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By R. J. Stevens

THE Roan Antelope Smelter commenced operations in October, 1931. As originally designed, its equipment consisted of one reverberatory furnace, 120 X 25 ft, two Peirce-Smith converters 12 X 20 ft, and one straight line casting machine. Since that time the following additions have been made: One reverberatory furnace 120 ft X 28 ft (1934) One reverberatory furnace 95 ft X 28 ft (1943) Two 12 X 20 ft Peirce-Smith converters (1934 and 1938) One 13 X 30 ft holding furnace 6 (1938) One straight line casting machine and 2 ladle tilting quadrants (1934) The metallurgy of the smelting process is comparatively simple. However, there are several features of operation which are uncommon to most copper smelters: (1) The high grade of concentrate treated; this has always been about 50 pct copper. (2) The high flux burden on the charge. This is necessary because of the deficiency of bases'in the concentrate and the high alumina content of the concentrate. (3) The frequent necessity of adding coal to the furnace charge to control the matte grade. (4) The high grade of matte produced. This has led' to unusual converter problems. From the commencement of operations, the ore mined has come from the Roan Basin orebody. The concentrate produced from this ore consists mainly of chalcocite and shale with small proportions of other copper minerals. As mining operations extend to the Roan Extension orebody, the proportions of bornite and chalcopyrite in the concentrate will increase with a corresponding decrease in the copper content of the concentrate. Because of the concentrate grade the capacity of the reverberatory . furnaces in terms of tons of copper produced per ton of coal burned is high.. This ratio is usually over 2.2, and on especially favourable runs has reached 2.6. Reference to Table , shows that the iron content of the concentrate is unusually low. Only part of this iron is available for slag formation, the balance going to the matte. To make up this deficiency in bases, limerock is added to the furnace charge. This flux ensures a slag that is of the correct silicate degree, is sufficiently fluid, of low specific gravity, and it counteracts the thickening effect of the alumina present. An ample supply of flux is obtainable from Ndola, 2 2 miles distant by rail. Although the reverberatory slag has a high copper content, the slag fall is low and the copper loss in the slag now rarely exceeds 1.0 pct of the total copper charged. The blister copper shipped is of such purity that only one fire refining operation has been necessary to produce a wirebar with properties comparable to electrolytic copper. Bismuth has always been the most troublesome impurity and consequently the problem of its control in the finished product has been of prime importance. Practically none is removed in the reverberatory furnace. The bulk of the elimina-

Jan 1, 1947

By R. J. Stevens

The Roan Antelope Smelter commenced operations in October, 1931. As originally designed, its equipment consisted of one reverberatory furnace, 120 X 25 ft, two Peirce-Smith converters 12 X 20 ft, and one straight line casting machine. Since that time the following additions have been made: One reverberatory furnace 120 ft X 28 ft ('934) One reverberatory furnace 95 ft X 28 ft (1943) Two 12 X 20 ft Peirce-Smith converters (1934 and 1938) One 13 X 30 ft holding furnace (1938) One straight line casting machine and 2 ladle tilting quadrants (1934) The metallurgy of the smelting process is comparatively simple. However, there are several features of operation which are uncommon to most copper smelters: (I) The high grade of concentrate treated; this has always been about 50 pct copper. (2) The high flux burden on the charge. This is necessary because of the deficiency of bases in the concentrate and the high alumina content of the concentrate. (3) The frequent necessity of adding coal to the furnace charge to control the matte grade. (4) The high grade of matte produced. This has led to unusual converter problems. From the commencement of operations, the ore mined has come from the Roan Basin orebody. The concentrate produced from this ore consists mainly of chalcocite and shale with small proportions of other copper minerals. As mining operations extend to the Roan Extension orebody, the proportions of bornite and chalcopyrite in the concentrate will increase with a corresponding decrease in the copper content of the concentrate. Because of the concentrate grade the capacity of the reverberatory furnaces in terms of tons of copper produced per ton of coal burned is high. This ratio is usually over 2.2, and on especially favourable runs has reached 2.6. Reference to Table I shows that the iron content of the concentrate is unusually low. Only part of this iron is available for slag formation, the balance going to the matte. To make up this deficiency in bases, limerock is added to the furnace charge. This flux ensures a slag that is of the correct silicate degree, is suficiently fluid, of low specific gravity, and it counteracts the thickening effect of the alumina present. An ample supply of flux is obtainable from Ndola, 22 miles distant by rail. Although the reverberatory slag has a high copper content, the slag fall is low and the copper loss in the slag now rarely exceeds 1.0 pct of the total copper charged. The blister copper shipped is of such purity that only one fire refining operation has been necessary to produce a wirebar with properties comparable to electrolytic copper. Bismuth has always been the most troublesome impurity and consequently the problem of its control in the finished product has been of prime importance. Practically none is removed in the reverberatory furnace. The bulk of the elimina-

