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By L. S. Austin

I. Introduction............ 431 II. Organization............ 432 III. Production............ 434 IV. Transportation............ 435 V. Sampling..........436 VI. Concentration............ 440 VII. Blast-Furnace Plant........... 442 1. Construction........... 442 2. Operation............ 450 VIII. Advantages of Large Furnaces........ 455 1. Saving in Fuel........... 455 2. Saving in Jacket.Water..... 455 3. Quick and Large Discharge of Matte and Slag... 455 4. Decrease of Incrustation... 456 5. Elasticity of Operation..457 6. Large Flow Through Fore.Hearths...4. 57 7. Alterations Without Interruption..458 8. Variations in the Composition of Slag....458 9. Less Labor-Cost.......... 458 10. Less Initial Cost.......... 460 IX. Briquetting.Plant........... 460 X. Roasting-Plant............ 462 1. Kilns............ 462 2. Reverberatory Furnaces...468 XI. Converter-Plant........... 474 1. Construction ..........474 2. Operation.......... 476 XII. Flues and Stacks........... 478 XIII. Arsenic-Plant............ 480 XIV. Coke-Washing Plant.... 452 XV. Slime.Ponds ........... 483 XVI. Brick-Plant............ 484 I. Introduction. The Washoe plant; in Anaconda. Mont., together with the local street-railroad, ranches. a foundry and machine-shop. A

Jan 1, 1907

By L. E. Young

IT has been said the British Empire was built on British Coal. In all the postwar planning for Great Britain the necessity for producing cheap coal and the prosperity of the coal industry are given first consideration. On Jan. 23, 1945, there was released in London a "Report to the Colliery Owners" which had been awaited with great interest. This was entitled "A Plan for Coal" and was the recommendation of Robert Foot, chairman of The Mining Association (Colliery Owners), prepared at their request. Presentation of the "Plan" at this time is particularly significant as it is an answer to the demand for nationalization of the coal industry by the Labour Party and at the same time is a carefully considered program for postwar reconstruction, prosperity, and stability. In the words of Mr. Foot, If the coal industry for the first ten years after this war is to find itself in a situation similar to the one it occupied for the ten years following the last war, with its record of disputes, strikes, stoppages, short-time working, unemployment, and, with it all, a completely insufficient margin of profit, and all the insecurity and instability in our basic industry that was brought with them, it is goodbye to any real prospect of full employment, social security, and high standard of living. To present an elaborate review of the conditions which have brought to a crisis the unfortunate situation in the British coal industry is here unnecessary, but certain of the salient points

Jan 1, 1945

By Robert K. Linn

The New ldria Mining District is in the southern part of the Diablo mountains of the California Coast Range, 140 miles southeast of San Francisco. The district, noted primarily for quicksilver, also has become important recently as a producer of short-fiber chrysotile asbestos. Between 1853 and 1966, the New Idria district produced 568,092 flasks of quicksilver valued at about $55,600,000, 99 per cent of which was recovered from one deposit, the New Idria mine. In 1944, the district was ranked third in all-time production of North American quicksilver districts, and, since that time, the New Idria mine produced an additional 129,045 flasks, placing the district and the New Idria mine second in all-time production. The major structure of the region is the northwest-trending Coalinga anticline consisting of an asymmetric dome of sedimentary beds ranging in age from Jurassic to Quaternary and marked at its northwest end by an oval body of sheared serpentine 14 miles long by 4 miles wide. The serpentine core, rimmed by Franciscan sandstone of probable Jurassic age, was uplifted in stages between Jurassic and Quaternary time and was intruded along a ring of faults into beds of the Panoche Formation of upper Cretaceous age. The core of serpentine and Franciscan rocks is the locus of about 20 quicksilver mines that rim the faultbounded core and lie within the serpentine mass. The host rock of the most productive deposits is altered Panoche shale and sandstone that lies intermittently along the perimeter of the core. Deposits of the New Idria group of mines and those of a few other small mines lie along the northeast contact in the footwall of the New ldria thrust fault, and a few others occur on steep normal faults around the south and southwest. The chief ore mineral in all quicksilver mines is cinnabar, but minor amounts of metacinnabar and native mercury are found in some of the mines. Ore shoots were deposited in fracture zones and stockworks in altered Panoche shale and sandstone and in definite fissure veins in Franciscan sandstone. Rocks made highly amenable to fracturing by hydrothermal alteration were fractured extensively by late faults. The resulting fracture zones, located along the late faults and at changes in strike or dip of the hanging wall or footwall, are the principal controls of most ore shoots. The largest and richest ore shoots are those of the New Idria mine. The major ore bodies occur in fractured shale and sandstone beneath the New ldria thrust fault at its junction with major tear faults.

