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. F. W. SPERR, JR.,* Pittsburgh, Pa.--Mr. Malcolmson states that the Carbocoal process produces ammonium sulfate in excess of that normally recovered in the ordinary byproduct coke process. Table 3 indicates that 20,000 to 25,000 lb. of sulfate of ammonia are obtained in carbonizing 1000 tons of Clinchfield coal. This is a high-grade coal and yields from 26 to 28 lb. of ammonium sulfate per ton in a modern byproduct coke oven. On the next page, 21 lb. is stated as the yield of ammonium sulfate per short ton of raw coal; this is less than the average production from any well operated byproduct coke-oven plant treating coal of the character usually coked, in Pennsylvania and Ohio. The statement as to the comparative yields of light oil is somewhat misleading in view of the results obtained during the past year or two by the more modern byproduct coke plants. The plants put in operation by the H. Koppers Co., during the past two years, are producing about 3.5 gal. of light oil per short ton of coal, and several of these plants are producing more than 4 gal. per ton. The yield of pure toluene runs from 0.45 gal. to 0.55 gal. per ton. .The quality of the light oil .obtained from the Carbocoal process is of much greater importance than would be inferred by one not closely familiar with the subject. The presence of paraffins in the benzol and toluol fractions seriously detracts from their commercial value; the benzol and toluol fractions derived fro in the Carbocoal process contain about 50 per cent, of paraffins. It should be thoroughly understood what these paraffins are. They are simply hydrocarbons that go to make up ordinary petroleum, and if a successful method for the removal of paraffins from benzol and toluol has been developed, this can at once be applied to several well known processes by which benzol and toluol can be made directly from petroleum, which have as yet been total failures on account of the contamination of these products by paraffins.

Jan 11, 1918

The Secretary : The work of Mr. A. E. Outerbridge, Jr., of Philadelphia, first made known in his paper on " The Mobility of Molecules of Cast-Iron," read at the Pittsburgh Meeting of the Institute, in February, 1896, has been reviewed by the Committee on Science and the Arts of the Franklin Institute, whose report, dated May 5, 1897, is accompanied with a table of tests made by the Committee, and amply confirming the statements of Mr. Outerbridge. Concerning the originality and novelty of his investigation, the Committee says: " The fact that a certain molecular change takes place in cast-iron in the course of time has been known and recognized by many persons for a long time, and that this change tends to relieve the internal strains and render the casting tougher has often been noticed and acted on, although in a very crude way; but, so far as the sub-committee has been able to learn, Mr. Outerbridge has been the first to make a careful study of this, and to note that the change may be hastened by impact, and the whole effect produced in a short time, and also to make a scientific study of the phenomenon. We believe great credit is due him for the initial observation and the careful work dependent thereon. The results were first given to the public in a paper read before the American Institute of Mining Engineers, on February 20, 1896. This aroused a wide-spread interest and discussion among users of cast-iron, and so far as the sub-committee has been able to determine, it has not been shown that anyone, either in this country or abroad, has antedated Mr. Outerbridge in his work in this line. The Franklin Institute therefore recommends the award to him of the John Scott Legacy Premium and Medal." This report has not been published, hut I have had the opportunity to read it in manuscript. The table of testa accompanying it comprises 91 tests of " rumbled" and an equal number of " not rumbled" companion-bars of cast-iron, 26 by 2 by

Jan 1, 1898

By H. J. Struth

The benefits of proration of oil production were perhaps more concretely realized in 1932 than at any time since the oil industry adopted nation-wide production control. Reduced output of crude petroleum, which brought the daily average of the United States down to approximately 2,000,000 bbl. from a peak in 1931 of more than 2,600,000, had a telling effect on the trend of oil prices. Mid-Continent crude was advanced in price from 776, for 36-gravity oil, to $1.04 a barrel. California crude, of 26-gravity at Signal Hill, moved forward from 736 to 976 a barrel. Pennsylvania crude, the only exception to the upward trend, rose in price from $1.82 per barrel to $2.02, only to react to $1.72. This was due to local conditions which necessitated an adjustment to overcome competition from other areas of the United States. East Texas continued to exert a far-reaching influence on the crude and gasoline market during 1932. Despite the fact that oil prices were advanced in most fields, large quantities of oil were produced in East Texas in violation of state proration orders, and sold in the market at prices considerably below official postings. This created competitive conditions in the gasoline market that were felt by all refining centers of the United States. The quantity of gasoline produced from cheap East Texas crude was not large, but the volume was sufficient to influence prices in practically all sections of the country. Thus, while the industry's' economic situation showed visible improvement statistically, the unreported and unseen statistics originating in East Texas proved to be an insurmountable obstacle to the economic betterment that was otherwise apparently justified. Somewhat surprising to many was the fact that gasoline consumption was maintained within 10 per cent of the preceding year. Domestic consumption showed only a net decline under 1931 of about 8.5 per cent; exports dropped in volume to the extent of about 23 per cent. As a matter of fact, domestic gasoline consumption was only about 1.4 per cent less than it was in the predepression year of 1929. Exports, however,

