specimen preparation. EXPERIMENTAL DETAILS 1) Materials. Binary alloys were made up from vacuum-melted electrolytic iron with 1 wt pct additions of Cr, Ti, V, Al, Mn, Mo, and Si of about 99.9 pct purity. In addition, three steels were similarly made up—a basis steel with 1 wt pct Cr and 0.4 wt pct C and two steels with further additions of 1.2 wt pct A1 or 2.0 wt pct Ti, respectively. The materials were vacuum-melted and cast as 11-lb heats into tapered square molds of about 2 by 2 in. average cross section. The castings were forged and hot-rolled to 11/4 in. rounds. Discs of 4 in. thickness by about 1 in. diam were machined from the rods. Some of these discs were hot-forged and hot-rolled to about 0.020 in. thick, sand-blasted, and then cold-rolled to about 0.003 in. thick. At this point, the surface was cleaned by light etching with HC1, then washed, dried, and vapor-degreased prior to nitriding. 2) Ion-Nitriding Procedure. The type of ion-nitriding equipment used here is similar to that described by Jones and Martin.8 Briefly, a mixture of nitrogen and hydrogen at 5 mm total pressure is placed in a vacuum chamber with a dc potential of 450 to 500 v applied between the work (cathode) and the grounded metal vacuum enclosure (anode). Nitrogen ions are accelerated to the work where a thin layer of Fe4N forms on the surface and thus sets up a nitrogen concentration gradient. This causes nitrogen atoms to diffuse into the surface layers of the alloy forming a finely divided dispersion of alloy nitrides, causing hardening of the surface. In the work to be reported here. the nitriding was carried out at 550° to 600°C to be consistent with commercial nitriding practice. The temperatures cited are those measured by a thermocouple located under a platform on which the work was sitting. Except where otherwise stated, the mixture used in nitriding the binary alloys contained -2.0 pct N, balance hydrogen. The nitrogen concentration in the nitriding gas mixture used for the binary alloys was purposely kept lower than normally used in nitriding steels. 10 to 20 pct, in order to minimize Fe4N formation. In this way only the alloy nitrides would be present as a second phase. However, in the case of steels which would contain a- carbide phase along with as

Jan 1, 1969

By H. L. Riley, B. W. Gandrud

AS far as the present writers know, this system of flotation has not been used elsewhere in this country, but in the last couple of years it has been introduced, with minor variations, at one plant in England and one in Wales.&apos; The system has been described and discussed in a number of publications.2-5 The following is quoted from an abstract of the latest of these,5 a paper presented at an International Conference on Industrial Combustion in 1952. On the basis of experience to date with the commercial plants, it is believed that the kerosene-flotation process incorporates all the necessary elements to make it greatly superior to anything else now available for treating of fines in wet processes of coal preparation. Additional study and investigation are still needed, however, to determine if certain phases of the process can be improved to such an extent as to make it generally satisfactory and acceptable to the industry. Further improvements will be needed with respect to the capacities of the flotation cells and the reagent consumption. The situation referred to above explains why an investigation is being made of the possibilities of achieving better cell capacities. Results obtained from this investigation, which is still in progress, are believed significant with regard to both cell capacity in general and the relation of cell design to cell capacity in particular. Commercial equipment now being used in a laboratory-type investigation should have performance characteristics similar to those of the larger machines. Equipment and Procedures: All flotation tests have been