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By D. B. Gillies

IN 1938 the Republic Steel Corp. announced that it had leased the ore mines and other property of the Witherbee Sherman Corp. at Port Henry, N. Y. The announcement brought forth an interesting reaction. Two questions were asked repeatedly: (1) Is the iron product high grade? (2) Is there a substantial reserve? The answer to both questions was and is a decided and emphatic "Yes."

Jan 1, 1943

By M. Murakami, Y. Murakami, O. Kawano

The formation and growth of Guinier-Preston zones in Al-Zn alloys containing 4.4, 6.8, 9.7, and 12.4 at. pct zn have been studied by the X-ray small-angle scattering method. Particular attention was paid to the effects of small amounts of third elements silver, silicon, and magnesium on the formation and growth of G.P. zones. It was noticed that an appreciable number of G.P. zones were formed during the course of rapid cooling and that the size, volume fraction, and number of these G.P. zones were influenced by the existence of the third elements. During subsequent aging it was also found that the addition of both silver and silicon lowered the temperature for the growth of G.P. zones, whereas the addition of magnesium raised it. These results were explained in terms of the mutual interactions among zinc atoms, vacancies, and the third elements. A number of studies on the formation and growth of Guinier-Preston zones in Al-Zn alloys have been reported.1-4 Panseri and Federighii have found that the initial stages of zone growth take place at temperatures as low as around -100°C. For investigation of the mechanism of the initial stages of zone growth, growth studies must be carried out at low temperatures. In order to investigate the possibility of the formation of G.P. zones by the nucleation mechanism or the spinodal decomposition during quenching which was reported by Rundman and Hilliard,5 the examination of the as-quenched structure must be performed. In this paper the investigation of the early stages of the formation and growth were determined by means of the X-ray small-angle scattering method. With this technique, change of X-ray scattering intensities was measured while quenched specimens were heated slowly from liquid-nitrogen temperature to room temperature. At as-quenched state and after heated to room temperature, investigation of zone size, volume fraction, and zone number per unit volume was carried out. Measurements on these specimens yielded information on the early stages of zone formation and growth. Measurements were made also on specimens quenched to and aged at room temperature. From these measurements the previously reported model6 for the later stages of growth is confirmed; namely, the larger zones grow at the expense of smaller ones. Three elements, silver, silicon, and magnesium, were chosen as the third elements for the following reasons: Silver. In the binary A1-Ag alloy the spherical disordered 77' zones were observed immediately after quenching.7 Therefore, in the Al-Zn-Ag alloys, it is suggested that silver atoms might induce cluster formation during quenching. Also, since the migration energy of the zinc atoms was found to be raised by the addition of silver atoms,' silver atoms may have a great effect of the zinc diffusion, especially during low-temperature agings. Silicon. The effects of the addition of silicon atoms were found to be marked, especially at low-tempera-ture aging. In the binary Zn-Si system, no mutual solid solubilities between silicon and zinc9 and no in-termetallic compounds10 are reported to exist. Shashkov and Buynov11 investigated the behavior of silicon atoms in Al-Zn alloys and showed that silicon was not in the G.P. zones. The interaction between silicon atoms and vacancies is strong enough to increase the quenched-in vacancy concentration.* Magnesium. Magnesium atoms are reported to trap quenched-in vacancies and after much longer aging times these trapped vacancies will become free and act as diffusion carriers.13 Therefore at intermediate aging times, the diffusion of zinc atoms in Al-Zn-Mg alloys will be slower than in the binary Al-Zn alloys, whereas at longer times zinc diffusion will become faster. EXPERIMENTAL PROCEDURE The alloys used in this investigation had compositions of 4.4, 6.8, 9.7, and 12.4 at. pct Zn with or without 0.1 and 0.5 at. pct Ag, Si, or Mg. The alloys were prepared from high-purity aluminum, zinc, silver, silicon, and magnesium, with each metal having a purity better than 99.99 pct. The analyzed composition of the specimens is given in Table I. The measurements of the X-ray small-angle scattering were carried out with foils of 0.20 mm thick. The change of the scattering intensity was always measured at the fixed scattering angle of 20 = 2/3 deg. This angle exists nearly on the position of the intensity maximum. The value of the interparticle interference function14 which has large effect in this range of angles may not change abruptly in the case of the spherical shape of small zones. Therefore, from the above considerations, it is concluded that an increase of the intensity measured at this constant angle corresponds to an increase of the average radius and volume fraction of G.P. zones. The specimens were homogenized at 500°, 450°, and 300°C for 1 hr in an air furnace. For the study of the formation and growth at low temperatures, the foil

Jan 1, 1970

By M. L. Sisson, G. H. Rupp, R. L. Hair

THE iron ore supply for the Pueblo plant of CF&I is obtained from the Sunrise mine in Wyoming and the Duncan and Blowout mines near Cedar City, Iron County, Utah. The Sunrise mine is an underground operation while those in Utah are open pit.