Jan 1, 1949

By Cadwallader Evans

MY endeavor in this paper will be to tell something of the accomplishments and current problems of the anthracite producer and to suggest some of the avenues for technical development that seem to me to be the most necessary and likely to bear fruitful results. The several subjects, that I find of most interest will be taken up individually with brief reference to the future trend. Underground Mining and Loading ?In this field great progress has been made in the last twenty years, beginning with the introduction of the scraper system. The electrical hoists for the operation of scrapers have been improved, and give little trouble, but there is an open field for the improvement of the auxiliary apparatus, particularly in the application of roller-hearing sheaves to the guiding of scraper ropes. Also notable in the last six or seven years is the introduction of shaker chutes, so that far more anthracite is now loaded over them than by scrapers. This trend should continue to be manifest, particularly if those who are looking ahead and who are charged with the development of this specialty continue constantly to study and improve the mechanical design of their shakers.

Jan 1, 1938

Carlisle: An old friend and good friend, Alan Bateman, is the Silliman Professor of Geology Emeritus at Yale and editor of the Journal of Economic Geology. Now, Alan, let's start off by telling us something about how you became interested in copper. Bateman: Well, after I left Yale in 1913, I was appointed one of the field members of the Secondary Enrichment Investigation. We spent three years in the field studying all the copper deposits of North America, trying to find out how secondary copper enrichment took place. As part of this investigation, I went up to Kennecott, Alaska, in 1916. After the trip I was asked by the president of the company to become consulting geologist to them. I accepted his offer, and to this day I'm still consulting geologist to the Kennecott Copper Corp. Up at Kennecott, there were both Henry Krumb and my good friend Henry DeWitt Smith, who was general superintendent. He and I had been together at Yale, and I had ushered at his wedding. Interestingly enough, Henry took his bride to Alaska and I took mine there two months later. My assistant was Don McLaughlin, and I think that was his first experience in a mining camp. We published a paper on Kennecott together and cemented a friendship lasting to this day.

Jan 11, 1964

CONTENTS PAGE MERRISS, M. H.-Direct Electrolysis of Black-copper Anodes of High Nickel-lead Content. Discussed by C. S. Witherell, C. P. Linville, G. E. Dalbey, M. H. Merriss 1 GRISWOLD, GEORGE G.-Calculating the Zinc for Desilverizing Lead Bullion by the Parkes Process. Discussed by C. S. Witherell, George G. Griswold, Milo W. Krejci, Lawrence Addicks, W. F. Gross, H. H. Alexander, A. F. Beasley, C. P. Linville 3 ALEXANDER, H. H. and STACK, J. R.-The Reduction and Refining of Tin in the United States. Discussed by Edward F. Kern, J. R.' Stack, R. L. Hallett, C. R. Hayward, William H. Bassett, R. C. Canby, H. G. S. Anderson 20 GREENAWALT, WILLIAM E.-Greenawalt Electrolytic Copper Extraction Process. Discussed by Stuart Croasdale, Colin G. Fink, Arthur L. Walker, Edward F. Kern, Henry A. Tobelmann, Oliver C. Ralston 26 BENEDICT, C. H. and KENNY, H. C.-Ammonia Leaching of Calumet and Hecla Tailings. Discussed by G. E. Dalbey, C. H. Benedict 34 RALSTON, OLIVER C.-Hydrometallurgy of Lead. Discussed by F. L. Bosqui, Jr., George D. Van Arsdale 34 TAINTON, U. C. and LEYSON, L. T.-Electrolytic Zinc from Complex Ores. Dis¬cussed by W. G. Woolf, C. A. Hansen 39 Direct Electrolysis of Black-copper Anodes of High Nickel-lead Content Discussion of the paper of M. H. MERRISS, presented; at the New York Meeting; February, 1924, and, issued, as Paper No. 1273-M, with MINING AND METALLURGY, September, 1923. C. S. WITHERELL, New- York, N. Y. (written discussion).-This paper is particularly valuable in that it gives the results of operations -carried out under conditions differing from standard practice. In the electrolytic refining of copper, as in other kinds of metal refining, it is occasionally necessary to treat extraordinary foul or complex material, in which cases 'it is valuable to know what other metallurgists have accomplished under similar conditions. As tapping the slimes-covered anodes brought the tank-voltage down to 0.45 to 0.50 volt, the counter electromotive force was, probably not more than 0.1 or 0.2 volt; hence the so-called polarization was, mainly,

