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By R. H. Dourson, B. H. Sage, W. N. Lacey

The compositions of coexisting phases in the methane-propane-n-pentane system were determined at 160° and -2 20°F. throughout the two-phase region, at pressures above 500 lb. per sq. in. The experimental results permitted the calculation of gas-liquid equilibrium constants as well as the establishment of the critical behavior of this ternary system. Although many binary paraffin hydrocarbon systems have been investigated, the experimental work relating to the phase behavior of ternary paraffin hydrocarbon mixtures at elevated pressures is relatively scarce, being limited to a study of the meth-ane-propane-PL-pentane system at 100°F.l,2 However, Guter and co-workers have studied the phase behavior of the methane-ethane-ethylene system at relatively low temperatures. Information concerning the phase behavior of ternary systems is of value in predicting the behavior of the components in multicomponent systems, since the influence of pressure, temperature, and concentration may be individually ascertained. In the light of the importance of such information, the study of this ternary system was extended to higher temperatures in order to increase the field of temperature in which the data could be applied. Since all states encountered in this investigation are above the critical temperature of methane, the details of its phase behavior are not of direct significance. The properties of propane in the heterogeneous region were taken from a correlation3 based upon recently published data. The corresponding information for n-pentane was taken from experimentally measured vapor pressures and volumetric data.4 The rnethane-propane system has been studied throughout the two-phase region at temperatures above 70°F.,5 while the phase behavior of the propane-n-pentane system has been established for temperatures above 160°F.6 The volumetric and phase behavior of the methane-72-pentane system has been studied in detai1.7,8 The experimental measurements serve to establish with adequate accuracy the phase behavior of the components and of the constituent binary systems for this ternary system. It is believed that, with the exception of the measurements for the methane-propane system, the uncertainties in the earlier data relating to the pure substances and the binary mixtures are probably less than those associated with the values reported here. Method The methods and apparatus employed in this investigation have been described.137 In principle, the method involved the withdrawal of samples of the coexisting gas and liquid phases from a vessel containing a heterogeneous mixture of methane, propane and n-pentane. Provision was made so that

Jan 1, 1943

By W. N. Lacey, R. H. Dourson, B. H. Sage

The compositions of coexisting phases in the methane-propane-n-pentane system were determined at 160° and -2 20°F. throughout the two-phase region, at pressures above 500 lb. per sq. in. The experimental results permitted the calculation of gas-liquid equilibrium constants as well as the establishment of the critical behavior of this ternary system. Although many binary paraffin hydrocarbon systems have been investigated, the experimental work relating to the phase behavior of ternary paraffin hydrocarbon mixtures at elevated pressures is relatively scarce, being limited to a study of the meth-ane-propane-PL-pentane system at 100°F.l,2 However, Guter and co-workers have studied the phase behavior of the methane-ethane-ethylene system at relatively low temperatures. Information concerning the phase behavior of ternary systems is of value in predicting the behavior of the components in multicomponent systems, since the influence of pressure, temperature, and concentration may be individually ascertained. In the light of the importance of such information, the study of this ternary system was extended to higher temperatures in order to increase the field of temperature in which the data could be applied. Since all states encountered in this investigation are above the critical temperature of methane, the details of its phase behavior are not of direct significance. The properties of propane in the heterogeneous region were taken from a correlation3 based upon recently published data. The corresponding information for n-pentane was taken from experimentally measured vapor pressures and volumetric data.4 The rnethane-propane system has been studied throughout the two-phase region at temperatures above 70°F.,5 while the phase behavior of the propane-n-pentane system has been established for temperatures above 160°F.6 The volumetric and phase behavior of the methane-72-pentane system has been studied in detai1.7,8 The experimental measurements serve to establish with adequate accuracy the phase behavior of the components and of the constituent binary systems for this ternary system. It is believed that, with the exception of the measurements for the methane-propane system, the uncertainties in the earlier data relating to the pure substances and the binary mixtures are probably less than those associated with the values reported here. Method The methods and apparatus employed in this investigation have been described.137 In principle, the method involved the withdrawal of samples of the coexisting gas and liquid phases from a vessel containing a heterogeneous mixture of methane, propane and n-pentane. Provision was made so that