made in a standard Denver sub-A 24x24-in. unit cell of 12-cu ft volume. Cell modifications to make it more suitable for the tests were an adjustable front-wall section for varying cell depth and a perforated scraper-drag assembly for removal of the float product. There is also an apron dry-coal feeder, a gravity-feed water supply, reagent feeders, and a centrifugal pump that feeds the mixture of coal, water, and reagents into the flotation cell. A wattmeter connected into the drive-motor circuit records the power requirements of the impeller throughout each run. Dry coal, water, and reagents are all fed through a pan-type intake to the feed pump. A Sturtevant blower was set up to furnish air for supercharging. A centrifugal pump with a garbage-can intake provides for disposal of refuse flow to an outside settling tank. Figs. 1 and 2 show the flotation cell; Fig. 2 also illustrates the blower for supercharging. For purposes of this investigation, the percentage by weight of the feed coal recovered in the float product under a standard set of conditions has been considered as the criterion of cell capacity. The authors realize that such a criterion may be somewhat unorthodox, as the term cell capacity is usually understood to refer to feed input and ordinarily takes into account the ash analyses of the float product and refuse. However, the word capacity is flexible enough so that Webster gives one definition as maximum output, a definition which seems to justify, at least partly, acceptance of the above criterion. It has been the authors&apos; experience in the Birmingham district that the ash-reduction efficiency of the coal-flotation process is generally satisfactory and that the only real problem is to increase the rate of float recovery so that the feed rate to any given bank of cells can be increased without undue loss of coal in the refuse. Originally it was planned to operate the flotation cell to simulate continuous operation during sampling periods. It was assumed that operating for reasonable time with feed coal, water, and reagents turned on would stabilize conditions so that the weight of float coal discharged during a fixed time interval would be an accurate measure of the rate at which the coal was being floated. It developed, however, that this supposition was erroneous. The float coal, caught for fixed time intervals and weighed, gave widely varying results in duplicate runs. Efforts to correct this trouble failed, and it was decided to try to operate on a batch-test basis, whereby all the float coal produced during a run on a known weight of feed coal would be caught in tubs, dewatered, and weighed. This method gives consistent and reproducible results, with total float product weight rarely varying by more than 3 or 4 pct on duplicate runs. The standard test procedure is as follows: A 132-lb sample of dry feed coal is weighed and placed in the feed hopper. The feeder is adjusted for a rate of 800 lb per hr. Feed water and reagents are turned on, and the feed and refuse pumps are started. One minute later the impeller is started. Six minutes are allowed for the cell to fill up with the water-reagent mixture. The feed of dry coal is started at the end of this 6-min period. One minute later the float-coal removal drag is started. The float coal is caught in one tub for the first 6 min after the flow of feed coal starts. Tubs are then changed, and the float coal is caught in a second tub until the feed coal runs out, when the tubs are again interchanged to catch the float coal for the remainder of the run in the first tub. The cell is kept running for 3 min with the water and reagents on after the feed stops to allow residual float coal to be removed. At the end of a test the wet float coal in both tubs is weighed and the total weight recorded. The product in the second tub is used for moisture determination and screen-size analyses. When the