Jan 1, 1933

By F. R. Hutto Jr., F. L. Kady Jr., L. E. Weymouth

The behavior of particulate non-metallic materials in moving contact with smooth surfaces is of interest and concern to manufacturers and users of abrasives, of fillers, and of pigments alike. The theoretical aspects of the subject have been treated to considerable extent in the literature, and correlatic,ns are available that attempt to relate various methods of hardness determination." 2 The particle size and friability are characteristics of the abrasive that are not related to the smooth surface. The hardness, on the other hand, may be visualized as relative to that of the smooth surface. In a study of abrasive action, the role that hardness, per se, plays is a complicated one. For it is necessary to compare the "hardness" of the abrasive, usually a non-metallic, with that of the smooth surface, generally a metal. Hardness of non-metallics is defined as resistance to scratch and is almost universally described with respect to the Mohs scale.3 Minerals have been rated by Mohs numerically from the softest (talc = 1) to the hardest (diamond = 10). By definition, a mineral has a designated hardness when it is scratched by the standard that is numerically just above it on the scale; and conversely, when it scratches the standard that is just below it. Hardness of metals. however.. implies resistance to indentation, a property that has been measured by a number of methods. In fact, the indentation hardnesses of the standard minerals on the hlohs scale have been determined by the Rockwell tester. Reproduced below are two versions of this correlation. 'A conversion chart, prepared by Wilson Mechanical Instruments Division of American Chain and Cable Co., merely gives the conversion from Rockwell to Knoop hardness. The relation between Knoop indentation hardness and Mohs scale has been reported by G. S. Smith — A New Scale of Hardness, The Engineer, Aug. 26. 1949. G. F. Kinney in Engineerin Properties and Aplications of Plastics reports the Rockwell hardness of the minerals directly in the Mohs scale. The question immediately arises as to whether this relation is valid when applied in reverse; namely,

Jan 1, 1961

By J. C. Swartz

Measurements of the effect of precipitation stresses on the solubility of cementite (Fe3C) precipitates in a iron are reported. Solubilities were determined from measurements of the Snoek relaxation due to interstitial carbon after quenching from various equilibrium treatments. Stress-free precipitates were obtained by a spheroidizing treatment of vacuum-melted Fe 0.06 wt pet C. Subsequent equilibration treatments were designed to suppress nucleation of other precipitates. The results for stress-free cementite give a heat of solution of 14.8 i 0.2 keal per mole and an entropy change of 1.1 i 0.2 eu in the temperature range 400" to 715°C. Comparison with previous data indicates that the heat of solution increases about 6 keal per mole as temperature increases from 700" to 1000°C. Data on self-stressed cementite in quench-aged specimens of Fe 0.013 wt pet C indicate 1) an apparent heat of solution of 12.1 i 0.4 keal per mole in the range 280" to 690°C, 2) a strain energy of- 1.1 keal per mole Fe3C accompanying precipitation at 280°C, and 3') a gradual decrease in the strain energy of precipitation with increasing equilibration temperature. In com-parison with 2 and 3 the strain energy calculated for an isotropic model is 1.7 keal per mole Fe3C. The lower values obtained from the experiment indicated substantial stress velaxation by dislocation motion. WHEN a supersaturated solution of carbon in a iron is aged at temperatures in the range 200o to 700oC, the carbon clusters by interstitial diffusion and forms cementite (Fe3C) precipitate particles. Unstressed cementite has a volume per iron atom 9 pet higher than that of a iron;' hence, cementite precipitate particles are usually under pressure from the iron matrix. The pressure would tend to increase the solubility of cementite in iron.' This report describes anelastic measurements of the solubilities of self-stressed and stress-free cementite in a iron. Previous determinations of the cementite solubility are summarized in Table I. The method of cementite formation for each reference was studied to ascertain the state of stress of the cementite. The results judged to be for stress-free and stressed cementite are distinguished in the table. In the next section an estimate of the stress effect is obtained which is clearly too small to account for the large difference between the previous results in parts A and B of the table. THEORETICAL Let AGO be the standard free-energy change of the reaction Fe3C (eem.) = 3Fe (a) + C (in a) [1] in the absence of stresses. Since cementite precipitates appear to be rather pure10 and the carbon is so dilute in the iron,8 the cementite and iron of Eq. [ I] for the stress-free case have essentially unit activities and the activity of carbon equals its atom fraction xoC Then the stress-free equilibrium is expressed by RT In XoC = -?GO 121 To first approximation the change in the chemical potential of carbon due to the precipitation stresses equals the elastic strain energy W accompanying precipitation of a mole of cementite.2 Hence, in the presence of the precipitation stresses the equilibrium is described by RT In x sq = -?G° + W [3] where xsC is the mole fraction of dissolved carbon in the stressed case. An approximate value of W can be obtained from analysis of the inclusion problem in elasticity theory. The inclusion is a small portion of the matrix phase which has suffered a transformation while still imbedded in the matrix. In the absence of the constraint of the matrix the transformation would be equivalent to a uniform dilational strain eT. Both the matrix (a) phase and inclusion (0) phase are assumed to be homogeneous, isotropic materials. When the a and 0 phases have the same elastic moduli, which is approximately true for iron and cementite,11 the total strain energy per mole ß is12 2µVß(eT)2(3 +4 µx)-I [4]