Jan 1, 1968

By Norman C. Stines

Russia's mineral potential is a secret that has been effectively kept by the Iron Curtain. There is no conclusive data and because of its extreme importance to the Free World, the subject is greatly discussed. Opinions range from those presented by Paul Tyler in his article "Russia's Mineral Potential," June issue of MINING ENGINEERING to those of Norman C. Stines, presented herewith. Mr. Stines is a consulting mining engineer of Los Gatos, Calif. He was in Russia, China, and Manchuria from 1909 to 1918 as a mining executive. From 1917 to 1919 he served as assistant military attache Intelligence Branch U. S. Army in Petrograd, Russia.

Jan 11, 1951

By D. Pearson

INTRODUCTION In 1975 278x10 3 tonnes of zinc was consumed in the United Kingdom, of which 69.3x10 3 tonnes was obtained from secondary sources. Of this secondary zinc 37.7x10 3 tonnes was used in brass making, the remainder was used in non metallic applications - eg oxides and salts. Many forms of zinc-bearing wastes arise, for example as galvaniser's drosses and residues, fumes from ferrous and non-ferrous metallurgical processes, and filter cakes from rayon manufacture and metal finishing. In the case of zinc-bearing dusts and fumes, the quantities available for recycle are at present restricted by the failure to collect them efficiently, hut environmental factors are leading to improvements in gas cleaning, with the result that quantities collected will increase and then exceed those required for the production of chemicals, so that some dusts may either have to be dumped or processed to metal. The recovery of zinc from steelmaking dusts is practised in W. Germany (1) and Japan (2) employing processes based on reduction in rotary kilns in order to produce sponge iron and a zinc- rich oxide suitable for feeding to the zinc-lead blast furnace. Although the zinc-lead blast furnace is the only zinc-making process used in the UK, no similar treatment of steelmaking dusts is carried out, a pilot scheme was tested by the British Steel Corporation, but development was abandoned for economic reasons. It appears to be cheaper to pelletise suitable dusts and export them for treatment elsewhere.

Jan 1, 1981

THE members arrived at Ticonderoga, N. Y., at noon, Tuesday, October 15th, and were received by Mr. Cyrus Butler, Chairman of the Local Committee of Arrangements. During the afternoon the works of the American Graphite Company and the Horicon Iron Company were visited under the guidance of Mr. Butler, President of both companies, and of Mr. William Hooper, Superintendent. An excursion was then made, in carriages, to old Fort Ticonderoga, on Lake Champlain, after which the party were driven to the Rogers Rock Hotel, on Lake George. The first session of the Institute was held in the parlor of time hotel on Tuesday evening. Mr. Eckley B. Coxe, President of the Institute, opened the proceedings with the following address: I shall ask your attention, this evening, to a few reflections upon the subject of mining engineering as a profession in the United States, its past, its present, and its future, and its duties and oppor¬tunities with reference to the proper development of our great min¬eral resources. Thirty years ago, there were scarcely any mining engineers in this country, and but few in England, and there were no institutions where young men could be educated for the profession in the Eng¬lish language. France and Germany have been able for about a century to boast of mining schools of a high character, that number among their graduates such men as Humboldt, Weisbach, Rittinger, Combes, and Gruner. Of the few we then had worthy of the name of "mining engi¬neer," some had studied in the continental academies, and others were graduates in the school of practical experience, and had learned their profession in mines and smelting-works. Their work con¬sisted principally in making surveys and maps of mines and mining properties, geological reports, and analyses of ores ; but the mining engineer whom we often meet with now, who has studied chemistry, physics, mineralogy, geology, mechanics, and drawing; who is more or less familiar with machinery and its construction, and with the practical management of mines or smelting-works, and who is an expert in some one branch of his profession, would have been very difficult if not impossible to find in the United States. The induce¬ments held out to ambitious and talented young men to enter the

Jan 1, 1879

By Kidd, Robert L.