Jan 1, 1956

By E. Breinan, M. Salkind

Al3Ni whiskers were chemically extracted from unidirectionally solidified Al-A13Ni eutectic ingots, bent into loops, and heated for 0.1 to 10 hr at 320°, 415", and 510°C. The initial strains ranged from 0.003 to 0.055. In all cases, permanent plastic deformation was noted after heat treatment. The deformation consisted of relatively uniform bending at low stresses and temperatures and short times and kinking followed by fracture at high stresses and temperatures and long times. After kinking, the whisker segments adjacent to the kinks were found to have straightened, which is evidence of a dislocation condensation mechanism. The range of temperatures and strains at which time dependent plastic deformation was found indicates that creep of whiskers probably plays a role in the creep of A13Ni whisker-reinforced aluminum. WHISKERS may be defined as nearly perfect single crystals which exhibit high strength. Because they can support high stresses at relatively low strains, they have been successfully employed in reinforcing metals at both ambient and elevated temperatures. In studying the creep behavior of A13Ni whisker-reinforced aluminum at elevated temperatures,1,2 it was noted that the composites exhibited measurable creep deformation. This investigation of the creep relaxation of individual A13Ni whiskel, extracted chemically from the composite was initiated to determine if creep of whiskers could con. "bute to the overall creep of the composite material. Many observations of plastic deformation of metal and halide whiskers have been made. Brenner3-8 noted that copper, silver, and iron whiskers exhibited heterogeneous plastic deformation at room temperature when strained beyond their yield points. Gyulai9 and Gordon10 observed plastic deformation of relatively large (>3 µ) NaCl and KC1 whiskers, although the smallest, most perfect whiskers were completely elastic. Eisner" noted plastic deformation and microcreep of iron and silicon whiskers at room temperature after straining beyond the yield point. Whiskers reported to exhibit creep at stresses below the yield point were zinc1&apos;-" and Silicon.15 Cabrera and price" observed some zinc whiskers which crept at room temperature after a short incubation period but then stopped creeping after a short time. Because some of their specimens exhibited no creep, they concluded that those whiskers that crept were relatively imperfect. Pearson, Reed, and Feldman15 observed similar creep behavior of silicon whiskers at 800°C. They also concluded that creep of the whiskers was a result of imperfections in their crystals. Brenner16 observed delayed failure of A12O3 whiskers at elevated temperatures but found no evidence of plastic deformation up to 2030°C (99 pct of E.EREINAN and M.SALKIND,JuniorMembers AIME,are Research Scientist and Chief, respectively, Advanced Metallurgy Section, United Aircraft Research Laboratories, East Hartford, Conn. Maunscript submitted April 5, 1968. IMD the melting temperature). Brenner also noted7 that some copper and iron whiskers exhibited delayed kinking above 350°C while others did not. One can conclude from these observations that small relatively perfect whiskers could exhibit completely elastic behavior during sustained elevated-temperature loading of composites. Since A13Ni whiskers tested in both bending and tension were found to exhibit no evidence of plastic deformation at room temperature&apos;7&apos;18 this study was initiated to determine whether or not creep of A13Ni whiskers occurred at the elevated temperatures at which creep in the composites was observed. Whiskers were chemically extracted from ingots of unidirectionally solidified A1-A13Ni eutectic, constrained in bending to various elastic strains and heat-treated. The bending constraints were removed after heat treatment and the amount of permanent set was taken as a measure of the time-dependent plastic deformation. EXPERIMENTAL PROCEDURES Ingots of eutectic Al-A13Ni containing nominally 6.2 wt pet Ni were unidirectionally solidified at approximately 11 cm per hr using a process described elsewhere.19,20 The starting materials were 99.99 pct pure. Cylindrical sections cut from the center of each ingot were placed in a 3 pct aqueous solution of hydrochloric acid and the whiskers were extracted as described previously.17 The whiskers nearest the surface were blackened somewhat due to overexposure to the acid while the center of the ingot was being dissolved These partially attacked whiskers were discarded. An intermediate zone of silver-gray-colored whiskers was collected and stored in methanol for use in relaxation experiments. Individual long pieces of A13Ni whiskers were placed on Fisher Precleaned Microscope Slides. These normally straight whiskers were bent elastically into arcs or loops of varying radii by manipulating their ends with a slender probe. The mass attraction between the whisker and the probe was sufficient to cause the whisker to follow the probe. The whiskers were retained in the elastic bend by the surface tension of a fine residual film on the slides. By using long whiskers, the action of the surface tension on the unlooped ends of the whisker allowed high elastic strains to be maintained in the loops. After each whisker was bent, a photomicrograph was taken for use in measuring the bending strain. The range of strains studied was 0.003 to 0.055. The bent whiskers were then encapsulated in Pyrex tubes at pressures between 10"6 and 5 x 10"6 mm of mercury and heat-treated at 320°, 415°, and 510°C (respectively 53, 61, and 70 pct of the peritectic decomposition temperature). After each heat treatment, the liquid film on the slides was found to have dried, but the whiskers were held in their original shapes by a residue on the slide. The minimum radius of curvature of each bent whisker was measured before and