Jan 1, 1968

By P. W. Andrews, R. B. Toombs

ECONOMIC STRUCTURE OF MODERN INDUSTRIAL ECONOMIES The role of minerals in modern industrial economies may be examined in several ways. There are relationships with the various sectors of the economy: the primary, secondary, and tertiary industrial groupings and activities. Mineral supply and demand activities can be measured in terms of national accounts criteria. The economic policy objectives of the modem industrial economy are based to a considerable extent on the needs of the nation for economic supplies of miner- al materials. There is an important role for minerals relative to national security in peace and in wartime and many national policies are directed toward ensuring adequate sup- plies of minerals. Environmental control in the modem industrial economy is increasingly concerned with matters related directly to the production and use of minerals and these matters, in turn, bear importantly on conservation in mineral supply and demand. Mineral polices include specific provision for research and development activities concerned with the production and the use of minerals. In all, national policy objectives will be shaped in considerable part by the circum- stances of mineral supply and demand: the relative degree of availability from domestic and foreign sources, the state of the mineral-processing industries, and the degree of development of the mineral-using industries, and per capita and total changes in requirements. Goods made from mineral raw materials are the basis of all advanced societies and although this is taken for granted, every country is continually dealing with problems of mineral supply and demand. Considering that in the first 50 years of this century the consumption of mineral materials in a highly Industrialized country such as the United States increased by six times while the population was doubling, it becomes apparent that if a country is to enjoy rapid economic growth it must have access to huge and ever-growing supplies of mineral materials at lowest possible cost. Adequate supplies of mineral materials and wise usage of mineral resources have always been among the most important determents of a nation's survival The importance of access to adequate mineral supplies is increasing every year and this has significant international, as well as national, implications because of the unique locational characteristics of mineral resources. It is generally acknowledged that no particular type of natural resource is essential to a high level of national income or to economic progress. A country's endowment of natural resources need not exercise a determining influence on the course of its national income over time, provided it is able to trade. What is required for economic progress is the availability of a substantial quanti-

Jan 1, 1976

By Gerald Edmunds

THE liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the com- position of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. APPARATUS By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 1 ¾ in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 18 ½ in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By Albert Ladd Colby