Jan 1, 1943

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 J. H. Frye, C. P. Sun

A PRIMARY substitutional solid solution is a solution that has the same crystalline structure as the solvent metal, and in which solute atoms have replaced solvent atoms at random on the host lattice. This replacement usually results in an increase in hardness as measured by conventional penetration tests. The factors controlling this hardness increase have been investigated in some detail for copper and silver aneys.1-5 It has been shown that at least, four factors are involved: (I) concentration of solute, (2) row of the periodic table from which the solute is taken, (3) increase in lattice parameter of the solvent produced by the solute, and (4) work-hardening produced by penetration of the hardness indenter.2,4 The last factor is of the utmost importance. An investigation of the available data2.4 leads to the conclusion that the solutes that produce large hardness increases in copper or silver do so principally because they increase the rate of work-hardening. Furthermore, it is doubtful whether any solute produces appreciable hardening in the absence of plastic deformation and hence work-hardening. Thus it is clear that an understanding of the effect of solutes on rate of work hardening is essential to an understanding of the hardness of solid solutions. This effect of solutes is also important in forming operations such as rolling or deep drawing. The presence of elements that confer rapid rates of work-hardening will increase power consumption and may well decrease the amount of deformation possible between anneals. This paper is the report of an investigation of the factors that control rates of work-hardening in copper and silver solid solutions. The silver and copper alloys considered are those in which all solutes are from the B subgroups or second short period of the periodic table. Experience with hardness, with structure of alloys, and with electrical conductivity has proved that results of a fundamental nature are most likely to be obtained if alloys are made up on the basis of the positions of the constituent elements in the periodic table. In previous work, Meyer analysis data on high-purity copper and silver solid solutions were obtained through careful measurements with fully calibrated equipment and these data were corrected to correspond to a standard grain size. From these corrected Meyer analysis data rates of work-hardening have now been calculated. CALCULATION OF RATES OF WORK- HARDENING The Meyer analyses, on which this study of rates of work-hardening is based, consisted in determining impression

Jan 1, 1944

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 George Fancher, R. L. Whitting

A typical drilling mud from the Hastings oil field, Brazoria County, Texas, containing only 8 per cent (dry basis) of material of colloidal dimensions, which is largely illite, was concentrated to a density of 10.2 lb. per gal. and used in this study. The effects of water dilution, treatment with complex polyphos-phates, temperature and the time of heating upon the rheological properties of the mud were investigated. It was found that water plays an important part in chemical treatment and that sodium acid pyrophosphate and sodium tripolyphosphate were more efficient than other complex polyphosphates for chemical treatment. Muds treated with either of these chemicals manifested maximum reduction in viscosity and minimum filtration rates at low concentrations. Furthermore, .mud treated to minimum viscosity with either of these two chemicals was virtually unaffected by heat-treatment. Introduction The drilling of deep wells is dependent upon the use of drilling mud, and problems frequently arise concerning the effects on mud of temperature, prolonged heating and aging. The use of chemicals to control the rheological properties of mud is a well-established practice. Salts of weak organic acids such as sodium tannate or gallate were used at first until the complex phosphates of sodium were found to be more efficient. Consequently, it seemed important to investigate the reaction of a mud to chemical treatment with phosphates, temperature, heat-treatment and aging, particularly since previous work in the laboratory at the University of Texas had provided the particle-size distribution and mineral composition of Hastings mud. Properties or Mud Used in Experiments A large sample of the mud from a drilling well in the Hastings field, Brazoria County, Texas, was obtained directly from the circulatory system. Some of the general physical characteristics of the mud and other data are presented in Table I. Table i.—General Properties of Hustings Drilling Mud Alex- Cur-ander keet Well Well Depth when sample was taken, It.. 5720 5700 Weight. lb. per gal............... 9.5 0.8 Viscosity, sec. A.P.I.............. 47 60 Viscosity, Stormer, grams......... 80 Viscosity, centipoises............. 13 Filtration rate, c.c. per 30 min.a. . . 19.6 22.8 Salt content (chlorides), per cent... 0.13 0.12 pH............................. 8.9 8.9 The Alexander mud was used for the experimental work. Comparison with Curkeet mud indicates a considerably greater dilution but otherwise suggests similarity. The mineral composition and particle-size distribution of Curkeet mud (Table 2) are available (Fancher and Oliphant6). It is suggested that Alexander mud would have a similar composition.