Jan 1, 1969

By C. T. Liu, J. Gurland

The deformation behavior in tension of spheroidized carbon steels was studied at room temperature as a function of carbon content, 0.065 to 1.46 wt Pct, and carbide particle size, 0.88 to 2.77 p. It was found that the Hall-Petch strength-grain size relation is directly applicable to the yield and flow stresses of the two lower-carbon steels , 0.065 and 0.30 pct C. The strength data for the medium- and high-carbon steels, 0.55 to 1.46 pct C, also satisfied the Hall-Petch relation, provided that these data are based upon the particle spacing. Beyond 4 pct strain, the flow stress data of all the steels studied could be represented by the same Hall-Petch relation with dinerent spacings for grain boundary and particle strengthening. The behavior of the higher-carbon steels was consistent with the postulated formation of a dislocation cell network during processing and initial deformation (up to 4 pct strain). The cell size was assumed to be equal to the planar particle spacing. The true stress at the ultimate tensile strength was also found to be a function of the particle spacing. At a given temperature and strain rate, the yield and flow stresses of carbon steels depend on the type and dimensions of the microstructure. Starting with the work of Gensamer et al. in 1942,&apos; experimental studies on pearlitic and spheroidized carbon steels revealed that the strength of steels is a function of two main parameters: the ferrite grain size2&apos;3 and the carbide particle spacing;1&apos;4&apos;5 on this basis, two different strengthening mechanisms have been developed to apply to steels of low and high carbon contents, respectively. In polycrystalline iron and mild steels the grain boundaries are regarded as the major structural barriers to slip. The relation between strength and grain size is generally represented by the Hall-Petch equation which is based on a linear proportionality between strength and the inverse square root of the average grain size.2&apos;3y677 However, Gensamer et al.&apos; and Roberts et related the yield strength of medium -and high-carbon steels to the carbide particle spacing alone, and they found a linear relation between the logarithm of the mean free path in the ferrite and the yield strength in both spheroidized and pearlitic steels. By means of the electron microscope, Turkalo and LOW&apos; extended the study to finer structures; they concluded that the logarithmic relation is not valid for the entire range of microstructures unless grain boundaries are also included in the measurement of the mean free path. For the specific case of spheroidized steels, Ansell and aenel&apos; found that the yield strength data,4&apos;5 when plotted as a function of mean free path, fit the Hall-Petch equation; however, T&apos;ysong found that the same data fit the 0rowanl0 relation if a planar inter-particle spacing is used. Recently Kossowsky and ~rown" studied the strength of prestrained spheroidized steels, 0.48 and 0.95 pct C, and concluded that the strength due to the carbide dispersions varies linearly with the reciprocal of the square root of the mean free path between carbide particles and dislocation networks. Such networks were first observed by Turkalo." The conclusion common to all these studies is that the available slip distance in the ferrite is the most important variable in determining strendh. Previous work on carbon steels is restricted to limited composition and strain ranges. The mechanism which governs the flow properties is not clearly understood, and, in particular, little is known about the composition dependence of the transition between grain boundary strengthening and particle hardening. The purpose of the present work is to investigate the strengthening mechanism in spheroidized steels over a wide range of carbon content, 0.065 to 1.46 wt pct, and plastic strain, yielding to necking. The spheroidized structure was chosen because of its relative simplicity and the relative ease of control and measurement of the structural parameters. The experimental work is limited to tensile testing at room temperature at constant extension rate. The effects of the carbide particles on the fracture behavior of spheroidized steels are discussed elsewhere.13 EXPERIMENTAL PROCEDURE Eight different grades of vacuum-cast carbon steels were supplied in the form of forged and rolled plate by the Applied Research Laboratory of the U.S. Steel Corp. The compositions furnished with these steels are given in Table I; the carbon content ranges from 0.065 to 1.46 wt pct, or from 1.0 to 22.3 vol pct of carbide. The steel plates were cut transversely into rods a little larger than the test specimens, 1 in. gage length, i in. diam. The rods were austenitized in air (enriched with CO by a consumable carbon-rich muffle) at 50° C above theA, orA., temperature for 2 hr and then quenched in oil with vigorous stirring. The as-quenched rods were tempered in two stages in order to obtain the desired distributions and sizes of carbide particles. The rods were first tempered at 460° C for 10 hr and then at 700" C for periods ranging from 4 hr to 3 days, in vacuum. After final machining, all specimens were vacuum-annealed again at 650°C for 1 hr in order to relieve residual stresses. The tension tests were carried out in two steps. The initial part of the load-strain curve, up to about 2 pct strain, was determined on a Riehle testing machine with an extensometer of small strain range, 4 pct strain, in order to obtain the yield and initial flow piopertiesi As soon as the first part of the test was finished, the specimen was placed in an Instron testing machine equipped with a strain gage extensometer with a maximum strain range of 50 pct. The load-strain curve to fracture was