PAGE I. Introduction,...........577 11. PRocess of Manufacture. 1. American Specifications. 2. Foreign Specifications, . ......... 580 III. Chemical Properties. I. Chemical Composition: (a) American Specifications ; (b) Foreign Specifications. 2. Chemical Analysis: (a) American Specifications ; (b) Foreign Specifications ; (c) Number of Analyses Required ; (d) Sample for Analysis ; (e) Check-Analyses Impracticable ; (f) Rejection Solely on Variation in Com-' position,............581 IV. Physical Properties. 1. Drop-Test and Drop-Testing Hachine: (a) American Specifications ; (b) Foreign Specifications ; (c) Limits in Deflection. 2. Tensile Test: (a) American Specifications; (b) Foreign Specifications ; (c) Test-Pieces are not Representative ; (d) Specified Tensile Strength is Affected by the Section ; (e) BpeciBed Tensile Strength is Often Inconsistent with Specified Chemistry ; (f) Specified Tensile Strength is Often Inconsistent with Specified Elongation ; (g) Amount of Tensile Testing Required is Excessive ; (11) Conclusions. 3. Dead-Weight Test: (a) American Specifications; (b) Foreign Specifications; (c) Number of Tests Specified. 4. Bending-Test: ((1) American Specifications ; (b) Foreign Specifications,..........589 V. Section. 1. American Specifications. 2. Foreign Specifications: (a) Templets ; (b) Sample Piece of Rail; (c) Allowable Variation from Templet,...........601 VI. Weight. 1. American Specifications. 2. Foreign Specifications,. . 603 VII. Length. 1. American Specifications. 2. Foreign Specifications, . . 604 VIII. Drilling. 1. American Specifications. 2. Foreign Specifications, . 604 IX. Finish. 1. American Specifications. 2. Foreign Specifications, . . 50.5 X. Branding. 1. American Specifications. 2. Foreign Specifications : (a) Data to be Rolled in Raised Letters on Web of Rail ; (b) Marking of the Blow-Number on Each Rail; (c) Additional Marking and Painting of Rails,........605 XI. Inspection. 1. American Specifications. 2. Foreign Specifications: (a) Prior Notice of Rolling; (b) Free Access to the Works ; (c) Cost of Inspection, Analyses and Tests to be Borne by the Manufacturer ; (d) Rails after Inspection by Manufacturer to be Sorted into Lots Prior to Inspection by the Engineer ; (e) Disposition of Rejected

Jan 1, 1907

By H. W. Highriter

THE method developed and used in this laboratory for the production of metallic uranium of such purity that it is ductile and can be cold-worked to fine wire or thin sheet by rolling has already been described1. It consists, briefly, in the electrolysis of potassium uranous fluoride (KUF5) in a molten bath composed of equal parts of sodium and calcium chlorides. The bath is contained in a graphite crucible, electrically heated to about 775° C., the crucible serving as the anode for electrolysis. The uranium deposits in finely divided form mixed with salts upon a molybdenum cathode suspended axially in the crucible. Upon com-pletion of the electrolysis the cathode is removed and cooled, the deposit broken and leached to remove salts. The metal powder is washed with water and dilute acetic acid and dried in vacuo to reduce oxidation. Suitable amounts are then pressed into pellets and heated in vacuo by high-frequency induction, using a thoria crucible. The uranium melts and flows away from the pellet, leaving a shell, which is largely oxide. In general, this method produced a satisfactory metal, although at times the uranium was not ductile. The investigations recorded here were made to find the cause of this embrittlement. It was known that the metal generally contained carbon, derived from disintegration of the graphite crucible in which electrolysis is conducted, in amounts dependent upon the thoroughness of washing the metal powder. Accordingly, analyses of several samples, both ductile and brittle, were made by combustion and absorption of C02 in Ascarite, using air instead of oxygen to reduce the temperature and rate of oxida-tion. Several of these metals were made with special precautions to reduce carbon content. The results show no relationship between ductility and carbon content in the range investigated (Table 1).

Jan 1, 1935

By N. F. Fiore, M. F. McGuire

THIS communication describes a series of experiments in which dislocation etch pitting was used to ascertain the depth of damage in crystals which were mechanically polished or which were cut with either a commercial metallographic cut-off wheel,* a com- All specimens were cut from single crystals of American Smelting and Refining Co. 99.999+ pct pure copper which were grown from the melt by the Bridge-man technique. The test specimens were disks, with faces being (111) planes and the disk axis a (111) direction. The disks were annealed in a vacuum of 10-5 Torr for 24 hr at 950°C prior to cutting or polishing and were given a light electropolishing in an ortho-phosphoric acid bath before etch pitting. Both Youngs1 and Livingston's2 reagents were used for etch pitting and the reagents gave identical quantitative results; however Livingston's reagent produced less staining and so all photomicrographs shown are of {111) surfaces etched with this solution. The surface of the annealed crystals showed well-defined subboundaries and a density of dislocations of about 1 X 106 per sq cm excluding those present in subboundaries, Fig. 1. The depth of cold work produced during mechanical polishing was determined after an annealed specimen was mounted in a paraffin holding block to protect it from extraneous damage. The exposed (111) surface was ground on metallographic papers and then polished on billiard cloth through 0.05-p alumina abrasive. It was necessary to remove about 0.3 mm (-0.01 in.) to obtain a structure representative of the annealed sur- face, indicating that the crystal was damaged to this depth during mechanical polishing. The cold work caused by standard cutting methods was measured in another series of tests in which cuts