Jan 6, 1924

By E. P. Sadowski, R. J. Raudebaugh

A study of micro structural characteristics of a 30 pct Cr, 42 pct Ni, 26 pct Fe alloy has been correlated with its behavior in creep and rupture tests at 1400°, 1600°, and 1800°F. Nitrogen pickup observed at 1600" and 1800°F was associated withfissur-ing of specimens prior to fracture. IN studying the high-temperature characteristics of a nominally 30 pct Cr, 42 pct Ni, 26 pct Fe alloy certain anomalies were observed, namely: The alloy had greater stress rupture and creep strength at 1800" than at 1600° F for time periods beyond 550 hr. As placed in test, this alloy was nonmagnetic. After test, some specimens were found to be fairly magnetic. The gain observed in magnetic response was not solely a function of time and temperature of testing. This is a report of the observations and a recounting of the results of studies made in an attempt to explain the behavior of the material under investigation. MATERIAL AND PROCEDURE All test material was taken from a production size heat of an experimental alloy melted and processed using commercial practice and having the following percentage composition: C Fe Cr Ni Ti 0.05 25.83 30.13 41.59 0.41 Al Mn Si S Cu 0.42 0.75 0.45 0.011 0.34 The material was tested in two conditions, namely mill-annealed and grain-coarsened. Mill annealing, which consisted of heating to about 1900° F in a continuous furnace for about 30 min and air cooling, gave a grain size of ASTM 8 and finer. To produce the grain-coarsened condition, mill-annealed material was soaked for 2 hr at 2050°F in a laboratory furnace and air cooled. This resulted in an ASTM grain size of 4 to 5. Rupture tests were carried out at 1400, 1600, and 1800° F in accordance with ASTM procedures. In tests where only rupture life and elongation at fracture were determined, specimens of 0.252 in. diam and 1 in. gage length were used. In tests where creep curves were obtained, specimens were of 0.375 in. diam and 4 in. gage length. Several of the tests under relatively low stress were discontinued short of rupture. Three low-stress tests are still in progress at this writing. Structural changes which occurred during testing were determined from examination of the tested specimens by light microscopy and X-ray diffraction. Diffraction pattern recordings were made with a diffractometer using copper radiation on samples heavily etched in a picric-hydrochloric