Jan 1, 1969

By John D. Hanks

INTRODUCTION Chevron&apos;s Uranium Mill is located near Panna Maria, Texas; 70 miles southeast of San Antonio. Designed by Kaiser Engineering, the Mill will process a nominal 2500 dry T.P.D. of uranium bearing ore containing 15% uncombined moisture. Earl Torgerson, San Mateo, California, is the consulting metallurgist on process design. Feed to the plant consists of a mixture of high, medium and low grade sandy day ore; the average grade of the ore will be 0.7% throughout the life of the project. The ore is delivered to the mill via truck and stored by type in individual piles on a flat storage area. The ore is fed by conveyor to a semi-autogenous grinding mill. The SAG mill discharge slurry is pumped either to a storage tank or to the first of five mechanically agitated leach tanks where both H2SO and NaC103 are added. Following leaching, the slurry is mixed with thickener No. 2 overflow before being pumped to a six-thickener, countercurrent decantation circuit where the solution containing uranium is separated from the leach residue. The residue is washed essentially free of solubilized U308 values at the sixth thickener and discharged to an adjacent tailings pond. The first thickener overflow, containing approximately 0.4 grams U308 per liter, is filtered for clarification and sent to the liquid ion exchange (solvent extraction) section. The pregnant aqueous solution is mixed with organic solvent containing amine on which the complex uranyl sulfate ions are absorbed. The immiscible aqueous and organic solutions are mixed and separated in each of the four stages of solvent extraction. The final pregnant organic is directed to a stripping section. A strip solution containing (NH4)2S04 (ammonium sulfate) and NH4C1 (ammonium chloride) is contacted and separated from the organic in each of the four mixer-settler units. The strip solution is mixed with NH3 and the uranium precipitates along with trace amounts of sulfate, chloride, and ammonia. After washing in a thickener, the uranium precipitate or yellowcake is centrifuged and dried in a multiple hearth roaster. Overflow from the yellowcake thickener is recycled back to the stripping section of the solvent extraction circuit. The dried yellowcake concentrate contains more than 98% U308; diluents include H20, ammonia, chloride, etc.. Impurity concentratons in the product are sufficiently low, after drying, to permit direct shipment to refinement installations. ORE RECEIVING Ore from one or more mines will be stored on a pad adjacent to the uranium processing mill. Ore stored in the area may total 200,000 tons or more, which is equivalent to over a two month treatment reserve for the mill. In addition to providing surge capacity, the proposed storage facility permits natural oxidation of the ore and affords an area which, in turn, improve plant U308 recovery and reduces consumption of oxidizing reagents. The uranium bearing ore is segregated at the storage area into several distinct types. One group can be identified by its sandy, clay-like matrix and will be distinguished by its U308 concentration of high, medium, or low. Other ores contain substantial quantities of carbonaceous shale, typical of ore in the area. Feed is recovered from any one or combination of piles, in accordance with operating requirements and recovery factors. The run-of-mine ore, at 15% moisture, is transferred to a stationary, 24-inch by 24-inch grizzly. Undersize material falls into a 280-ton surge hopper located below grade, while oversize material is removed for preliminary size reduction. A sump-pump is located at the reclaim hopper to recover excess mositure and ore spillage for processing. Plant feed is continuously drawn from beneath the hopper at an average rate of 120 tons per hour by means of an apron feeder. The hopper is equipped with a low level safety system to protect the apron feeder assemble. The ore is transferred to a belt conveyor, elevated and discharged into a semi-autogeneous grinding (SAG) mill. Water addition at the discharge point is automatically controlled by a feed rate, moisture analyzer system located on the belt conveyor. GRINDING Minus 24-inch ore, at a rate of 120 mosit tons per hour and cyclone underflow at a rate of 137 moist tons per hour are combined with a controlled 186 gallons per minute fresh, warm plant process water. The mixture, at an average 68% solids, is fed to the SAG mill. The viscous mass is subjected to grinding at a temperature moderately above ambient resulting from use of the 140ºF well water. The 16.5&apos;x5.0&apos; Marcy Mill is driven by a 500 H.P. A.C. Motor. The mill will rotate at 73.4% of critical speed or 14.06 R.P.M. Eight percent of the mill&apos;s volume will be occupied by steel grinding balls; 22% by pulp. The mill is designed to rotate in either direction, in order to obtain maximum lifter and liner life. The SAG mill is equipped with a trommel having ½ -inch slots for removal of oversize material at its discharge and the large or oversize material is collected and either recirculated periodically or discarded. The undersize slurry is diluted to 64% solids with the addition of hot well water or mine water to the mill discharge sump. The flow is automatically controlled utilizing data from a gamma density meter. The slurry from the mill discharge sump is pumped to hydrocyclones to classify the particles. Underflow from the cyclones, at 80% + 28 mesh, is recycled to