Jan 11, 1953

By J. Chipman, N. J. Grant, J. H. Walsh, T. B. King

WITH the development of adequate sampling and analysis techniques, much information has been obtained concerning the behavior of hydrogen in the steel bath during the course of steelmak-ing operations. From studies of this type it has become clear that the slag has an important role to play in determining the hydrogen content found in commercial products. A knowledge of the behavior of hydrogen in slags is necessary to round out our knowledge of hydrogen in steelmaking practice; with this information we are better able to assess practical methods of control. In this paper a method developed for analyzing slags for hydrogen content, studies of the solubility of hydrogen in synthetic slags, and studies of the variation of hydrogen content in slag and steel in industrial heats will be described. Previous Work—While very little has been done in the past to determine the hydrogen content of metallurgical slags, measurements have been made on such slag-like materials as geologic magmas and glasses. Goranson as made extensive studies of the solubility of water in natural and synthetic granites. Many workers have investigated the solubility of gases in synthetic and commercial glasses, but the recent work of Russell" is the most extensive. Russell found that the solubility of water in glass was proportional to the square root of the water vapor pressure in water vapor-oxygen mixtures. It was found that the solubility could either increase or decrease with temperature depending on the glass composition. Wentrup, Fucke, and Rief,' and Piper, Hagedorn, and Backes' have extracted hydrogen by holding a slag at 1300" and 800°C respectively in vacuum. Wentrup et al. reported hydrogen and water vapor as evolved together while Piper et al. passed the evolved gases from the hot extraction treatment over hot ferromanganese to reduce the evolved water vapor to hydrogen and, therefore, reported the analyses in terms of total dissolved hydrogen. Yavoiskii has reported hydrogen and nitrogen analyses on steelmaking slags. Dobrokhotov, Povol-skii, and Khan have studied the hydrogen content of basic open hearth steel under slags of varying viscosity. These authors reported that the hydrogen content of the steel bath increased as the fluidity of the slag was increased by the addition of bauxite. They recommended that a viscous slag be used and the steel tapped without deoxidation in the furnace to ensure a low final hydrogen content. Analysis of Slags for Hydrogen Development of Apparatus—The vacuum fusion analysis equipment described by Shields, Chipman, and Grant" was modified for the analysis of slags." This method depends upon the reduction of water in the slag to hydrogen, which is readily determined by the method used for hydrogen in steel. Preliminary experiments were made with a eu-tectic ferrosilicon melt as the reducing agent. Other experiments included the use of graphite and molybdenum crucibles. The ferrosilicon alloy bath was found to produce a thick coating on the furnace tube which could adsorb hydrogen. Graphite produced CO by the reduction of FeO, MnO, and SiO2 in such quantities that analysis for hydrogen was virtually impossible. Molybdenum, while giving a low blank value, could reduce the slag sufficiently to produce a volatile oxide which again was found to adsorb hydrogen. The arrangement finally adopted is shown in Fig. 1. The molybdenum sheet served as the induction-heated susceptor, and was separated from the escaping gases by alumina guide tubes. An outer jacket of alumina protected the quartz furnace tube, and alumina and quartz stools completed the assembly. The falling sample is shown wrapped in aluminum foil, 0.002 in. thickness, which acted as the reducing agent' This foil was careful'~ washed in acetone and an d and then dried in hot air before wrapping the weighed slag sample for charging into the apparatus. Investigation of the hydrogen content of the aluminum foil itself showed that a small quantity of hydrogen was released in vacuum, but had no relation to the weight of the aluminum charged. This quantity of hydrogen was

Jan 1, 1957

By M. M. Fine

Normally the U. S. produces less than 10 pct of its annual manganese requirement. About 95 pct of domestic consumption is used by the steel industry.1 The strategic and critical nature of manganese has been recognized by its inclusion in the national stockpile and by intensified research directed toward cataloging and evaluating domestic manganiferous deposits. The USBM has participated in these activities for many years with field and laboratory studies to assess the extent and potential utilization of domestic manganese ores. One area of particular interest is in the vinicity of Batesville, Ark., where deposits have been mined since 1849 for both manganese and ferruginous manganese ores. Production is centered in Independence County, but deposits are also found in Sharp, Izard, and Stone counties in north- central Arkansas. Miser has described the geology and manganese mineralization in some detail.2,3 The rocks of the area are sedimentary, consisting of sandstone, limestone, shale, and chert. The two formations of greatest importance,4 Fernvale lime- stone and Cason shale, are host rocks of the primary manganese mineralization.