Jan 1, 1967

By T. L. Fritzlen

Extrusion of aluminum alloys in this country is performed mainly by direct extrusion, therefore this paper is confined only to factors affecting the rate of extrusion by this method. Many factors affect the rate of extrusion of aluminum alloys. It is the purpose of this paper to present a discussion on the factors that are subject to technical control. Most of them are closely related, so that a clear-cut distinction between them is rather difficult. However, an attempt will be made to evaluate the effect of each factor separately, as far as possible. The most important factors only will be considered, and these will be discussed in detail under three general headings: (I) characteristics of the equipment, (2) size and structure of the ingot, and (3) temperature of ingot, cylinder, and other parts. It is a well established fact1 that the pressure and the speed of extrusion are related and are exponential functions of one another. Therefore, whenever a certain condition tends, for instance, to increase the pressure required for extrusion, it will reduce the extrusion speed if the pressure is maintained constant. For this reason, in this paper the effect of various conditions is expressed either in regard to their effect on the pressure required or the extrusion speed. Another established fact is the relation- ship between the temperature of the material being extruded and the pressure required to extrude. According to Schi-shokin,= this relationship is of the exponential type, and as the temperature is increased the pressure required is decreased. It would seem from the preceding that the greatest rates of extrusion can be obtained by the use of higher temperatures. However, as is well known, other factors intervene to limit the rate of extrusion of aluminum alloys when increasing the temperature. These factors will be discussed in detail later. Characteristics of the Equipment The capacity of the press determines * the maximum unitary pressure that can be applied for any given cylinder diameter. Pressures used for extrusion of aluminum alloys range from approximately 50,000 lb. per sq. in. to 150,000 lb. per sq. in., dependent upon the alloy and the size of the shape extruded. Higher pressures could be used to advantage, but existing steels limit pressures employed in the production of extrusions. Numerous mechanical characteristics of the extrusion press affect extrusion rate. The most important characteristics of the press itself are: (I) sensitivity of the main pressure valve and accuracy of pressure gauges, (2) accuracy of equipment to heat the cylinder uniformly and to control cylinder temperature, and (3) accuracy of means of measuring the speed of extrusion. The variables subject to control during the extrusion operation are pressure, temperature, and speed, and it is evident that the preceding characteristics

Jan 1, 1946

By T. L. Fritzlen

Extrusion of aluminum alloys in this country is performed mainly by direct extrusion, therefore this paper is confined only to factors affecting the rate of extrusion by this method. Many factors affect the rate of extrusion of aluminum alloys. It is the purpose of this paper to present a discussion on the factors that are subject to technical control. Most of them are closely related, so that a clear-cut distinction between them is rather difficult. However, an attempt will be made to evaluate the effect of each factor separately, as far as possible. The most important factors only will be considered, and these will be discussed in detail under three general headings: (I) characteristics of the equipment, (2) size and structure of the ingot, and (3) temperature of ingot, cylinder, and other parts. It is a well established fact1 that the pressure and the speed of extrusion are related and are exponential functions of one another. Therefore, whenever a certain condition tends, for instance, to increase the pressure required for extrusion, it will reduce the extrusion speed if the pressure is maintained constant. For this reason, in this paper the effect of various conditions is expressed either in regard to their effect on the pressure required or the extrusion speed. Another established fact is the relation- ship between the temperature of the material being extruded and the pressure required to extrude. According to Schi-shokin,= this relationship is of the exponential type, and as the temperature is increased the pressure required is decreased. It would seem from the preceding that the greatest rates of extrusion can be obtained by the use of higher temperatures. However, as is well known, other factors intervene to limit the rate of extrusion of aluminum alloys when increasing the temperature. These factors will be discussed in detail later. Characteristics of the Equipment The capacity of the press determines * the maximum unitary pressure that can be applied for any given cylinder diameter. Pressures used for extrusion of aluminum alloys range from approximately 50,000 lb. per sq. in. to 150,000 lb. per sq. in., dependent upon the alloy and the size of the shape extruded. Higher pressures could be used to advantage, but existing steels limit pressures employed in the production of extrusions. Numerous mechanical characteristics of the extrusion press affect extrusion rate. The most important characteristics of the press itself are: (I) sensitivity of the main pressure valve and accuracy of pressure gauges, (2) accuracy of equipment to heat the cylinder uniformly and to control cylinder temperature, and (3) accuracy of means of measuring the speed of extrusion. The variables subject to control during the extrusion operation are pressure, temperature, and speed, and it is evident that the preceding characteristics