Jan 1, 1979

By Don L. Kendall, Martin G. Buehler

A simple physical model has been developed to fit carrier-removal data in silicon irradiated near room temperature with reactor spectrum neutrons. Commonly observed donor and acceptor defect energy levels are assumed to be introduced linearly with neutron fluence. The donor levels (in ev) are Ev + 0.16, Ev + 0.27, and Ev + 0.31 and the acceptor levels are Ec - 0.55, Ec - 0.40, and Ec - 0.1 7, where Ev and Ec are the valence and conduction band energies, respectively. The introduction rates of each level are adjusted to fit literature initial carrier-removal rate data. When normalized with respect to the Ev +0.27 level, the relative values of introduction rates are 5.3, 1.0, 3.1, 1.0, 2.0, and 20.0, respectively for the six levels indicated above. To fit p-f (hole concentration vs neutron fluence) and n-f (electron concentration us neutron fluence) data, the introduction rates are multiplied by a factor which preserves the relative values given above. This factor depends upon irradiation temperature, reactor energy spectrum, neutron fluence calibration, and oxygen content of silicon. An extensive study of the effect of neutrons on carrier-removal in silicon irradiated with reactor spectrum neutrons (E > 10 kev) has been given by Stein and Gereth1 (SG) and Curtis, Bass, and Germano&apos; (CBG). They measured initial carrier-removal rates for both p- and n-type silicon over an impurity range typical of silicon devices. In this work, we attempt to fit a simple theory to this data to establish a usable relationship between hole and electron concentration, p and n, respectively, and neutron fluence f. The p-f and n-f relations are needed to assist in the design of neutron tolerant silicon devices and are needed to clarify presently used empirical resistivity-fluence relationships.3 Neutron damage in silicon produces a variety of defects ranging from simple point defects to defect clusters. For the purpose of this treatment, we assume that simple point defects dominate carrier-removal effects. In contrast to this view, stein4 has proposed that defect clusters are responsible for a significant portion of carrier-removal effects. In the following section, it is shown that the carrier-removal effect in n-type silicon with an electron concentration less than 1015 cm-3 can be explained adequately by assuming that the divacancy is the dominant defect and that its introduction rate is independent of the electron concentration. For electron concentrations greater than 1015 cm-= an additional acceptor defect center is needed, and for simplicity the A-center (vacancy-oxygen pair) has been chosen. Although the E-center (vacancy-phosphorus pair) can account for some of the results, the A-center was chosen because the E-center requires a more involved treatment which the presently available data do not justify. In p-type silicon three radiation-induced donor levels are assumed, namely the divacancy and two other centers of unspecified nature located at Ev + 0.16 ev and Ev to 0.31 ev. The donor divacancy at Ev + 0.27 ev is assumed to be introduced at the same rate in p-type as in n-type. However, this rate is too low to fit p-type initial carrier-removal data. The dominant centers in p-type silicon are assumed to be the Ev + 0.16 ev and Ev + 0.31 ev levels where the latter is not the divacancy. The introduction rates are chosen to fit initial carrier-removal rate data. Assuming that the introduction rates are independent of Fermi level, the ratio between them is fixed for subsequent p-f and n-f calculations. Using the same ratios, the initial carrier-removal rate data1,2 as well as p-f and n-f data1,5 can be fit provided the absolute value of the introduction rates are adjusted to account for irradiation temperature, reactor energy spectrum, neutron fluence calculation, and the oxygen content of silicon. THEORETICAL ANALYSIS This analysis is basically the same as that used by Hi116 to analyze electron damage in silicon except we express the degree to which an impurity level is ionized not in terms of the Fermi level, but in terms of carrier concentration. Landis and pearson7 have used the latter approach to analyze y-damage in silicon. Neutron-induced defects responsible for carrier-removal at room temperature are assumed to be simple point defects with no interaction between defects so that they may be represented by discrete energy levels. It is also assumed that no constituent of a defect complex is used up and defects stabilize shortly after irradiation. Defects are assumed to be introduced linearly with fluence according to the product Rtf where Rt is the defect introduction rate and f the neutron fluence. Taking into account the ionization of defects according to Fermi statistics, and considering charge neutrality where minority carriers are neglected, the n-f relation is where no is the preirradiation electron concentration. The parameter Nt is the electron concentration at which the ionized defect concentration is one-half the total defect concentration (Rtf) or where Et is the defect energy level. For silicon at 300°K, ni = 1.45 X 1010 cm-3 and Ei = Ev+ 0.542 ev which was determined using Ec — Ev = 1.11 ev and me* = 1.07 mo and mh* = 0.558m0. The spin degeneracy factor, which usually appears as a number multiplying the Nt/n term of Eq. [1], is taken as unity. In effect, this factor has been incorporated into the defect en-

Jan 1, 1970

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.&apos; In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/&apos; in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about &apos;/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By Ashok K. Sinha