Jan 8, 1959

By John D. Wiebmer

Kansas, with its thin seams and tough overburden, may not be anyone's first choice for a coal mining operation. But there are operators making it pay through careful attention to mining techniques and aggressive marketing in the local region. One of the few Kansas coal operators is Bill Patch, who has been in the business for 28 years. Beginning with a single dragline operation near his home in Welch, Okla., Bill's Coal Co. weathered some lean times during the "soft" coal market of the 1950's and 1960's. But his tenacity paid off when new markets began opening up, and the company has grown by leaps and bounds in recent years. In 1975, the Fort Scott mine opened in Bourbon County, Kansas; in 1976, the Porter mine began production in Wagoner County, Okla.; in 1977, the Fulton mine opened near Fulton, Kansas. In addition, the original Welch mine in Oklahoma is still a producer, and this year the company will open a new mine at Chetopa, Kansas.

Jan 9, 1978

By R. N. Edmondson, L. Mair, M. Tenenbaum

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhord Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chipmon, Vice President; T. D. Jones, Treosurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. w. Thornton, Chairman; Dennis Carney, John Chipman, J. C. Fulton I. H. Hollomon H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supenision of the following Publications Committees: Extractive Metallurgy Division: T. 0. King Chairman; S. J. Dickenson, R. P. Hermsdorf R. Schuhmann. Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman F. Lincoln Vogel Jr., Vice-chairman, W. A. Baikofen, R. W. Boliuffi J. H. Bechtold M. B. Beyer. R S. Busk, C. G. Gaetzel, Paul Gordon C. D. Groham, Jr., Robert F. Hehe-mann,' R. I. Joffee, F. c. Joumot Jr lrving R. Kramer A. J. Lena Harold Morglin, C. J. McHargue, Russell A: Meussner, J. B. Newkirk H. W. Paxton, G. E. Pellissier, I. S, Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. 0.. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephon: pEnnsvlvanio 6-9220. Subscription 522 Per year for non-AIME members in United States and North South and Central America; $25 foreign;, $5 for AIME members. Single copies, 54.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed In its publications . . . Copyright 1958 by the American lnstltute of Mining Metallurgical and Petroleum Engineers Inc. . . . Registered cable address AIME New York , . . lndexed in Engineering Index Industrial Arts Index and Chemical Abstrats . . . Application for second class mail privileges ii pending at New York, N. Y. Volume 212, Number 4.

Jan 1, 1959

By R. T. Hukki

John F. Myers (Consulting Engineer, Greenwich, Corm.)—Since the art of comminution has lain practically dormant for many years, it is very interesting that R. T. Hukki approaches the subject with a new concept. One is reminded of the research carried on by A. W. Fahrenwald of Moscow, Idaho, a few years ago. Fahrenwald mounted a steel bowl on a vertical shaft. The balls and ore placed in the bowl were rotated at fast speeds, thus simulating the supercritical speeds used by Hukki. The rolling action of the balls against the smooth shell liner has pretty much the same effect. The action is horizontal in one case and vertical in the other. Both researchers report good grinding activity. It is also constructive that such able investigators give to the students of comminution their interpretation of their laboratory results in terms of large-scale operation. History shows that it takes a lot of time for such radically new ideas to be absorbed by the industry. Typical of this is the present-day activity of cyclone classification in primary grinding circuits. The idea of cyclone classification has been kicking around for 30 or 40 years. Certainly we all suspect that the ponderous grinding mills of today, and their accessory apparatus, large buildings, etc., will ultimately give way to small fast units, just as this has occurred in other industries over the past 50 years. At the moment there is no evidence that ball and liner wear is prohibitively high. In fact, at the time Fahrenwald was demonstrating his high-speed horizontal machine at the meeting of the American Mining Congress, several years ago, he assured this writer that the balls retained their shape much longer than they do in conventional tumbling mills. Rods and balls that slide (as some operators in uranium plants are experiencing) get flat. Apparently the balls have a rolling action. Mr. Hukki's references to the processing capacity of the Tennessee Copper Co. mills is adequate. Those studying this subject will be greatly interested in the paper presented by Richard Smith of the Cleveland-Cliffs Iron Co. at the annual meeting of the Canadian Institute of Mining and Metallurgy in Vancouver April 24, 1958. This paper will be published during the latter part of 1958 in the Canadian Institute of Mining and Metallurgy Bulletin. Hukki's pioneering spirit is to be commended. R. T. Hukki (author's reply)—It has been heartening to read the objective discussion by J. F. Myers. The sincerity of his opinions is further strengthened by the fact that the article he has discussed contradicts in a major way the parallel achievements of his life work. Myers is right in his opinion that in general it takes a long time before new ideas are accepted by the industry. On the other hand, revolutions usually take place at supercritical speeds. There are many indications at present that both the unit operation of grinding and the related subject of size control are now just about ripe for a revolution. In grinding, brute force must ultimately give way to science. Rapid progress can be anticipated in the following fields: 1) Autogenous fine grinding at supercritical speeds will be the first advance and the one that will gain recognition most easily on industrial scale. At this moment, little Finland appears to be leading the world. Crocker recently made a statement that in nine cases out of ten, your own ore can be used as grinding medium more effectively and far more economically than steel balls. This is true. The present author would like to introduce a supplementary idea: In eight cases out of the nine cited above, it can be done at the highest overall efficiency in the supercritical speed range. Fine grinding must be based on attrition, not impact. The path of attrition may be vertical, horizontal, even inclined. 2) In coarse grinding, the conventional use of rods is sound practice. However, even the rods can be replaced by autogenous chunks large enough to offer the same impact momentum as the rods. To obtain the momentum, the chunks must be provided with a free fall through a sufficient height in horizontal mills operated at supercritical speeds. Coarse grinding must be based on impact. Detailed analysis of the subject may be found in a paper entitled "All-autogenous Grinding at Supercritical Speeds" in Mine and Quarry Engineering, July 1958. 3) All conventional methods of classification, including wet and dry cyclones, are inefficient in sharpness of separation. Continuous return of huge tonnages of finished material to the grinding unit with the circulating load is senseless practice. In the near future the present methods will be either replaced or supplemented by precision sizing. These three fields are also the ones to which J. F. Myers has so admirably contributed in the past. Fine Grinding at Supercritical Speeds. By R. T. Hukki (Mining EnGineERInG, May 1958). Eq. 9, page 588, should be as follows: T , c, (a — 6') n D Ltph On page 584 of the article the captions for Figs. 4 and 5 have been placed under the wrong illustrations and should be interchanged.