INASMUCH as galena and sphalerite flotation concentrates are being produced that contain over 95 per cent galena or sphalerite, it is not unreasonable to believe that a flotation concentrate assaying at least 80 per cent of native gold can he secured provided the gold is free. As yet, little if any fundamental information has been published concerning the flotation of free gold either alone or in the presence of sulfides. So far, we are unable to make as complete a separation of gold from sulfide minerals by flotation as is possible in, the separation of one sulfide from another by this method. An introductory study of the flotation of several free gold ores has been made in our Utah laboratories. For this study three general types of gold ores were chosen, namely: (1) Quartzite containing 0.26 oz. gold per ton in which no base metals are present; (2) sulfide ore (2.04 oz. Au; 1.31 oz. AO containing pyrite as the only sulfide present and the gold free; and (3) oxidized ore (1.10 oz. Au; 0.70 oz. Ag) from an oxidized zone of the vein from which sulfide ore (No. 2) was taken; little sulfide iron was present.

Jan 1, 1932

By Nicholas J. Grant, H. C. Chang

TRANSCRYSTALLINE fracture surfaces of the cleavage type have been examined by microscopy and X-rays for several metals.' These investigations revealed that the fractured surfaces were not flat and invariably had cleavage and other deformation markings on them. On the other hand, the study of inter crystalline fracture surfaces has been limited. Perryman, in a recently published paper on the inter crystalline fracture of ß-brasses,' found that a thin layer of heavily deformed metal was invariably associated with these surfaces. Furthermore, the thickness of this layer was found to depend on the orientation of the grain boundary surface with respect to the applied stress. The mechanisms of grain boundary sliding and intercrystalline fracture have been presented in two previous papers,which described certain aspects of the deformation of a 20 pct Zn-A1 alloy. It is the purpose of this paper to present some observations on the structure of intercrystalline fracture surfaces and to correlate the structure of such surfaces with the mechanism of intercrystalline fracture. Experimental Techniques—The high purity 20 pct Zn-Al alloy was generously supplied by the Research Laboratories of the Aluminum Co. of America. Two sizes of specimen were used; the first had two parallel flat surfaces of dimensions 1x0.17x0.09 in. and the second was round with a 0.25 in. diam. A grain diameter of 1 to 3 mm was obtained by annealing the specimens at 1000°F for 24 hr. The specimens were then air cooled. The specimens were subjected to creep at 500°F and 2300 psi. The rupture times ranged from % to 3 hr, with one room temperature tensile test. It has been mentioned previous1y" that the intercrystalline fracture surfaces of this alloy, when tested under the conditions given above, are sharply defined. In the optical examination of the fracture surfaces, whenever possible, magnifications of at least X250 were used. The locations of the regions examined, both optically and by X-rays, were selected to give several fracture surface orientations with respect to the stress axis and to the specimen surfaces. This was possible for the X-ray studies since the grain diameters were large compared to the X-ray beam. A film to specimen distance of 3 cm, a 1 mm pinhole and Cr radiation were used for the Laue back reflection pictures.