Jan 1, 1960

By A. H. Bell

Continued low prices and restricted markets for crude oil discouraged drilling activity in Illinois oil fields during 1933. Only 36 wells were completed in the state, the smallest number since 1904, and of these the majority were scattered wildcat wells, only 10 having been drilled in producing fields (Table 2). Production was curtailed approximately 40 per cent for the first half of the year. During July, August, and the early part of September there was no restriction on production. On Sept. 8, under the "code of fair competition for the petroleum industry," the quota of allowable production for Illinois was fixed at 12,000 bbl. per day. The state's production in 1933 was 9 per cent less than in 1932. What it would have been had there been no curtailment of production and if economic conditions had permitted a normal amount of cleaning out and repairs to wells, it is not possible to estimate, but it would no doubt have been considerably more than the actual figure. No new pools or new producing horizons were discovered in 1933, but the deepening of a Robinson sand well in Crawford County to the McClosky "sand" horizon (St. Genevieve limestone of the Lower Mississippian) resulted in a production of 3 bbl. per day (Fred Patchel, Savilla Shipman No. 5, NE. 1/4, SW. 1/4, sec. 26, T.6N., R.l3W., deepened from 1122 to 1388 ft., to be tested to the McClosky horizon, and, owing to the rapid variations in porosity within short distances, as shown in the Lawrence County field to the south, one test may not be considered as proving or condemning any large area. The average price of Illinois crude oil in 1933, calculated from the posted prices as published in the Oil and Gas Journal and Oil Weekly, was $0.862 per barrel. This compares with a calculated average price of $1.032 in 1932 and 0.852 in 1931. The total value of Illinois crude oil produced in 1933 obtained by multiplying the average price (0.862) by the total production (4,227,000 bbl.) was $3,643,674. Of the 26 wildcat wells drilled in 1933, only one was drilled on known favorable structure. This was the Walmar Oil Company's William Pepple well No. 1, sec. 12, T.4N., R.12W., Hancock County, which tested

Jan 1, 1934

By Thomas A. Wright

No symposium on die-casting could be complete without consideration of the methods of formula and impurity control. No corisideration of control would be complete without discussion of that new tool of the analytical chemist and inspector, the quartz spectrograph. Just as there is an increased appreciation of the possible applications of the die-casting process and of die castings, so too is there, slowly but surely, of the spectrograph. At present the role of the instrument might well be compared with that of brass or magnesium die castings. Neither is as widely understood or known as they will be. Product specifications are increasing and are getting more explicit and often more rigid. The designer, metallurgist and production engineer or superintendent will be forced to depend more and more on the chemical laboratory. Sampling, as well as analyses, testing and inspection problems will grow. The chemical laboratory must meet its increased responsibility and use of the spectrograph will become more common. Advantages of increased precision, greater speed, lessened labor and often lower costs cannot be ignored. It will be the purpose of this paper in part to outline the respective fields of chemical and spectrographic analyses and to indicate where one may overlap the other and in part to indicate certain possible sources of contamination of zinc-base die-cast alloys in particular. Composition Aluminum.-Aluminum die die castings are expected to conform to the specifications of the Amcrican Society for Testing Materialslt and the Society of Automotive Engineers2. The A.S.T.M. has recognized seven aluminum alloys in Tentative Specification B85-33-T. TWO are straight silicon and the remainder are of the copper-silicon type of which alloys VIII and IX have in addition respectively 2 and 4 per cent of nickel, but unlike the others are not covered by S.A.E. as well. All seven call for rigid control of certain impurities. With the exception of alloy XII,

Jan 1, 1935

By Thomas A. Wright

No symposium on die-casting could be complete without consideration of the methods of formula and impurity control. No corisideration of control would be complete without discussion of that new tool of the analytical chemist and inspector, the quartz spectrograph. Just as there is an increased appreciation of the possible applications of the die-casting process and of die castings, so too is there, slowly but surely, of the spectrograph. At present the role of the instrument might well be compared with that of brass or magnesium die castings. Neither is as widely understood or known as they will be. Product specifications are increasing and are getting more explicit and often more rigid. The designer, metallurgist and production engineer or superintendent will be forced to depend more and more on the chemical laboratory. Sampling, as well as analyses, testing and inspection problems will grow. The chemical laboratory must meet its increased responsibility and use of the spectrograph will become more common. Advantages of increased precision, greater speed, lessened labor and often lower costs cannot be ignored. It will be the purpose of this paper in part to outline the respective fields of chemical and spectrographic analyses and to indicate where one may overlap the other and in part to indicate certain possible sources of contamination of zinc-base die-cast alloys in particular. Composition Aluminum.-Aluminum die die castings are expected to conform to the specifications of the Amcrican Society for Testing Materialslt and the Society of Automotive Engineers2. The A.S.T.M. has recognized seven aluminum alloys in Tentative Specification B85-33-T. TWO are straight silicon and the remainder are of the copper-silicon type of which alloys VIII and IX have in addition respectively 2 and 4 per cent of nickel, but unlike the others are not covered by S.A.E. as well. All seven call for rigid control of certain impurities. With the exception of alloy XII,