Jan 1, 1959

By C. S. Finney, John Mitchell

On December 31, 1959, there existed in the United States 15,993 slot-type coke ovens capable of producing 81,447,700 net tons of coke. These ovens were concentrated in 74 coke plants in 21 different states. As of the same date, there were 7448 beehive ovens in existence at 45 plants in the states of Pennsylvania, Virginia, West Virginia, and Kentucky. Total annual capacity of the existing beehive ovens was 4,368,800 net tons, but only 5148 ovens with a capacity of 3,131,600 tons were in operating condition. It is interesting to compare the average dimensions of slot-type ovens built during recent years with the 30 ft x 5 ½ ft x 16 ½ in. ovens erected at Syracuse, N. Y. in 1892. A composite oven built according to the average dimensions of all those erected between 1954 and 1958, for instance, would be 39 ft long. 12 ft high, and 18 in. in width. The coal capacity would be 16 tons as against the 4.4 tons which could be charged to the Syracuse ovens. Of the 15.993 slot- type ovens in existence at the end of 1959, by far the greater number were built by the Koppers Co. whose total of 11,280 ovens included 7891 Koppers- Becker and 3389 Koppers ovens. Of the remainder, there were 3260 Wilputte, 1350 Semet-Solvay, 63 Otto, and 40 Simon Carves ovens. By-product coke oven plants are usually classified either as furnace or merchant plants. According to the definitions used by the US Bureau of Mines, the former are "those that are owned by or financially affiliated with iron and steel companies whose main business is producing coke for use in their own blast furnaces. All other coke plants are classified as merchant. They include those that manufacture metallurgical, industrial, and residential heating grades of coke for sale on the open market; coke plants associated with chemical companies or gas utilities; and those affiliated with local iron works, where only a small part (less than 50 pct of their output) is used in affiliated blast furnaces." The annual coke capacity of the merchant plants during 1959 was 10,393,000 tons. However, the by-product oven of today is essentially an appurtenance of the iron and steel industry, rather more than 87 pct of total by- product coking capacity being concentrated at furnace plants. This was not always so. There was a time when the merchant plants played a much greater part in meeting the US demand for coke and gas. High noon for the merchant plants was reached during the early 1930's. By 1932 there were as many by- product oven installations being operated by the merchant sector of the industry as by the coke divisions of the iron and steel industry (44 of each), and in the same year the merchant plants produced 46.5 pct of all by-product coke made in the country. Since that time their contribution has drastically declined. In 1940 merchant plants were responsible for only 23.2 pct of total US production, and by 1950 their number had decreased to 30 plants which turned out 18.5 pct of the total by-product coke made. At the end of 1959 only 20 of the 74 existing by-product oven installations were merchant plants. They ac- counted for 12.5 pct of the year's production, or 6,849,786 net tons. This percentage has remained fairly constant since 1954. There are several reasons for the decline of the merchant coking industry. For example. On the grounds of economy, quality control, continuity of supply, and so on, the iron and steel industry usually prefers to control its own mines and carbonize its own coal at or near to the blast furnace rather than rely on independent operators for metallurgical coke. As the steel companies have enlarged their own coking facilities, so has the need for coke obtained from other sources declined. Furthermore, not only has the steel industry increased in self-sufficiency by building mare coke ovens during recent years, but it has also progressively improved the fuel efficiency of its blast furnaces. During the years 1947-49 the average coke consumption per ton of pig iron was 1892.8 lb. During 1958 the corresponding figure was 1613.4 lb. There are many individual furnaces where still better results are being obtained, and further reductions in the average may be expected. Perhaps the greatest threat to the merchant coking plant has been the fantastic increase in the use of natural gas and petroleum products for purposes which manufactured gas once served. So deadly has the com- petition from natural gas and oil been that it has almost eliminated by-product oven installations owned by public utilities. In the peak years of the early 1930's there were 23 such public utility plants. In 1960 only two were left. One of these, owned by the Citizens Gas and Coke Utility, was at Indianapolis, Ind.; the other was the plant operated by the Philadelphia Electric Co. at Chester, Pa. The non-utility merchant plants have also been sorely hit. With gas sales revenues reduced, domestic