Jan 1, 1957

By A. C. JR. Boyle

I. INTRODUCTION THE geological field work of the Bully Hill district, upon which this paper is based, was begun July 1, 1908, and covered a period of three months. The time was found too short for a complete report and the district was again visited in the early part of July, 1912,. from which time detailed study of the locality continued until September of the same year. This paper is the result of observations made in the mines in the immediate vicinity of Winthrop, Shasta county, Cal., during these two periods of study. The preparation of this report has been greatly facilitated by various courtesies rendered the writer by D. M. Riordan, President of the Bully Hill Copper Mining & Smelting Co., and by John B. Keating and Herbert R. Hanley, managing officers actively in charge at the mines. The elaboration and further study of the notes and collections were carried on in the laboratories of the Departments of Geology and Mining at Columbia University, and the writer takes pleasure also at this point in expressing his acknowledgments to Profs. James F. Kemp, A. W. Grabau, Charles P. Berkey, and William Campbell, for advice and assistance. In order that one may appreciate at first reading the significance of some of the details which follow, and for the sake of clearness, a brief outline of the geological relationships is here given, together with certain conclusions which have been reached regarding the genesis. of the ores and the gypsum masses. In the Bully Hill mining district an associated series of Triassic lavas and tuffs, chiefly andesites, is preceded as well as followed by sediments. The entire system is tilted so that the original bedding planes dip in general to the southeast. The surrounding region has been greatly disturbed, and in the immediate vicinity of the mines close folding of the later sediments and extreme shearing of the igneous rocks locally is a striking feature. Into the nearly vertical shear zones have been intruded post-Triassic dikes of various rock types in the following order: alaskite-porphyry and andesite-porphyry. Outside the area under consideration diorite dikes are known, but they will not receive attention further than to note that' they, probably, represent a differentiation product of the same magma from which the other two dikes came. In this connection all the dikes have an important bearing on the origin of the ores and of the gypsum found in the mines.

Jan 1, 1914

By H. F. Gossenberger, J. J. Tietjen, J. J. Gannon, C. J. Nuese

External quantum efficiency measurements at 300" and 77°K are presented for vapor-grown GaAs and GaAs1-xPx electroluminescent diodes as a function of junction depth and doping. In GaAs, external efficiencies are found to decrease exponentially with increasing junction depth, defining an average absorption coefficient of 900 cm-1 at 300°K and 350 cm-1 at 77°Kfor epitaxial layers of p-type GaAs. It is shown that photon absorption losses dominate at room temperature and, in fact, account for most of the external efficiency degradation between 77° and 300°K. Healever, the internal ('junction) quantum efficiency is also found to decrease by a factor of 3.5 between 77" ALTHOUGH rapid progress has been made in recent years with GaAs, Gap, and their alloys for use in electroluminescent diodes, there are still important unknown factors related to the performance of these de- and 300°K. The dependence of GaAs efficiencies on donor and acceptor concentrations is presented, illustrating best efficiencies at donor concentrations of 1.5 to 2x 1018 cm-3 . External efficiencies are found to be independent of acceptor concentrations less than 3 x 1019 cm-3 but to degrade at higher doping. The fabrication of GaAsi-xPx electroluminescent diodes is briefly discussed. External efficiencies here for planar uncoated diodes are about 0.035 pct at 300°K and 0.4 pct at 77°for x = 0.42. A brightness of about 8500 ft-Lamberts is attained at 77°K and of 315 ft-Lamberts at 300° K. for curvent densities of 10 amp per sq cm. vices. For example, although the external efficiency is known to decrease by factors of typically 10 to 30 between 77°K and room temperature, the exact causes of this are still uncertain. Experimental results of ill' and carr2 with zinc-diffused electroluminescent diodes suggest that this external degradation is almost entirely due to increased absorption losses at room temperature, with a relatively temperature-independent internal efficiency; recent calculations by Gonda et al.3 corroborate this hypothesis. In contrast, Pilkuhn and Rupprecht4 find the internal efficiency of solution-grown GaAs laser diodes to degrade from 100 to 66 to 40 pct as the temperature is increased from

Jan 1, 1969

By Sherwin F. Kelly

THE present lull in engineering activities presents an advantageous moment for inquiring into the position now occupied by geophysics in its various fields of application. The recent over-expansion in all lines of work resulted in an uncritical employment of these methods of exploration which was bound to have its harmful reaction. The pendulum has now swung back, producing a decidedly hypercritical attitude toward the new science that had been recently welcomed so joyfully as the panacea for prospecting troubles. The severe retrenchment in exploration has forced upon us a period of waiting and, it is to be hoped, of profitable contemplation. This can well be employed in trying to pass a reasoned judgment on what position geophysics should occupy in the new geological exploration programs that will inevitably ac- company the looked-for industrial recovery.