During the course of an in~*estigation into the occurrence of ordered AB3 structures, the following new phases have been found —CrRh3 (AuCu3 type), CrCo3 (MgCd3 type), HfCo4 (Ths Mn23 type), and WPt, MoPh type). The composition of the TiPt3-x phase (TiNi, type) is close to Ti23Pl77. The alloy chenzistry of transition rnetal AB3 structures is rezliewed in the light of electron concentration correlations of hex-agonality recently obtained for quasi-binary alloys. The relatizte colurne contraction in the AB3 structures increases with increasing difference in volume of the conzponents. A family of ordered close-packed layered structures is formed by stacking identical layers of composition AB, in various sequences, such that the coordination is twelvefold throughout and there are no A-A contacts. Previous work&apos; on quasi-binary AB3 alloys has led to the conclusion that the stacking sequence of the AB, structures changes with increasing radius ratio RA/RB from a purely cubic, through different mixtures of hexagonal and cubic stacking to a purely hexagonal stacking. However. for binary AB3 alloys, a correlation between the type of the crystal structure and the position of the components in the various volumns of the periodic table has been noted.2-5 It has been noted6 that this correlation appears to hold even though the radius ratio RA/RB may vary over a considerable range with the location of the components in the three long periods. Another study7" of several quasi-binary systems led to the conclusion that an increase in hexagonality of the stacking is associated with increase in the electron concentration e/a. as defined by the average per atom of the total number of electrons outside the inert gas shells. In apparent conflict with this conclusion, it is known that seven binary alloy structures isotypic with TiNi3 which is 50 pct hexagonal occur at a higher electron concentration (e/n = 8.5) than that (e/a = 8.25) for the 100 pct hexagonal MgCd3 type structure present in seven binary AB3 alloys. Table 111. In the present work, an investigation into the occurrence of binary AB3 structures in transition metal alloys was made, and a survey of binary AB3 structures is presented. EXPERIMENTAL The starting materials were pure metals of 99.9 wt pct purity. The alloys were arc-melted under partial pressure of argon and annealed in sealed silica capsules lined with molybdenum foil under argon at- mosphere. The total weight loss upon melting and subsequent annealing was always less than 1 pct and hence the alloys will be referred to by their intended (unanalyzed) compositions. Wherever the constitution permitted. the alloys were given a homogenizing treatment at 1200°C (3 days) prior to annealing. Unless otherwise stated all alloys were annealed at 900°C for 1 week and water-quenched. Sometimes the final annealing treatment was carried out on powders to accelerate the attainment of equilibrium. X-ray powder patterns were taken using a Guinier-de Wolff focusing camera (CuK, radiation) or an asymmetrical focusing camera (Co or CrK, radiation). For lattice parameter determination. internal silicon standards were employed. The intensity calculations were made using a Fortran IV program written by Jeitschko and parthe.9 RESULTS Twenty AB3 and three AB4 alloys were investigated. Table I lists the crystallographic data on some of the intermediate phases encountered in the present work. Table II contains the X-ray data for HfCo, (Th,,Mn,, type). The positional parameter, x. was assumed to be 0.378. the value for Th6Mnn2310 The X-ray pattern of ZrCo, was very similar to that of HfCo, and the previous structure determination of ZrCo, by Kuzma el al." was confirmed. Ordering in the alloy CrCo could be ascertained by the presence of only one weak super lattice line (101). the others being too weak presumably owing to the small difference in the scattering powers of chromium and cobalt. This line was observed in the X-ray pattern of powder from the massive sample annealed at 830°C (7 days) after the powder had been reannealed at 600°C (24 hr). The diffraction pattern of the powder similarly reannealed at 830°C (24 hr) contained only the lines due to a mixture of hcp and fcc Co(Crj solid solutions. Therefore, it appears reasonable to assume that O2 and/or N2 contamination which would be less likely to occur during the 600°C anneal was not responsible for the observed weak reflection. Also. this reflection cannot be identified with any of the strong lines of the neighboring s phase which is present in the Co-Cr system at higher chromium contents. The composition corresponding to the TiNi3 structure observed by Raman et al.12 in the two-phase alloy Ti,zt,, has been established in the present work as being between There was satisfactory agreement for the low-angle lines (up to d = 1.997A) between the observed diffraction pattern of TiCua and that calculated assuming the ZrAu, structure. as recently proposed by Pfeifer-et a1.I3 However. some of the superlattice lines. e.g., at d = 1.937 and 1.919A. predicted by the ZrAu, structure were not actually observed eve? though neighboring lines. at d = 1.947 and 1.986A. of comparable calculated intensity were present. The ZrAu