Jan 1, 1961

By M. L. Holzworth, Philip R. Sperry, Paul A. Beck

INTRODUCTION THE basic work of Z. Jeffries1,2,3 has long ago established the main features of grain growth in the presence of a dispersed second phase. Working with sintered specimens of initially fine grained tungsten, to which various amounts of thoria have been added, Jeffries found that grain growth was inhabited, that is, practically prevented, up to a certain annealing temperature. When this temperature, which increased with the thoria content, was exceeded, extremely large grains developed abruptly from the fine grained matrix. Such a "coarsening temperature" was later found by Gross mann13,14 in certain types of steel, while Bain showed" that in other steels grain growth was gradual, without inhibition and abrupt coarsening. Later work16,17,18,19,21 demonstrated the connection between coarsening and aluminum additions. The viewpoint that the direct cause of inhibition and coarsening in aluminum killed steels is a fine dispersion of aluminum oxide21 appears to be held quite generally, although some doubts have been voiced even very recently.20 In steels with Ti additions the titanium carbide phase is considered responsible for the inhibition effects found.20 The coarsening temperature increases, with the titanium content. That coarsening may occur, as a result of certain heat treatments, even in low carbon rimmed sheet steel, was shown by Samuels,22 He also detected coarsening in a steel ingot of similar composition, after giving it the same heat treatment as that used by him for the sheet material, In this instance the identity of the inhibiting phase has not been determined, However, Tangerding found 23 that even the few small carbide particles, which occur in carbonyl iron, have a very marked inhibitive effect. As a result of an oxidizing anneal at 850°C, large grains begin to form at the surface of the carbonyl iron specimen, and gradually grow inward as the subsurface oxidation of the carbide particles progresses and eliminates the obstruction, The carbide particles can be removed also by annealing in hydrogen, with similar results. But if the oxidizing anneal of 10 hr at 850°C in air, is followed by annealing in hydrogen for 75 hr at the same temperature, grain growth is more spectacular; usually the whole specimen is transformed into a single crystal (approx. 1,5 cm X 5 cm). The reversed procedure, that is, hydrogen annealing followed by oxidizing annealing leads to smaller grains. Tangerding arrived at the logical conclusion that there must have been in his specimens some additional obstruction to grain growth resulting from a minor impurity, other than carbon. It seems likely that this obstruction was caused by an oxide formed during the oxidizing anneal and gradually reduced during the subsequent hydrogen-annealing. Other instances of grain growth inhibition of varying severity, associated with a dispersed second phase, have been described by several authors. Notable examples: lead with 0.06 pct Cu or Ni,24 cartridge brass with 0.12 pct Cr,25 or with up to 0.15

Jan 1, 1948

By C. W. Spencer, J. T. Smith

GRAIN-BOUNDARY surfaces are penetrated by a liquid phase when the liquid-solid interfacial tension is less than one-half the tension of the grain-boundary surfaces. Grain growth may occur in the presence of this liquid phase. burke1 reports that grain growth of this nature has been observed in two-phase ceramic systems. He suggests that the presence of a grain-boundary liquid may accelerate or decelerate the