Jan 1, 1931

By AIME AIME

AT FOUR O'CLOCK members gathered in the auditorium for the annual business meeting of the Institute which, according to its charter, must be held on the third Tuesday of February each year. President Turner presided and after the usual formal action on minutes announced that he would create a precedent by transferring the President's annual address (which by tradition has always been delivered at the banquet on Wednesday evening) to the business meeting, and, furthermore, would only present a brief abstract of it. Since it appears in full on pages 127-131 of this issue it can be followed with the careful attention its thoughtful analysis of current conditions deserves.

Jan 1, 1933

By C. H. Mathewson

EXCEPTING the joint sessions on gases in metals held during the day on Tuesday, the Institute of .Metals opened its activities with a division dinner at the Commodore on Tuesday evening, with Sam Tour, retiring chairman, presiding. W. M. Corse, secretary-treasurer, outlined the financial status of the division and stated the investment fund is becoming large enough so that in the near future it will be possible to pay all expenses of a foreign lecturer once in two years and not rely on an extended speaking tour to cover expenses. W. B. Price reported on his attendance at the Zurich, Switzerland, meeting of the International Society of Testing Materials and gave a graphic account of his visit to the Grand Salon, his meeting with Mussolini, and his audience with the Pope. Buffalo was announced as the place of the fall meeting, to be held during the week of Oct. 3.

Jan 1, 1932

[ ] John M. Davis has left Western Machinery Co. to take a job as project engineer with Baroid Sales Div., National Lead Co., and is now located at Houston, Texas. C. W. Allen, general manager of the mining dept. of the Cleveland Cliffs Iron Co., visited the firm's iron mines on the Mesabi iron range of Minnesota recently. Thomas P. Anderson, mining engineer and geologist, has resigned from the Raw Materials Div. of the U. S. Atomic Energy Commission where he was assistant chief of the Denver Exploration Branch. He will enter private practice in Golden, Colo. James E. Atkinson, consulting mining engineer and geologist, left New York for Colombia, S. A., as general manager for Cia Minera Choco-Pacifico, S. A., operating five dredges in gold and platinum on the Pacific coast of Colombia. Russell H. Bennett has been elected a director of Placer Development, Ltd. with head office in Vancouver, B. C., and is also a director of its subsidiary, Canadian Exploration, Ltd., which mines and mills lead, zinc, and tungsten ores at a property near Salmo, B. C.

Jan 1, 1952

By A. Coskun, J. F. Elliott

The activity of aluminum in liquid Al-Fe alloys .has been measured by an improved version of the transportation method in which the metallic vapor has been collected by its solution in a metallic condenser. The results can be represented by the equation: log yAl = -3.0(1 - xAl2) (0.6 < XAl < 1.0) This equation applies at 1315°C. MORRIS and zellarsl adapted the transportation method for measuring the vapor pressure of a com- ponent of an alloy at high temperature. We have modified their technique further2 for use with metals that are strong oxide formers. In the present case the method has been applied to the Al- Fe system to obtain the activity of aluminum in the liquid region at 1315°C. Dried ultrahigh-purity hydrogen (Matheson) is the carrier gas. The operations, Fig. 1, of deoxidizing the gas, equilibrating the gas with the sample at 1315";, and then collecting the aluminum vapor are all accomplished within a single, continuous alumina tube to avoid contamination of the system by leaks. De-oxidation to a very low level of PO2 (<10-25 atm) is Obtained by passing the hydrogen through a tightly packed bed of aluminum powder. The temperature of this bed increases to approximately 550°C in the direction of the gas flow. The boat containing three pellets of the alloy is supported on the end of a