Jan 1, 1943

By R. L. Whitting, George Fancher

A typical drilling mud from the Hastings oil field, Brazoria County, Texas, containing only 8 per cent (dry basis) of material of colloidal dimensions, which is largely illite, was concentrated to a density of 10.2 lb. per gal. and used in this study. The effects of water dilution, treatment with complex polyphos-phates, temperature and the time of heating upon the rheological properties of the mud were investigated. It was found that water plays an important part in chemical treatment and that sodium acid pyrophosphate and sodium tripolyphosphate were more efficient than other complex polyphosphates for chemical treatment. Muds treated with either of these chemicals manifested maximum reduction in viscosity and minimum filtration rates at low concentrations. Furthermore, .mud treated to minimum viscosity with either of these two chemicals was virtually unaffected by heat-treatment. Introduction The drilling of deep wells is dependent upon the use of drilling mud, and problems frequently arise concerning the effects on mud of temperature, prolonged heating and aging. The use of chemicals to control the rheological properties of mud is a well-established practice. Salts of weak organic acids such as sodium tannate or gallate were used at first until the complex phosphates of sodium were found to be more efficient. Consequently, it seemed important to investigate the reaction of a mud to chemical treatment with phosphates, temperature, heat-treatment and aging, particularly since previous work in the laboratory at the University of Texas had provided the particle-size distribution and mineral composition of Hastings mud. Properties or Mud Used in Experiments A large sample of the mud from a drilling well in the Hastings field, Brazoria County, Texas, was obtained directly from the circulatory system. Some of the general physical characteristics of the mud and other data are presented in Table I. Table i.—General Properties of Hustings Drilling Mud Alex- Cur-ander keet Well Well Depth when sample was taken, It.. 5720 5700 Weight. lb. per gal............... 9.5 0.8 Viscosity, sec. A.P.I.............. 47 60 Viscosity, Stormer, grams......... 80 Viscosity, centipoises............. 13 Filtration rate, c.c. per 30 min.a. . . 19.6 22.8 Salt content (chlorides), per cent... 0.13 0.12 pH............................. 8.9 8.9 The Alexander mud was used for the experimental work. Comparison with Curkeet mud indicates a considerably greater dilution but otherwise suggests similarity. The mineral composition and particle-size distribution of Curkeet mud (Table 2) are available (Fancher and Oliphant6). It is suggested that Alexander mud would have a similar composition.