Jan 1, 1935

By C. G. Cheriton

The Bathurst mining district is located near the town of Bathurst on the north shore of the province of New Brunswick in eastern Canada. This region is the northeasterly extension of the Appalachian mountain system. The area is heavily forested and covered with a fairly uniform layer of glacial gravels and boulder clay. The relief is low, increasing to a few hundred feet in the north west and several hundred feet in the extreme southwest. Thus, rock outcrops are scarce and occur mostly along streams and ridges. These factors made conventional prospecting difficult and resulted in the district becoming an excellent place for the application of regional geological studies, air photo techniques, airborne and gound geophysical methods and soil sampling. Late in 1952, The Brunswick Mining and Smelting Company discovered a very large base metal sulphide body presently known as their No. 6 orebody. Early in 1953, another and even larger sulphide body was discovered and is known as the No. 12 ore body. Mining exploration was very active thoughout 1953 and in 1954, The American Metal Company discovered the orebodies which have been developed into The Heath Steele 'Mines. The location of these deposits is shown on figure one. In the latter part of 1954, The Anaconda Company became interested in the district and decided to make a geological study of this new and promising base rrietal area. The following paper presents the story of the application of modern geological and geophysical techniques, leading to the discovery of a large sul-nhidp liodv. The Bathurst district is generally underlain by the Tetagouche group of Middle Ordovician rocks.

Jan 1, 1961

By W. F. Boericke

AT Kellogg, Idaho, J. Fred Johnson is driving the 5000.-ft Hooper Tunnel under contract for the Bunker Hill & Sullivan Mining Co. This was visited by a group of engineers during the recent meeting of the A. I. M. E. at Spokane, who were impressed with several features of the work. An excellent record of advance is being made by the contractor, over 47 ft. being driven in 3 days during October, and 223 ft. advanced in 29 shifts. The size of the tunnel is 8 by 9 ft. The ground is Wallace quartzite and, save for the first hundred feet, stands well and does not require timbering. The grade is held uniformly at 0.5 per cent. Two shifts are employed, with two sets of machine men to the shift. Ingersoll-Rand S-70 drills are used. each machine being set up independently in the heading; 26-30 holes are drilled to the round; using 1 1/4: in. round hollow drill steel. A 7-hole cut is required, and these holes are blasted simultaneously, using 60 per cent gelatine, 12 sticks to the hole. Instantaneous and fire delays of electric detonators are used for the complete round. A feature of the drilling is the use of long carriage drills, necessitating fewer changes of steel, and more time spent on drilling, with less time consumed taking steel back and forth from the face. Of course, this means better blacksmithing so that the drill steel shall stand up for the added footage.

Jan 1, 1930

By W. V. Long, D. H. Reynolds, R. B. Bhappu

Equilibrium distribution coefficients were determined for some monovalent and polyvalent ions for several absorbing and exchanging media as functions of pH and initial ion concentration. Among ions studied were NH4 (I), K(I), Ni(II), Ce(III), Th(IV), and Mo(VI). Absorbents used were: ion exchange resins; a tertiary, and a quaternary amine in an inert solvent; and some activated carbons. The ions studied were in aqueous HCI, HNO3, H2SO4, or HC104 solutions. The classical mass action expression proved of little value in describing the variations observed. The data indicate that the determining factors in absorption and ion exchange may be the ionic species in the aqueous solution, which in turn depend upon pH, dilution, and perhaps other conditions. Three sorption processes have become prominent in recovering values from leach solutions. These are: 1) ion exchange, 2) solvent extraction (liquid ion exchange), and 3) physical adsorption by materials of high specific surface. In the first two of these processes the exchange reaction is considered chemical in nature, and is discussed in terms of the mass action principle. The third is considered a surface phenomenon and is discussed in terms of surface areas and various forms (Gouy, Stern, Grahame, etc.) of the Helmholtz double-layer theory. Generally speaking, we have found in chemical analysis and hydrometallurgical studies that there are close similarities between the three sorption processes, and also differences which are difficult to reconcile with any of the usual theoretical treatments. That others have experienced the same troubles is shown by the fact that usable processes, in chemical analysis as well as in hydrometallurgy, generally are discovered by empirical procedures. EXPERIMENTAL CONSlDERATlONS The gaps between theory and practice have allowed many conflicting statements to appear in the litera- ture. To learn, in particular, the behavior of some metallic ions on a cation exchange resin at a constant pH, equilibration studies were made over a wide range of concentrations.' Results are shown in Fig. 1 for four metals in hydrochloric acid solution on a strongly acidic cation exchange resin, AG 50W-X8 (Bio-Rad). The distribution coefficient, defined as D = amount of metal extracted per g of resin/amount of metal unextracted per ml of solution is seen to vary in a way to support all manner of reports about its behavior with changes in solution concentration. The metals used were chosen from those least likely to form stable chloro-complexes. The changes of slope in the various isotherms may reflect formation of unsuspected chloro-complexes of low stability (ion-pairing for example) whose concen-