Jan 1, 1946

By JULIAN HINDS

Industrialization is raising the standard of living of people everywhere. The common man is demanding and getting more of everything. Perhaps more markedly than most other things, he is consuming more water. A hundred years ago water for domestic use, in all but a few large centers, was lugged from wells in buckets. This still is true in many rural areas, even in the enlightened United States of America. but pumps and pressure systems are rapidly replacing the "old oaken bucket," even on farms and in isolated country homes. Nevertheless, many still fail to see water as a ?commodity? in the same sense that coal, lumber, fertilizer, and bread are considered as commosities. Water is too frequently taken for granted.

Jan 1, 1949

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N',N'-tetraacetic acid and N'-(2-hydroxyethyl)ethylenediarnine-N,N,N '-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1'9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH's in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH's. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By William Priestley

The author has shown, by .practical experiments, how the rate of cooling steel in the mold governs ingotism, segregation, the formation of dendrites, and the distribution of intergranular material; and the resulting effect these conditions have on the physical qualities of the steel before annealing, after annealing, and after forging. The paper also describes how the structure of steel is affected by the design of the mold and the method of pouring. It is shown that the various constituents of carbon steel segregate differently under different rates of cooling. For the classes of steel covered in this paper, it is concluded that the best physical structure and the most uniform chemical composition is obtained by pouring the steel at a low temperature and solidifying as rapidly as possible in the mold. MUCH time has been devoted, by metallurgists, to the study of steel after solidification and remarkable strides have been made in the heat treatment of steel, but less knowledge is available of the thermophysical, activity of the constituents of steel prior to solidification in the mold. It is known that certain elements added to steel produce marked changes in physical properties, also that other elements added to steel produce similar changes, but we have only meager knowledge as to how these elements combine in steel under different conditions of solidification. It is not sufficient to know, from chemical analysis, that a certain element is present in steel. We should know how this element is in combination with the other elements and whether the combination is such as will give the greatest physical properties. Certain elements go into solid solution with the iron, while others segregate to the grain boundaries and combine with the impurities collected there. Until it is known where an alloy produces the most beneficial effect and a means, is determined for controlling its physical location by altering solidification conditions, or otherwise, we will not obtain the maximum value from our alloys.

Jan 2, 1924

By Basil B. Zavoico

PRODUCTION of crude it in the United States during 1939 totaled about 1.255,776,000 barrels, an average of 3,440,482 barrels per day, 3.41 per cent above the 1938 output of 1,214,355,000 barrels but 1.83 per cent below the record pro¬duction of 1,279,160,000 barrels, in 1937. However only the two-week shutdown of oil fields in the Southwestern States in August and September prevented the domestic crude production from establishing an all-time record in 1939. Demand for all petroleum products for the first ten months of 1939 showed an increase of 7.04 per cent over the similar period of 1938. Domestic demand for all petroleum products was particularly benefited by the increasing industrial activity, advancing 8.37 per cent above the like period of the preceding year equivalent to a volume increment of 256,810 barrels per day; with motor-fuel demand gaining 5.83 per cent and demand for all fuel oils gaining 12.15 per cent over the corresponding period of 1938. The export demand for the first ten months of 1939 was slightly below the export movements during the same period of 1938, declining 0.56 per cent. The European war was a major factor in 1939 for the petroleum industry in the United States, even if, at the end of the year, the war had not yet resulted in the expected large shipments to England and France.