Jan 1, 1943

By M. R. Lorenz

Efficient visible light emission from p-n junctions in semiconductors is currently achieved in the four materials, Sic, GaP, ]Ga1-xAs and GaAs1-x,. Recent advances in materials preparation and p-n junction formation are briefly reviewed. The radiative recombination processes in the different materials depend largely on the band structure and the impurity states of each material. The spectral distribution of the emission ranges from the blue in Sic, to green in Gap, yellow in Sic and red in Gap, Ga1-x AlxAs and GaAs1-x Px. The origin of the various processes are discussed. The conversion of the electrical power into optical power and the measurement of the conversion efficiency are reviewed. The currently maximum quantum efficiencies at 300°K are: 3 pct in GaP(red), 1 pct in SiC(yellow), 0.1 pct in GaP(green), 0.2 pct in Ga1-x AlxAs at 66001, and 0.1 pct in GaAs1-x Px at 6800. The brightness and the interplay of the quantum efficiency and the luminous efficiency are given detailed consideration. VISIBLE light generated by the application of a direct current to a semiconductor crystal was first observed by Lossev1 in 1923. Light emission came from naturally occurring junctions in Sic crystals but little was known then with regard to the mechanism of charge transport and light emission. Some nearly 30 years later and with a vastly increased understanding of semiconductors the phenomenon of electroluminescence was studied in more detail, for example in p-n junctions of germanium.2 In these early studies, the efficiency of converting the electron current into a photon current was very low and therefore aroused little interest toward practical application. More recently it became apparent that in certain materials, for instance GaAs, and under certain conditions, the conversion efficiency was not low at all.3 The subsequent discovery of the p-n junction laser4-6 provided the impetus for increased studies of electroluminescence. Light emitted from GaAs occurs in the infrared region of the electromagnetic spectrum and is not visible to the eye. At nearly the same time the use of GaAs1-xPx led to laser action at low temperatures which was visible to the eye.7 Later a red light emitting diode, made from Gap, was reportedS which emitted incoherent radiation at 300°K with an external quantum efficiency of about 1.5 pct. The fact that such efficient devices were obtainable led to a more concentrated effort in the search for highly efficient room-temperature semiconductor light sources. It is some of this later work on p-n junction luminescence with which we will be concerned here. Since our aim is centered on visible light, with hv =1.8 ev ( ?=7000?), only the wider band gap semiconductors are of interest, i.e., Eg 1 1.8 ev. Although many compounds meet this criterion, only a limited number of those are also good semiconductors, i.e. contain low resistance n and p regions. Some of the more promising candidates are listed in Table I. We will only be concerned with light generation from a p-n junction. This limitation excludes essentially the group II-VI binary compounds, although we will briefly review the case of ZnTe and the solid solution ZnTe1-xSex. As we will show they may contain a p-n junction but only of a special kind. Most of the discussion will deal with the four materials, Sic, Gap, Gal-xAlxAs, and GaAs1-xPx. These appear to be at the present time the best visible light emitting semiconductors. In the following sections we will briefly consider: 1) the electrical properties of p-n junctions; 2) some recent advances in materials preparation; 3) the formation of p-n junctions; and then in somewhat greater detail we will consider: 4) the various radiative recombination processes; 5) the measurement and observation of the external quantum efficiency; 6) the luminous efficiency; 7) the brightness of light emitting diodes (LED'S). THE P-N JUNCTION The p-n junction in a semiconductor crystal is the interface between two differently doped regions. More specifically the p region is doped predominantly with acceptor impurities and the n region contains predominantly donor impurities. The energy band structure of a degenerate p-n junction at thermal equilibrium is shown in Fig. l(a). The excess electrons on the n side of the junction are confined to this region by the barrier potential Eg. Similarly the excess holes on the p-side of the junction are confined to the p-region by a similar potential barrier. If we now apply a dc voltage V such that the p region is made positive and the n region negative, the barrier potential EB is reduced by the applied voltage, V and the junction is said to be forward biased. With the barrier potential lowered, electrons and holes can drift toward the p region and n region, respectively, see Fig. l(b). The current voltage characteristics of p-n junctions in most wide band gap materials can be described by the relation: J = Joexp(eV/BkT) [1] where the functional form of Jo is determined by the recombination mechanism. Jo is generally a complicated parameter which depends on a number of different factors including temperature, junction width, bias voltage, and carrier lifetimes. The parameter B also depends on the recombination mechanism but