Jan 1, 1967

By Olav Mellgren

Part I. The interaction between potassium ethyl xanthate and lead salts has been studied thermo-chemically. It is shown that ethyl xanthate reacts with lead carbonate, basic carbonate, thiosulfate and sulfate according to principles of simple chemistry, whereas reactions with lead sulfite, metasulfite, basic thiosulfate and hydroxide at high pH are associated with secondary reactions. A new compound "xanthogen thiosulfate" is postulated. Part 11. Adsorption of ethyl xanthate on galena has been studied quantitatively and thennochemi-cally. It is shown that an ion-exchange mechanism governs the adsorption process and that the heat of adsorption of xanthate on galena is equivalent to the heat of reaction of ethyl xanthate with bulk lead salts. It is concluded that the entropy content of the surface "compound" on galena is different from that of a corresponding bulk lead salt. Alkali depression is in part shown to be due to the instability of the xanthate-galena system at high pH and to the formation of basic lead salts. Sulfate and carbonate ions are shown to have a stabilizing effect on the xanthate-galena system. PARTI. THERMOCHEMISTRY OF ETHYL XANTHATE AND OF ITS REACTION WITH LEAD SALTS In the past little attention has been paid to the chemistry of lead xanthate. It is known that xan-thates form slightly soluble compounds with lead and that suspensions of lead xanthates in alkaline solution decompose rather readily.' The solubility of lead ethyl xanthate is of the order of 2.6 x 10-6 moles per 1. At increasing pH the xanthate concentration of a saturated solution contains more xanthate. Thus at pH 11 this xanthate content is about 100-fold larger than at pH 7.1 Xanthates are known to be consumed when added to a suspension of slightly soluble lead salts such as lead sulfate and lead carbonate. It is unknown to what extent this xanthate consumption is due to a simple chemical reaction because, frequently, observations are made which reveal secondary reaction products in such reactions. Thermochemical study of the reaction between xanthate and lead salts offers a means to clarify the significance of these reactions as the enthalpy changes can be accurately predicted from heat of formation of lead salts in pure solution reactions. In the present work the heats of formation of lead ethyl xanthate from potassium ethyl xanthate and lead salts are determined and some thermochemical aspects of xanthate in solution are studied. The results of these investigations are presented in Part I. In Part II the heat of adsorption of ethyl xanthate on galena surfaces is presented. All enthalpy changes were measured directly in a microcalorimeter. Calorimeter: The calorimeter used for measuring enthalpy changes was similar to that used by Redinha and Kitchener2 which was based on a description by Derbyshire and Marshall.3 Other useful references4,5 are listed. A sketch of the calorimeter