Jan 1, 1963

By Robert K. Steunenberg, Irving Johnson, James B. Knighton

The activity coefficient of plutonium in liquid magnesium, over the temperature range 650° to 800°C, was obtained from measurements of the distribution of plutoninm between a 50 mole pct MgC12-30 mole pct NaCl-20 mole pct KC1 molten-salt mixture and liquid Zn-Mg alloys. For dilute solutions (0.08 at. pct Pu) the activity coefficient of plutonium was found to vary from 10.1 at 650°C to 12.2 at 800°C. The activity coefficients of plutonium in dilute liquid solutions of plutonium in uranium, silver, lanthanum. cerium, and calcium were estimated to be. The distribution data indicate a value of about 0.1 at 800°C for the activity coefficient of PuCl3 dissolved in the above ternary salt mixture. LIQUID magnesium and several liquid alloys of magnesium with metals such as zinc and cadmium have been shown to be useful solvents in pyrochemical processes for the recovery of uranium and plutonium from discharged nuclear fuels,' and for the separation of transuranium elements.' The present study was undertaken to determine the activity coefficient of plutonium in liquid Pu-Mg alloys in support of process-development work. The activity coefficient of plutonium in liquid magnesium was determined from experimental data on the distribution of plutonium between a liquid ternary MgC12-NaC1-KC1 salt mixture and various liquid Zn-Mg alloys. The distribution data were used to calculate the ratio of the activity coefficients of plutonium in liquid zinc and in liquid magnesium. The activity coefficient of plutonium in liquid magnesium was then computed from the known activity coefficient of plutonium in liquid zinc. It was not necessary to know the thermodynamic properties of the molten-salt system explicitly. The major features of the Pu-Mg system have been reported by Schonfeld.3 At the temperatures of interest in the present study, i.e., above about 600°C, the phase diagram indicates the existence of a wide liquid-miscibility gap, with the plutonium-rich liquid containing about 8 at. pct Mg and the magnesium-rich liquid containing about 10 at. pct Pu at the intersection with the solidus regions. Additional data on the compositions of the two equilibrium liquid phases obtained in this laboratory4 have defined the miscibility gap up to the consolute temperature (at about 1040°C). EXPERIMENTAL PROCEDURE AND RESULTS Materials. The 50 mole pct MgC12-30 mole pct NaC1-20 mole pct KC1 salt mixture was prepared by melting the required proportions of reagent-grade NaCl and KC1 with anhydrous MgC12. The molten salt was then purified by contacting it with liquid Cd-30 wt pct Mg alloy (at 450°C) to reduce oxidizing impurities, followed by filtration through a stainless-steel frit (pore size, 65 µ) to remove solid MgO formed during the reduction. The purity specifications of the zinc, magnesium, and plutonium were 99.999, 99.8, and 99.85 pct, respectively. Apparatus. The liquid salt and metal were contained in a tantalum crucible inside a graphite secondary vessel. The crucible assembly was located inside a resistance-heated stainless-steel furnace tube. The furnace tube was closed by means of a stainless-steel cover, which was attached by bolts, with a neoprene O-ring serving as a gas-tight seal. The top of the furnace tube was water-cooled to protect the O-ring. The furnace-tube cover was provided with a tantalum thermowell, a tantalum stirrer, and a port through which sampling tubes could be inserted and materials could be added to the melt without admitting air to the furnace tube. Vacuum and an argon atmosphere were available through a side-arm on the furnace tube. The furnace temperature was regulated by a proportional controller that was actuated by a chromel-alumel thermocouple between the furnace tube and the heating elements of the furnace. The melt temperature was measured by means of a chromel-alumel thermocouple in the tantalum thermowell. The accuracy of temperature measurement was ±3°C. The salt and metal phases were intermixed by a motor-driven tantalum paddle positioned at the liquid interface. The tantalum crucible was provided with four baffles to increase the turbulence. The sampling tubes consisted of 1/4-in.-OD tantalum tubing that terminated in a tantalum frit (Kawecki Chemical Co.; average pore size, 30 µ). Procedure. The zinc, magnesium, plutonium, and salt were charged to the tantalum crucible; then the system was evacuated and filled with argon. The melt was brought to the desired temperature, and agitated for 1 to 2 hr. After allowing the salt and metal to separate, both phases were sampled. Filtered samples were obtained by immersing the end of the sampling tube in the liquid and increasing the argon pressure sufficiently to force the liquid salt or metal through the frit into the tantalum tube. The sample was then partially withdrawn into the cooler portion of the furnace tube and permitted to solidify before being removed. The temperature sequence for sampling at each magnesium concentration was 800°, 700°, 600°, 650°, and 750°C. The composition of the liquid-metal phase was varied by incremental additions of magnesium in a series of experiments at low magnesium

Jan 1, 1967

By Charles Frey

TIE fundamental principle of resistance thermometry lies in the determination of temperatures by the measurement of an electrical conductor subjected to various temperatures and the translation of the resultant changes, in ohms, into temperature equivalents. Such resistance measurements can be made with maximum precision by the use of a standard Wheatstone bridge and a reflecting galvanometer of high sensitivity. Under such conditions, results are obtainable that may be accurate within 0.1 or even 0.01 per cent., and the "idiosyncrasies" of heated electrical conductors can be studied with advantage and profit, even if the latter is not of a financial nature. The chief requisites for producing a serviceable -commercial instrument may be enumerated as follows: First, there must be a resistor or "bulb" that can stand the maximum temperature without deterioration and which has a pronounced temperature coefficient. Second, there should be constructed an "even" bridge, having two fixed arms of equal values, in ohms. Third, a rheostat, the maximum resistance of which will be equal to the total change in the resistance of the bulb, between temperature extremes, is required. Fourth, there must be a sensitive galvanometer which is aperiodic, or nearly so. Finally, there should be a fairly steady source of direct current. The general scheme of this type of apparatus, in its simplest form, can be readily understood by reference to Fig. 1. Resistors A and B are constructed of manganin, therlo, or some other resistance wire having a negligible temperature coefficient. The sensitive D'Arsonval galvanometer G has its zero in the center. R is a rheostat and X is a resistor or bulb made of insulated platinum wire, or else of nickel, copper, or some alloy, according to requirements. K is a battery, but a direct-current service line is often used instead, with sufficient ballast in series to properly reduce the current.