Jan 1, 1940

By R. W. Kewish

The preparation of massive uranium metal containing very low concentrations of a number of light elements by bomb reduction of UF4, with calcium is described. Details of procedures are given for preparing high-purity ingredients for the bomb reduction. The as-reduced uranium metal contained, on the average, less than the following amounts of light element impurities, in ppm: Li, 0.1; Be, 0.1; B, 0.1; C, 25; 0, 70; Na, 1; Mg, 3; Al, 2; and Si, 7. Other impurities for which the metal was examined averaged, in ppm: Ca, < 10; V, < 10; Cr, 2; Mn, 6; Fe, 50; Co, < 5; Ni, 8; and Cu, 1. THE preparation of very high-purity uranium metal in massive form for research purposes is of great importance. Recently the kilogram-scale preparation of uranium metal containing less than 70 ppm of detected impurities was accomplished by Blumen-thal and coworkers by vacuum remelting of high-purity crystals of uranium obtained by fused salt electrolysis.1"3 Albert and coworkers4 have reported successful experiments in lowering the concentrations of certain impurity elements in uranium, notably iron, to a few ppm by the zone-melting method. The present paper describes the preparation of high-purity massive uranium metal by the bomb reduction of UF4, with calcium. Early in 1951 a program was undertaken at the Los Alamos Scientific Laboratory to prepare uranium metal of very high purity with respect to a number of the light elements. The methods considered for this purpose were 1) bomb reduction of a uranium halide with calcium, 2) electrolysis of fused salts, and 3) hot wire decomposition of UI4, The first of these processes had been used extensively at Los Alamos since 1943 (and still is used) for the production of uranium metal.5 In considering the three processes it was evident that either of the last two would require an extensive development program with no certainty of success. On the other hand, a study of available data showed that uranium metal of very high purity with respect to some light elements had occasionally been made in routine processing by the first method. It was therefore decided that an intensive study of the bomb-reduction process would be made to see if it could be improved to yield uranium metal with very low concentrations of light elements. DEVELOPMENT OF PROCEDURES The bomb-reduction process used at Los Alamos consists of reducing UF4 with calcium, using iodine as a booster. The reaction is carried out in a magnesium-oxide crucible enclosed in a steel bomb. Argon is used in the bomb to avoid objectionable side reactions which would occur in the presence of air. All ingredients for this bomb-reduction process were examined as possible sources of light elements. It was known that high-purity UF4 was required. The calcium used in the reductions was a source of carbon and magnesium. The magnesium-oxide crucibles were sources of boron, silicon, and magnesium. The iodine did not appear to be a source of any impurities. Pure UF4- The UF4 for bomb reduction is prepared from U3O3 , by successive reduction to UO2, with hydrogen and hydrofluorination of the UO2, with anhydrous HF. Since it was known that no impurities were normally introduced during the gas-solid reactions, effort was directed toward the preparation of high-purity U3O3. Of the many possible procedures for the purification of uranium solutions the following were investigated: 1) Precipitation of uranium peroxide. (Two procedures were tried. The first consisted of simultaneously adding hydrogen-peroxide and ammonium-hydroxide solutions to a uranyl-nitrate solution, containing citric and malonic acids, at such relative rates that precipitation was carried out at a constant pH of 1.5 The second consisted of simultaneously adding uranyl-nitrate, ammonium-hydroxide, and hydrogen-peroxide solutions to an aqueous solution