Jan 1, 1967

By R. R. Joseph, K. A. Gschneidner

The solid solubility of magnesium in the close-packed modifications of lanthanum, cerium, praseodymium, neodymium, gadolinium, dysprosium, and lutetium was determined from approximately 250°C to the eutectoid temperature by the X-ray parametric technique. The maximum solubility at the eutectoid temperature was found to be 9.4 at. pet in La, 8.2 in Ce, 9.2 in Pr, 8.2 in Nd, 14.1 in Gd, 13.5 in Dy, and 11.5 in Lu. The solubility when compared at a homologous temperature was found to increase in a smooth manner with decreasing size factor from lanthanum to lutetium. It was found that the apparent atomic radius of magnesium when dissolved in the lanthanide solvent was constant and could be accounted for by consideration of several models dealing with departures from Vegard's law. The eutectoid temperatures for the lanthanide-rich La-Mg, Ce-Mg, and Nd-Mg systems were found to be 544", 505°, and 551°c, respectively. A study of the solid solubility of magnesium in the lanthanide metals was initiated because the valency and electron egativity difference are essentially constant and favorable for solid-solution formation, and thus one could examine the effect of size on terminal solid solutions. The size factors based on metal radii range from 14.6 pet for lanthanum to 7.5 pet for lutetium. Since the electronegativity difference is small, 0.06 unit or less, application of the Hume-~othery' and Darken and Gurry2 criteria for solid-solution formation indicates that the solubility of magnesium would be expected to be small for lanthanum (between 5 and 10 at. pet) and to increase as we proceed along the lanthanide series. A search of the literature revealed no data on the solubility of magnesium in the lanthanide metals except for the solubility of magnesium in cerium at 450oCA typical phase diagram for the lanthanide-rich end of the lanthanide-magnesium phase diagram is shown in Fig. 1. EXPERIMENTAL PROCEDURES Preparation of Alloys. The lanthanide metals used in the preparation of alloys for this investigation were prepared from the corresponding fluoride by metallothermic reduction techniques previously described by Daane.4 The chemical analyses of the metals used are listed in Table I.

Jan 1, 1965

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

Jan 1, 1963

Preheating Feature of Leyner Oil Furnace for Heating Drill Steel The No. 3 Leyner oil-burning furnace, used for heating drill steel, is now made with a preheating chamber. By this addition it is claimed that the heating capacity and, effeciency of the furnace are increased about 50 per cent. This preheater is a section which fits between the body and cover of the furnace of the old design. It may be attached to an old furnace by simply changing a few bolts. Referring to the illustration, it will be seen that the lower chamber is used for the final heating and the upper one for preheating. The type of burner now furnished with this furnace is suitable for either high- or low-pressure air. It hats merely to be throttled for high pressures and when this is done, it, is as efficient as burners designed especially for high pressures and eliminates the noise common to such burners. This furnace burns petroleum or any of its oils, such a, gasoline, kerosene, distillate, etc. Oil heating has many advantages. The steel cannot be injured by absorbing injurious elements such as sulphur, phosphorus or other impurities which :ire present in nearly all coals, nor from unequal heating since the flame imparts a uniform temperature; further, o lie steel is in full view of the operator at all times.

Jan 3, 1916

By Grafton Thrasher

For the proper discussion of this subject it is necessary to incorporate in this paper the substance of part of an article published by rite in Metallurgical and Chemical Engineering for January, 1915. CAST-IRON TEST PLUG, SHOWING LOW MOTTLED AND MOTTLED FRACTURES. Several years ago, while I was thief chemist for a malleable-iron company, it occurred to me that the mere regulation of silicon was not sufficient to produce the desired degree of chill. But only after repeatedly encountering this fact in befit open-hearth and air-furnace, as well as cupola metal, was I led to regard variation in the total carbon as the principal cause of disturbance; and I resolved to determine the total carbon as well as the sill on ill every heat, and by a carefully prepared test piece to gauge the approximate degree of chill. The test piece selected was a round plug, 2 in. in diameter and 12 in. long, cast on end