Jan 8, 1919

By Merrill Horine

IT has been stated and accepted for many years that the automotive industry was the instigator, the principal sponsor for and the largest user of alloy steel and nonferrous alloys. The only universally recognized standard specifications and heat-treatments for these materials are those adopted by the Society of Automotive Engineers. It is this same auto-motive industry that has been the chief inspiration for and consumer of modern production machine tools. The production curve of steel ingots is more sensitive to fluctuations in automotive production than any other influence or group of influences. In every other important steel-con-suming industry, automotive materials and automotive processes are the outstanding features of modern progress. In this connection I need only mention the prefabrication of buildings, following the automotive system of straight-line, interchangeable mass production; the motorization of ships and railroads, employing automotive types of prime movers; the production of pressed-steel stoves, plumbing and furniture by methods originated in the automobile-body industry and the extensive use of rubber for the cushioning of all manner of machinery as pioneered by the automotive and tire industries. Dr. Jeffries has brought out this point in his address (p. 21), assuring us that the transportation industry is the largest user of these materials. In the transportation industry, or as we might more accurately express it, the transportation group of industries, the. automotive industry pre-dominates as a user of light alloys. One out of every four tons of aluminum produced is consumed by the automotive industry. Similarly, the automotive industry ranks first in the consumption of the following metallurgical materials: steel, 24.04 per cent; malleable iron, .57; alloy steels, 72.2; nickel, 30; lead, 39 per cent.

Jan 1, 1936

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20'- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes'5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1'8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.' Esin and his coworkers5'10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,'~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,'~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "'~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

Large deposits of manganiferous iron ores, representing several million tons of metallic manganese, occur in the United States. The Minnesota deposits of such ore are of outstanding importance because of their size, state of development, ease of mining and proximity to the Great Lakes, which permits water transportation to steel centers. In view of the fact that our steel industry requires large quantities of manganese, for which no satisfactory substitute has been found, and because our reserves of ferro-grade ore are comparatively small, the development of methods that will make our large deposits of manganiferous iron ores available as a source of ferromanganese is an important problem. Realizing the importance of this problem, some years ago the North Central Station of the U. S. Bureau of Mines and the Minnesota School of Mines Experiment Station undertook jointly the development of methods for recovering the .manganese content of manganiferous iron ores in a form suitable for the production of ferromanganese, the 80 per cent. alloy indispensable in producing steel. Two types of manganiferous iron ores have been described in previous reports.' The brown ores are higher in iron and lower in manganese than the black ores; the black ores are more siliceous but contain less phosphorus. The utilization of the iron content of the brown ores in the production of steel appears to furnish the best basis for their treatment. The method of attack has been to work out modifications in iron and steel practice so as to recover manganese in the form of slag comparable to ferro-grade ores. The greater part of the experimental work has been conducted with a 6-ton blast furnace and a 1/2-ton basic open hearth. This paper is devoted mainly to open-hearth tests in which high-phosphorus spiegel

Jan 1, 1930

By R. J. Wysor

MORE than two years ago, in making efficiency tests on our hot-blast stoves, I was surprised to discover a marked difference in temperature as indicated by a pyrometer inserted near a stove on blast, and the regular recording instrument situated near the bustle pipe. A special hole was then provided at the junction of the hot-blast main and the bustle pipe, and portable pyrometers with bare fire ends were used, both at this point and in the stove necks. I had occasion to make a number of such tests on various stoves on the same furnace, the difference in temperature as shown by the two pyrometers varying chiefly with the temperature of the blast, and the distance of the stove from the furnace. However, this difference was always great, often averaging above 100° F., for the entire period of a stove on blast. Later, experiments were made with similar results on another group of stoves. The pyrometers used were properly standardized and checked against each other before and after each test. However, there was still a slight doubt as to the accuracy of the results obtained, as subsequently explained. But I have obtained corroboration of the magnitude of heat losses from blast-furnace hot-blast mains from two independent sources. I have learned from H. A. Brassert, Superintendent of Blast Furnaces, South Works, Illinois Steel Co., that he has recently clone some experimental work similar to my own, and found temperature drops of the same order of magnitude. Also, C. R.. Lyle, of the Armstrong Cork Co., has made some interesting theoretical calculations, based oil the thermal conductivity of fire brick, for the particular conditions of several of our tests; and his theoretical interpolations, all facts being considered, check our actual observations fairly well. I understand that Mr. Lyle expects to publish the results of his investigations.