Jan 1, 1969

By H. M. Morse

This report covers the period from Jan. I, 1943 to Dec. 31, 1943. During the year, II2 wells were drilled in Mississippi, as foilows: wildcats drilled and abandoned, 54; wildcats producing oil, 4; oil wells drilled in oil fields, 26; oil wells drilled in fields, dry and abandoned, 10; sulphur-test wells drilled, 14; salt-water-disposal wells, 3; core tests, I. Prospecting Geophysical work in Mississippi during 1943 amounted to 1127 crew weeks, divided as follows: reflection seismograph, 809 weeks; gravity meter, 285; magnotometer, 30; torsion balance, 3. A considerable amount of core drilling was done over a large part of the state. The complete data on this activity are not available at the present time. Salt Domes To date, the following salt domes have been discovered in Mississippi: Midway, Edwards, Glass, Newman, Tatum, Oak-vale, Kings, Halifax, D&apos;Lo, Hazlehurst, Byrd, Leedo, Prentiss, Carson, Moselle, Monticello, Ruth, Keno, Taylorsville. New Oil Fields Lincoln County.—On March 10, 1943, the California Company completed its Smith No. I in sec. 4, T. 7 N., R. 7 E., Lincoln County, as an oil well and produced 29 bbl. of 25" gravity oil in 24 hr. through a fi-in. choke. Two outpost wells have been drilled in this area by the California Company, and both have been abandoned as dry holes. Madison County. —Love Petroleum Co. completed its J. R. Anderson No. 2, sec. 2, T. 8 N., R. I W., Madison County, on Sept. 7, 1943. This well produced 135 bbl. of approximately 30" gravity- oil in 24 hr. through a )/4-in. choke. The production comes from a sand or porosity in the upper part of the Chalk formation of the Cretaceous age. Adams County.—The California Company drilled its National Gasoline Co. of Louisiana No. I in sec. 52, T. 7 N., R. I W., to a total depth of 10,383 ft., and at 10,280 ft, it perforated and obtained gas and a condensate. The well had several showings in the Wilcox of the Eocene age. Several of these showings were tested and the well finally was completed at 5888 ft. on Oct. 6, 1943, producing 44" gravity oil in the second sand in this formation. No other wells were completed in this field during the year. However, a number of wells are contemplated in the near future, and locations have been staked by the California Company. The Oklahoma Pipe Line Co. will market the oil through its pipe-line facilities. Wayne County.—The Gulf Refining Co. drilled Davis No. I in sec. 2, T. 9 N., R. 9 W. in Wayne County. After several stem tests 545&apos;-in. casing was set at 6850 ft. and production was obtained in the so-called Massive Sand of the Lower Tuscaloosa. The well produced 359 bbl. of oil in 24 hr., and it Was completed on Oct. 4, 1943. Other locations have been staked ill this area and probably will be drilled in 1944 by

Jan 1, 1944

By H. M. Morse

This report covers the period from Jan. I, 1943 to Dec. 31, 1943. During the year, II2 wells were drilled in Mississippi, as foilows: wildcats drilled and abandoned, 54; wildcats producing oil, 4; oil wells drilled in oil fields, 26; oil wells drilled in fields, dry and abandoned, 10; sulphur-test wells drilled, 14; salt-water-disposal wells, 3; core tests, I. Prospecting Geophysical work in Mississippi during 1943 amounted to 1127 crew weeks, divided as follows: reflection seismograph, 809 weeks; gravity meter, 285; magnotometer, 30; torsion balance, 3. A considerable amount of core drilling was done over a large part of the state. The complete data on this activity are not available at the present time. Salt Domes To date, the following salt domes have been discovered in Mississippi: Midway, Edwards, Glass, Newman, Tatum, Oak-vale, Kings, Halifax, D&apos;Lo, Hazlehurst, Byrd, Leedo, Prentiss, Carson, Moselle, Monticello, Ruth, Keno, Taylorsville. New Oil Fields Lincoln County.—On March 10, 1943, the California Company completed its Smith No. I in sec. 4, T. 7 N., R. 7 E., Lincoln County, as an oil well and produced 29 bbl. of 25" gravity oil in 24 hr. through a fi-in. choke. Two outpost wells have been drilled in this area by the California Company, and both have been abandoned as dry holes. Madison County. —Love Petroleum Co. completed its J. R. Anderson No. 2, sec. 2, T. 8 N., R. I W., Madison County, on Sept. 7, 1943. This well produced 135 bbl. of approximately 30" gravity- oil in 24 hr. through a )/4-in. choke. The production comes from a sand or porosity in the upper part of the Chalk formation of the Cretaceous age. Adams County.—The California Company drilled its National Gasoline Co. of Louisiana No. I in sec. 52, T. 7 N., R. I W., to a total depth of 10,383 ft., and at 10,280 ft, it perforated and obtained gas and a condensate. The well had several showings in the Wilcox of the Eocene age. Several of these showings were tested and the well finally was completed at 5888 ft. on Oct. 6, 1943, producing 44" gravity oil in the second sand in this formation. No other wells were completed in this field during the year. However, a number of wells are contemplated in the near future, and locations have been staked by the California Company. The Oklahoma Pipe Line Co. will market the oil through its pipe-line facilities. Wayne County.—The Gulf Refining Co. drilled Davis No. I in sec. 2, T. 9 N., R. 9 W. in Wayne County. After several stem tests 545&apos;-in. casing was set at 6850 ft. and production was obtained in the so-called Massive Sand of the Lower Tuscaloosa. The well produced 359 bbl. of oil in 24 hr., and it Was completed on Oct. 4, 1943. Other locations have been staked ill this area and probably will be drilled in 1944 by