Jan 10, 1915

The State Mining Experiment Station, Missouri School of Mines and Metallurgy, Rolla, Mo Charles H. Fulton, Director of the School of Mines Martin H. Thornberry, Director of the Mining Experiment Station. From the State Mining Experiment Station are issued all the general and technical bulletins of the School of Mines The latest bulletin containing a complete list of publications will be sent upon application to the Director of the Station Residents of the state may obtain bulletins as issued without charge, or may ask to be placed on the mailing list. Nonresidents should write to the Director for further information concerning specific bulletins. From the long list of bulletins the following have been care¬fully selected as being most likely to interest the geologist and the mining engineer. Vol 8, No. 1 (1916), Bibliography of concentrating ores by flotation, by J Cunningham, vol 1, No 3 (1912), Some apparatus and methods for demonstrating rock drilling and the loading of drill holes in tunneling, by L E Young, vol 2, No 1 (1915), Comparative tests of piston drill bits, by C R Forbes and L M Cummings; vol 2, No 3 (1916), Cupellation losses in assaying, by H. T Mann and C. Y Clayton; vol 4, No 1 (1917), The hydrometallurgy and electrolytic precipitation of zinc, by F D. James; vol 4, No 2 (1917), The effect of additional agents in flotation, pt 1, by M. H. Thornberry and H T. Mann, vol 5, No 1 (1919), The carbonization of Missouri cannel coals, by H L. Dunlap, K. K. Kershner and V. X Smiley. Vol 5, No. 4 (1921), Coal mining methods in Missouri, by W W Weigel, vol 6, No 1 (1921), The problem of the St Peter sand¬stone, by C L Dake, 50 cents, vol 6, No. 2 (1922), Bibliography on the electrothermic metallurgy of zinc, by B M. O'Harra, vol 6, No. 4 (1923), Experiments on the distillation of zinc from complex zinc-lead-silver ores, by B M. O'Harra and E S. Wheeler, vol 7, No 3 (1924), Underground loading devices, by C. E. van Barneveld, 81; vol 7, No. 4 (1924), Briquetting of zinc ores, by B. M. O'Harra; vol. 8, No 2 (1925), A treatise of Missouri clays, by M. H. Thornberry.

Jan 1, 1933

P. W. BRIDGMAN.-Owing to a misunderstanding, I did not see Dr. McAdam's and Dr. MacGregor's remarks on my paper on Flow and Fracture (Metals Technology, December 1944, Pp. 32-38), until after their publication. Both Dr. McAdam and Dr. MacGregor speak of my analysis for the stress distribution at the neck of a tension specimen as containing several assumptions; in particular, that the strain is uniform across the section of the neck, that there is no hoop tension at the periphery, and that the plasticity conditions of von Mises hold. As far as the mathematics goes, the situation is no different in this problem of plastic flow than in a conventional problem of elasticity. That solution is unique which satisfies the boundary conditions on the stresses, the stress equations of equilibrium, and in addition the constitutive equations connecting stress and strain in the elastic case, or a corresponding set of equations, of which the von Mises relations are a special form, in the plastic case. In the particular case of the necked tension specimen I have found that there is a solution satisfying the boundary conditions, the stress equations of equilibrium, and the von Mises plasticity conditions in which the strain is uniform across the section, and there is no hoop tension at the periphery. This is therefore the solution, and the uniformity of strain and vanishing of hoop tension at the periphery are to be described as discoveries, over which the operator has no control, rather than as assumptions. The only part of the solution that can properly be described as an assumption is the von Mises plasticity condition. With regard to this it is to be noted that the condition is needed only in a much weakened form, for the analysis uses the condition only at the neck, where the strain is approximately constant. Thus, in the extreme case referred to in a footnote of my paper (p. 37, Met. Tech. Dec. 1944) the actually measured strain across the section varies from 2.4 to 2.6. Obviously it is a much weaker assumption to postulate that the von Mises condition holds in the strain range 2.4 to 2.6 than to assume it to hold for the entire range of strain from o up to 2.6, which would be necessary if the solution applied to the entire tension specimen rather than to the immediate region of the neck only. Furthermore, it is to be commented that under the special conditions of this problem the von Mises condition becomes identical with the maximum shearing-stress criterion of plastic flow; this amounts also to a weakening of the restrictions imposed by the von Mises condition. Dr. MacGregor refers to actual experiments of his own in which the strain was found not to be uniform across the neck. It is to be emphasized, however, that these were experiments on bars of rectangular section, and that the nonuniformity established was a nonuniformity around the perimeter, not a nonuniformity from the surface toward the axis. My method of solution applies only to a circular cross section. It can be said that the solution that satisfies the boundary conditions, etc., would definitely not be expected to demand a uniform strain for noncircular sections. In discussing my results, Dr. McAdam uses a definition of "flow stress" different from mine, so that the immediate applica-

Jan 1, 1945