Jan 10, 1915

By A. J. Weinig

The Liberty Bell cyanide precipitate is unique in that it is apt to vary widely in composition in the course of very short periods of time, and a method of refining and melting that would prove highly satisfactory at one cleanup would yield7almost a hopeless "mess" at a second. Table I gives a general conception of the wide range in grade and composition of those raw precipitates. It is evident that no one standard flux could be expected to produce a high-grade bullion with such a widely variable precipitate, and that any method of treatment with acid requires most careful consideration. Refining by Acids Naturally, our first efforts to improve our precipitates were directed along the lines of acid treatment. Table II embodies the results of careful sampling and analysis of one cleanup at the time when wet refining reached its maximum development at this mill. We have now discarded all methods of wet refining, successfully replacing them by a more scientific method of flux calculation described herein, but it is believed that a general description of this wet refining is warranted as it throws some interesting side lights on acid refining in general. Table I.—Range of Composition of Raw Precipitates Per Cent. Gold and silver.................................... 25.0 to 75 Zinc.............................................. 18.0to 30 Lead............................................. 0.5 to 52 Copper........................................... 0.5 to 20 Silica............................................ 1.0 to 5 Calcium oxide...................................... 4.0 to 8 Sulphur.......................................... 0.5 to 8 Column A gives the analysis of the raw precipitate; column B, that of the precipitate after heating with steam, with frequent addition of hydrochloric acid until a point was reached where the batch had a strong tend-

Jan 1, 1917

By Martin Mayers

IT has long been recognized that it would be highly desirable to be able to predict the temperatures at various points in a burning fuel bed and their variations with changes of the properties of the fuel and the rate of air supply. Experimental investigations of fuel-bed tempera-tures1-4 have not been lacking, but the absence of any theoretical back-ground has made it impossible to use the results of these tests as a basis for prediction, except in a very general way. A mathematical analysis5, based on a somewhat simplified theory of the distribution of heat in a, fuel bed, has recently been completed by the author. Even though numerical values of some of the coefficients are not. known, the calcula-tions result in some conclusions of general significance. Thus, for example, it appears that when the temperatures throughout the fuel bed can be calculated, the rate at which ignition of the fuel by underfeed action can be maintained can also be calculated. The uncertainty concerning the values of the coefficients referred to above is a serious limitation on the use of that method. The following paper presents a discussion of these coefficients and includes estimates of their values based on the data now available. A brief description of the theory on which the analysis is based, and some results of the calculations showing their degree of agreement with experimental results, are presented by way of introduction to the discussion of, the coefficients. For a more extended discussion of the theory, see the A.S.M.E. paper5.

Jan 1, 1937

By W. S. Steele

Vermiculite is a nonmetallic mineral of the mica family, probably related to biotite mica. Its occurrence has been noted at numerous places in the United States and in some foreign countries, but it can be said that vermiculite is of only moderately wide distribution. A laboratory and field survey of over 60 deposits in the United States by F. 1;. Schundler & Co., of Joliet, Ill., indicates that the purest deposit represented in this survey is on the property of the Zonolite Company at Libby, Montana The Zonolite Company is commercially active and the vermiculite it produces is sold as Zonolite. Hereafter, in this report, the word "Zonolite " will be used to designate the vermiculite produced by the Zonolite Company. Values given herein to Zonolite are peculiar to the vermiculite produced from the Zonolite Company's deposits. References to " vermicullite," are to he interpreted as covering the broad field covered by the Schundler survey. Composition and Characteristics of Vermiculite Vermiculite is an aluminum-nmgnesium silicate. The following typical analysis is published by the United States Bureau of Standards: silica, 41 per cent; iron oxide, 7; aluminum oxide, 18; magnesium oxide, 21; calcium oxide, 1; alkalis (sodium and potassium), 1; moisture, 11. Vermiculite breaks down into platelike formation in crushing and grinding operations. Its cleavage is basal. Crude, screened, dry Zonolit,e weighs between 80 and 90 Ib. per cubic foot; its specific gravity is 2.8 and its specific heat is approximately 2. The fusion point of Zonolit'e is 2462" F. Crude vermiculite contains between 7 and 9 per cent of chemically combined moisture. The instantaneous introduction of crude Zonolite into an expansion furnace at a temperature of between 1800" and 2000" F. transforms the combined moisture into steam, which in an effort to liberate itself forces all explosive expansion of the platelike crude material

Jan 1, 1934