Jan 1, 1970

By H. Udin

G. KUCZYNSKI* and B. H. ALEXANDER*—This paper represents a most noteworthy attempt to evaluate experimentally the surface tension of a solid metal. Because of the great importance of such measurements, any proposed method should receive the closest scrutiny before the results can be considered reliable. In regard to the experimental method, we think that the marking of the gauge length by means of tieing knots in the wire may be the cause of some of the spread in the results. Such a knot may be expected to tighten slightly, and thus increase the gauge length, when placed under stress at high temperature. Although this effect would be very small, amounting at most to only a few times the wire diameter. A fairly tight knot in a wire will decrease the wire length by about ten times the wire diameter, thus only a slight tightening of the knot would cause considerable spread in the results. Upon plotting the stress strain curves from the authors&apos; data, the writers found that there was a fairly consistent tendency towards an S-shaped curve, instead of a straight line. Such an effect could be caused by the tightening of the knots. The writers think, however, that the experimental results are fairly reliable, but that there may be other methods of interpreting them depending upon what mechanism is assumed to be responsible for the shrinkage of the wires. The authors have assumed that the stress due to surface tension results in viscous flow. It should be made clear that it has never been demonstrated that viscous flow can occur in metal crystals even at very high temperatures. The experiments of Chalmers13 on tin, which are so frequently quoted as giving evidence of viscous flow at low stresses are by no means satisfactory. In his experiments, Chalmers found that only the initial rate of flow was approximately proportional to stress. He also found that the rate of flow varied markedly with time which, in his experiments, was less than 2 hr. Inasmuch as there is no proof of viscous flow in metals, and the authors have brought forth no conclusive evidence on this point, it may be worth while to investigate other possible mechanisms of material transport which would account for the shrinkage of the wires. The writers wish to point out that in these experiments the shrinkage of the wires can be adequately explained, according to a self diffusion mechanism. Thus, if we assume a concentration gradient for self diffusion which is a function of the radius of curvature of the wires, and assume that diffusion will occur so that the total surface area is decreased, we find the following expression for the self diffusion coefficient: where k = Boltzmann constant r0 = initial radius of the wire T = absolute temperature ? = surface energy 8 = interatomic spacing t = time e = strain at zero applied stress Eq 19 may be used to evaluate the self diffusion coefficient of copper, using the strain measurements obtained by the authors for zero stress as obtained by extrapolating their curves for 5 rail wires. By inserting a reasonable value for the surface energy (1500 ergs per cm2) we find: -66,000 D = 5 X 10e RT [20] The activation energy is of the correct order of magnitude, but the frequency coefficient is much too high, indicating that surface diffusion may be playing an important role. This discrepancy in the action constant is much smaller than the corresponding discrepancy obtained by the authors for the viscosity coefficient. The writers by no means propose that this proves that the shrinkage of the wires is due to self diffusion but we merely wish to point out that there are explanations other than that given by the authors. In this, as in any kinetic phenomena, it is necessary to study the rate of the process before anything can be said about the mechanism. The determination of surface tension given by the authors is based upon an interpretation of the data which embody the concept of viscous flow. The final proof of this concept will be obtained only after the time relationships confirming the authors&apos; Eq 15 have been conclusively established. The rough linearity of the stress strain curves obtained by the authors for experiments run the same length of time should not be considered as proving that viscous flow is occurring. H. UDIN (authors&apos; reply)—All of the test specimens were annealed at 1000°C for an hour or more before preliminary measurements were made. During this anneal the wires recrystallize, and the greatest part of grain growth takes place. Also, the knots sinter at the cross-over points. This does not in itself eliminate the possibility of end errors, although it greatly decreases their probable magnitude. It is still possible that some extension occurs due to creep in shear at the sintered points. If so, this effect would be quite independent of and superimposed on the normal shrinkage or extension of the wire itself. Within the precision of the experimental results, straight lines satisfy the data as well as do any other simple curves. Until data of greater precision are obtained, it is futile to discuss any possible trends away from linearity. The disagreement between Kuczynski and Alexander&apos;s Eq 19 and our Eq 18 is one of semantics and mathematics, not mechanism of flow, since Eq 18 is based on the self-diffusion concept of viscous flow. It would be interesting to learn how the mathematics leading to Eq 19 deviates from that of Eyring and of

Jan 1, 1950