Jan 1, 1944

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&apos;,N&apos;-tetraacetic acid and N&apos;-(2-hydroxyethyl)ethylenediarnine-N,N,N &apos;-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&apos;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&apos;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&apos;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 R. F. Hehemann, D. J. Cometto, G. L. Houze

The w transformation in the Zr-Nb system was studied using X-ray diffraction, dilatometric, re-sistornetric, hardness, and metallographic techniques. w forms in a diffusionless, completely reaersible manner on quenching and in a diffusion-controlled manner- on aging. The temperature at which w begins to form on quenching was determined as a Junction of composition and was found to decrease with increasing solute content. w formed bv aging establishes a metastable equilibrium with an enriched ß phase. The ß/w + ß transus has been determined for this metastable equilibrium and employed to rationalize retrogression and reversion phenomena observed in these alloys. The decomposition mechanism is discussed in terms of a gradual or continuous transformation from ß to the w state. BETA- stabilizing alloying elements lower the MS temperature of the martensitic bcc (ß) to hcp (a&apos;) transformation in zirconium and titanium alloys. In certain titanium alloys, a lower symmetry modification of the martensitic structure, termed (a"), also has been reported.1,2 These martensitic transformations are suppressed when the amount of the ß-stabilizing element exceeds a critical level. However, the high-temperature ß phase cannot be quenched to room temperature without change. At alloy contents just above the critical level, |ß trans-forms to the w phase when cooled rapidly.3-6 The amount of w in quenched alloys is reduced by increasing alloy content, and this phase virtually disappears above a critical composition.5 In addition to the transformation during cooling, w also can be formed by aging ß at temperatures below approximately 500°C, and significant alloy enrichment of retained 13 accompanies the isothermal transformation.1-8 The structure of LC is closely related to that of the ß from which it forms.9-15 The bcc (ß) lattice can be generated using a hexagonal cell with three atoms located at (000) and ±(2/3, 1/3, 1/3). This cell has an axial ratio of 0.612 and is oriented with respect to the cubic cell such that (0001)H (111)C and [1120]H [101]C. Consequently, there are four possible orientations of the hexagonal cell, associated with the four (111) planes of the bee lattice. Formally w can be obtained from 0 by allowing the two atoms at the ±(2/3, 1/3, 1/3) positions to approach the coordinates ±(2/3, 1/3, 1/2) and there are four equally probable orientations of w for each 0 grain. In titanium alloys w retains the cubic axial ratio of 0.612" and hence also can be indexed as triply cubic, but this is not the case for aged Zr-Nb alloys where w is clearly hexagonal with an axial ratio of 0.622." The lattice parameters and atomic positions of w depend on thermal history and alloy content. The atomic positions (000), ±(2/3, 1/3, 1/2) provide reasonable agreement between calculated and observed diffracted intensities for w in the fully aged condition.10,14 In the quenched condition, on the other hand, the atoms appear to be displaced from the central plane12,13,15 and assume positions ±(2/3, 1/3, Z = 0.42-0.48) rather than ±(2/3, 1/3, 1/2). This results in a structure with trigonal rather than hexagonal symmetry. The readily detectable parameter and axial-ratio changes of w in Zr-Nb alloys make this system especially attractive for studying the structural changes that occur in the formation and aging of w. Particular attention in this investigation has been directed to the relationship between the structure of w in the quenched and aged conditions, and to certain aspects of the reaction kinetics. MATERIALS AND PROCEDURE Zr-5, 12, 17.5, and 25 pct Nb alloys were prepared by a double arc-melting practice, encased in stainless-steel cans and hot-rolled to 1/8-in.-thick sheet.* Charged weights have been employed for the niobium contents and interstitial analyses are reported in Table I. Dilatometric, X-ray diffraction (filtered CuK, and MoK, radiation), metallographic, and hardness techniques have been employed to follow the transformations during isothermal and quench-aging heat treatments. In quenched specimens, the electrical resistivity also was studied. Betatizing was conducted for 1 hr at 900°C. With the exception of the isothermal dilatometric studies, samples were