Jan 1, 1970

By A. U. Seybol

Eight binary iron alloys were examined after ion nitriding experiments to determine the behavior of the following elements: Al, Mo, Mn, Si, Ti, V,Cr, and C. Only Al, Cr, Ti, and V additions caused hardening in binary iron alloys. A few steels were examined to see the effect of Cr, Cr + Al, Cr + Ti, and Cr + V. It is suggested that a useful new class of ni-triding grade steels might be those containing about I pct V. The nitriding of steel, first described by Fry1 about 45 years ago, rapidly attained commercial application with very little knowledge of the fundamentals involved. While Fry,' in describing the status of nitriding in 1932, apparently correctly postulated hardening by precipitated nitrides, the details of the nitriding process were not understood, nor has the situation changed much since that time. It is also interesting to note that the compositions of some typical nitriding steels given by Fry at that time have changed little in the intervening years. Currently used nitriding steels owe their surface hardening to either chromium (as in 4340 steel) or aluminum plus chromium as in the Nitralloy grades, where both CrN and AlN appear to contribute to harden ing. Titanium additions have been studied experimentally, but thus far titanium steels have not won wide commercial acceptance. This subject will be expanded later. The orthodox ammonia nitriding process has been reviewed very adequately many times as in Jenkins3 and Case and VanHorn,4 and their is no need to outline the process here. Ion nitriding is not as well-known, although there have been several descriptions5-9 of the process given, sometimes with comparisons with the ammonia process. Most of these papers are primarily concerned with a description of the equipment, or of the physics or electrical engineering aspects of ion nitriding, but Noren and Kindbom9 gave the results of a metallurgical investigation using both processes. In brief, ion nitriding is carried out in a vacuum chamber from which the air is exhausted and replaced by a N2-H2 mixture, typically containing 10 to 20 pct N2, at about 5 to 10 torr pressure. While ammonia gas has also been used in ion nitriding, there is no evidence that ammonia makes any improvement in the ion nitriding process. A few hundred volts dc is applied between the grounded container wall (positive) and an insulated center post supporting the work (negative) to be nitrided. A glow discharge is created in the ionized gas, accelerating positive nitrogen ions to the work. These ions contain enough energy to form the normally unstable Fe4N "white layer", thus establish- ing surface nitrogen solubility characteristic of the a Fe/Fe4N equilibrium. This creates a substantial concentration gradient, driving dissolved nitrogen into the steel. The temperature employed is in the same range (around 500" to 550°C) as in ammonia nitriding, but because of factors which are not understood at present the nitriding time is ordinarily considerably reduced in ion nitriding. Other advantages have been cited,9 but it is not the purpose of the present work to contrast the two processes. The present objective was to examine the behavior of binary iron alloys during ion nitriding with respect to the microstructure, hardness level, and depth, and to examine some of these factors in steels as well. In this way it was hoped to be able to find out something about the individual role of these elements in steels. While all the work was done by ion nitriding, there seems to be no reason why any conclusions reached would not equally apply to ammonia nitriding, excepting only the kinetic aspects of the process. Another objective was an exploration of the critical-ity of the ion nitriding variables: gas composition, pressure, temperature, and time. EQUIPMENT AND MATERIALS The equipment used was substantially as described by Jones and Martin.8 The vacuum tank was about 12 in. in diam by about 18 in. high, and consisted of water-cooled stainless steel, with a single small window at the top for viewing inside. This sat on a heavy mild steel base equipped with the main pumping port, pressure control port, and vacuum gaging. A series of variable resistances was interposed between the glow discharge and a large-capacity -40 amp variable primary transformer feeding a 1000-v transformer, but 600 v were about the maximum ordinarily used. With the small l-in.-round, 4-in.-thick discs used for nitriding, the electrical load was usually about 500 v at 0.8 amp. The specimen temperature was controlled by a stainless-steel sheathed chromel-alumel couple, whose junction was in the steel stool upon which the flat discs were placed. These were ground through 400 Sic paper. Cycling of the temperature controller caused -0.2 amp variation in ion current, providing an ample control band. The binary iron alloys were made from vacuum-melted hydrogen-deoxidized electrolytic iron and alloys of 99.9 pct purity. Cast ll-lb-square tapered ingots were forged and hot-rolled to about 11/4-in.-diam rounds. Discs of 1/4 in. thickness by about 1 in. diam were machined from the rods for nitriding specimens. The following alloys were prepared: 1 pct each of Mn, Mo, Cr, Ti, Al, V, Si, and an Fe-0.8 pct C alloy. EXPERIMENTAL VARIABLES Of the variables total gas pressure, nitrogen partial pressure, temperature, and time, only nitrogen partial pressure was found to be critical to the operation. A critical nitrogen partial pressure was found corre-

Jan 1, 1970

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.' 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' 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 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,' experimental studies on pearlitic and spheroidized carbon steels revealed that the strength of steels is a function of two main parameters: the ferrite grain size2'3 and the carbide particle spacing;1'4'5 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.2'3y677 However, Gensamer et al.' 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' 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' found that the yield strength data,4'5 when plotted as a function of mean free path, fit the Hall-Petch equation; however, T'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 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.' 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/' 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 '/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