Jan 1, 1960

By B. E. Sundquist

The various methods based on solution models for obtaining free energies of mixing from miscibility-gap data have been applied to a number of binary-alloy systems. For nine of these systems there exist experimental thermodynamic data that permit a comparison of the results to experiment. It was found that the method of van der Toorn and Tiedema almost invariably leads to results that are physically unacceptable and that vary drastically with small changes in the miscibility-gap parameters. The subregular solution model is found in all cases, except the Al-Zn, Fe-Cr, and Cu-Pb systems, to exaggerate the free energy of mixing by 30 pct or more. The model developed by Lumsden is found to give results that are often in excellent agreement with experiment and which exaggerate the free energy of mixing by no more than 30 pct. These results and others give evidence that the Lumsden treatment of the effect of unequal atomic sizes and of imperfect configurational randomness due to deviations of AB bond energies from the mean of AA and BB bond energies is adequate for most systems. ANALYTIC expressions are frequently proposed for the dependence on composition of the activities of the components of a solution. Because the development of solution theory is incomplete, these expressions contain parameters which must be determined by experiment. The measurement of activities is often difficult and consequently such measurements are less readily available than are measurements of phase equilibria which, under certain conditions, can also be used to evaluate these parameters. For example, suppose it is known that two structurally dissimilar phases, each of known composition, in an n-com-ponent system are at equilibrium at a given temperature and pressure. n equations can be set up in terms of these parameters expressing the equality of the chemical potential of each component in the two phases. In addition, one can write the Gibbs-Duhem equation for each phase that also contains these parameters. Thus, if these n + 2 equations contain n + 2 parameters, these parameters can be determined (at the temperature in question) from the phase diagram alone. If the average number of parameters in each expression for the activity of a given component in a given phase is V then there will be 2nV parameters involved. Equating 2nV to n + 2 shows that, for n + 2, V = 1. If the temperature dependence of each parameter were to be expressed in some explicit form one could use equilibrium conditions at a number of temperatures to increase V. The situation is much improved when the two phases in equilibrium are structurally similar. It can then be assumed that, stably or metastably, two phases will become one at higher temperatures. Thus the number of parameters involved becomes nV instead of 2nV. Hence, V = 2 for n = 2 using only one temperature. (It is implied here that the activity expressions used are valid over the entire composition range.) In this investigation only the equilibrium of two structurally similar, two-component phases (miscibility-gap systems) will be considered. The various proposed solution models will be applied to a number of these systems and the results compared with available experimental results. All of the analytic expressions that have been proposed for the free energy of mixing of a two-component system are of the form where ?Gmix is the free energy of mixing per mole of solution, N1 and N2 are the mole fractions of components 1 and 2, respectively, and f(Ni, T) is some function of composition and temperature. In the "ideal" solution model f = 0. In the "regular" solution model f = a constant. Since these two models permit only a symmetric equilibrium diagram they will not be considered further here. The simplest model that permits a nonsymmetric miscibility envelope is the so-called "subregular" solution model proposed by Hardy.1 This model gives where the Ci(T) are functions of temperature only. The same expression for f is obtained from the "linear a function" model proposed by Darken and Gurry2 and applied to miscibility-gap systems by Wriedt.3 This model requires that the a function defined by be a linear function of composition (yi is the activity coefficient of component i). This model is not purely hypothetical for it has been found2 to hold true for a number of systems. It is readily shown3 that the f(Nl, T) obtained from this model is of the form given in Eq. [2]. It will be noted that the subregular solution model contains only two parameters and hence both of them can be determined at any desired temperature below the critical temperature, Tc, for a miscibility-gap systems in the manner described previously. At T, the two constants can be determined by equating the second and third derivatives of ?Cmix with composition to zero. Another two-parameter model was proposed by Lumsden4 who set

Jan 1, 1967

By J. W. Mills

This paper&apos;s aim is to demonstrate, by reviewing findings and conclusions of earlier authors and through recording and interpreting the outcome of recent laboratory study of the ores, that the ores around the Gem stocks are metamorphosed equivalents of common siderite-sulfide ores far from the stocks, as was first proposed by Hershey (1912, 1913). That is, all the ores probably have the Precambrian age of 1250 million years reported by Long et al. (1960). Those near the Gem stocks, however, were extensively metamorphosed in Cretaceous time during the emplacement of stocks so their resemblance and relation to other veins in the district are camouflaged.

Jan 1, 1985

By V. Jares

DESPITE the fact that a combination of metals-aluminum-zinc-tin, and sometimes aluminium-zinc-cadmium-is extensively used for aluminum solders, as well as for die-castings, the constitution of these alloys has not yet been made clear. I. BINARY SYSTEMS The system aluminium-zinc is the basis of the ternary alloys under consideration. Their composition was made sufficiently clear by the investigations of Roscnhein and Archbutt,1 Bauer and Vogel,2 Sander .and Meissner,3 Hanson and Gayler4 and Isihara.5 Only the temperature of decomposition of the crystals s seems still to be doubtful, whether it is considered as a compound of Al2Zn3 (according to Bauer and Vogel) or as an intermediate phase of variant composition (according to Hanson and Gayler). This temperature is given by most of the authors, as in the neighborhood of 256° C., only Isihara giving 280° C. As its accurate determination is of special importance in the study of the ternary alloys under consideration it was experimentally controlled in the following manner: An alloy corresponding in composition to the formula Al2Zn3 was made, in which the temperature effect was found to be the greatest. This was drilled and a silver-constantan thermoelement inserted into the cavity so as to be in direct contact with the alloy. The whole was then very slowly heated and the heating and cooling curves determined. The transition temperature from the heating curve was found to be 281° C., whereas-from the cooling curve it was 252° C.

Jan 10, 1926