Jan 1, 1965

By M. E. Wadsworth, J. R. Lewis, J. M. Quets

Samples of snythetic magnetite were reduced in hydrogen at various partial pressures and temperatures. The reaction mas found to be surface controlled and directly proportional to hydrogen partial pressure over the temperature range studied (400° to 1000°C). A transition in the mechanism occurred at approxirnately 590°C. This has been attributed to a change in the slow step of the reduction reaction resulting from the presence of stable wüstite at higher temperatures. Below 590°C the heat of activation for the reduction was found to be 14,700 cal per mole and it was 3,200 cal per mole above 590°C. THE reduction of the oxides of iron has been a subject of study and interest for many years. Edstrom1 has reviewed the work up to 1953 and his findings provide much basic information concerning details of the reduction of hematite (Fe2O3 ) and magnetite (Fe3O4) with both H2 and CO. He concluded that below 600°C the reduction of both hematite and magnetite was essentially identical, since the rate was controlled by a surface reaction at a magnetite gas interface and the iron formed was very porous. The decrease in the reduction rate for both hematite and magnetite immediately above 600°C was attributed to the formation of a stable wüstite phase across which diffusion was very slow. The wide difference in reduction kinetics for hematite and magnetite above 600°C was explained in terms of the character of the wüstite formed. The rate of magnetite reduction increased slowly with temperature beyond the minimum immediately above 600°C and rates equivalent to those observed at 550°C were not obtained until the temperature was increased beyond 850oC. Edstrom and Bitsianes2 studied the solid-state reduction of magnetite, the reaction of which can be written (4x-3)Fe + Fe3O4—4 FexO [1] where x is between 0.83 and 0.95. The rate was found to be controlled by the kinetics of transport of iron ions through the wüstite phase. Bogdandy and Riecke3 studied the kinetics of reduction of small grains of iron oxide in hydrogen and qualitatively attributed the slow step in the reduction process to the diffusion of hydrogen and water vapor through pores. McKewan4 has analysed the data of Joseph,5 Stalhane and Malmburg,6 and Lewis7 and has demonstrated that the kinetics of reduction of both hematite and magnetite are controlled by surface reactions and also that the variation in surface area during reduction must be accounted for. McKewan was able to correlate the reduction data by the equation rodo[1-(1-R)1/3] = Kt [2] where ro is the initial particle radius, do is the density of the iron oxide, R is the fraction reduced at time t, and K is a rate constant. The applicability of Eq. [2] for temperatures above 600°C where a stable wüstite phase is present, indicates the slow step in the over-all kinetics does not result from diffusion unless diffusion occurs laterally along the oxide metal interface or through a wüstite layer of constant thickness. Diffusional control through a layer of wüstite is unlikely, however, in view of the pressure effects demonstrated by Tenenbaum and Joseph,&apos; Diepschlag,9 McKewan,10 and the results of the present study. McKewan has demonstrated a linear rate dependence on the hydrogen partial pressure over the temperature range 400" to 1050°C for the reduction of hematite.

Jan 1, 1961