Search Documents

By Charles Law McCabe, Lyndon H. Everett, Edna A. Dancy

It has been found that the carbide phase present at equilibrium in the system M-H2-CH4, at about 600°C, is MC for the rare-earth metals Ce and Pr. X-ray diffraction analysis showed that the monocarbides have fcc structures with lattice constants of 5.036 + 0.009Å and 5.131 + 0.001Å for CeC and PrC respectively. Gaseous equilibrium measurements were used to calculate the standard free energy of formation of the monocarbides from the elements. for the formation of (+ 1300) for the formation of PrC. THE rare-earthdicarbides, and their crystal structures, have been known for some years,l but only more recently were the carbides CeC,2,3 Ce2C3 2 and CeCS3 reported. In 1958 to 1959, Spedding et al. published work on the lanthanum-carbon system4 and other rare-earth metal-carbon systems,5 proving the existence of M2C3 and MC2, and measuring the lattice constants. They also demonstrated that tri-rare earth carbides, M3C, exist for the rare-earth metals samarium through ytterbium. However, they concluded that the cerium monocarbide reported by Brewer and Krikorian2 and by Warf,3 and given a fcc structure with a lattice constant of 5.130Å bythe former workers, was, in fact, cerium metal with carbon dissolved in it. They were also unable to find any evidence for the existence of Warf's CeC3, for which no structural details had been given. Even more recently, Palenik22 reported the existence of only M2C3 and MC2, having been unable to find any evidence for the existence of any other rare-earth carbides. There are no published experimentally derived thermodynamic data for the formation of any of these carbides, although Brewer and Krikorian6 have estimated values of for CeC, Ce2C3 and CeC2. The objective of the present investigation was; to determine experimentally the free energy of formation of any of the reported carbides of cerium and praseodymium, through a study of the rare-earth metal-hydrogen equilibrium. EXPERIMENTAL A methane-hydrogen mixture was circulated, in a closed system over previously prepared cerium or praseodymium hydride, and when equilibrium had been attained, the gas mixture was analyzed by selectively oxidizing the hydrogen and condensing out the water formed. The metal hydrides were used as starting material for convenience because, otherwise, the hydrogen in the gas mixture would immediately dissolve in the metals; in addition, the metals would not react with methane alone at the experimental temperature (around 600°C). The circulating system was based on that used by Browning, DeWitt, and Emmett7 for similar studies on iron carbides. It consisted of a quartz reaction vessel, all-glass circulating pump, analysis tube containing copper oxide that could be heated to 300" C by means of a small furnace, a solid CO2-methanol trap, and a double limb absolute manometer, Fig. 1. A cathetometer, capable of reading to 0.005 cm, was used to measure the difference in height between the two columns of mercury. In its final form, the reaction vessel was enclosed in an outer jacket, containing approximately the same pressure of hydrogen as that within, to reduce errors due to diffusion of hydrogen out through the fused silica of the reaction vessel., The circulating system was supplied with

Jan 1, 1962

ALABAMA. Aldrich, Aldrich, W. F. Anniston, Noble, A. E. Auburn,' Brown, R. L. Bessemer Abbott, C. E., Ferguson, V., Williams, E. P. Birmingham, Aldrich, T. H., Aldrich, T. H., Jr., Allen, A. W., Bowron, J., Burbidge, T. A., Crawford, G. G, Crockard, F. H., Dimmick, F. D., Ellis, E.,E., Hiller, E., Johnson, G. R., Ludwig, C. P., McCormack, G B., McCrery, Moffett, C. A., Morris, B.H, Peters, R., Jr., Pill, J. R., Ramsay, E. Gadsden, Hudson, J. B. Helena, Squire, J. Holt, Shook, J. W. Huntsville, Moss. Lehigh, Toulmin. Rock Run, Garvin, J. M. Thomas, Kluttz, W. L., Johnson, J. E., Jr. University, Litchman, H. B., Smith, E. A. Woodward, Woodward, A. H.

Jan 1, 1910

By J. Campbell

Long freezing range casting alloys are particularly susceptible to a type of porosity which is observed to form in layers parallel to the supposed position of the isotherms in the solidifying casting. Under favorable conditions (which appear to be typified by low-temperature gradients in the casting giving rise to a wide and more or less uniform pasty zone, and which arise from several factors, particularly: a) wide freezing range alloy, b) high thermal conductivity of metal, c) low thermal conductivity of mold, and d) high mold temperature3) layer porosity has been observed in many different casting alloys: copper,' aluminum, magnesium,' steels, and high-temperature alloys.3 Baker4,5 and later cibula6 argue that layer porosity occurs because of thermal contraction, in a manner analogous to hot tearing. In outline, the theory consists of the establishment of a coherent dendrite network by the impinging of dendrite tips. Subsequent shrinkage imposes tensile stresses on the network which tears perpendicularly to the stress, i.e., parallel to the isotherms. If these tears are not filled by the inflow of residual liquid then layers of porosity result. Baker7 attempted to test whether the porosity was the result of thermal contraction by casting test pieces in a mold designed to accentuate hot tearing. However, no significant increase in porosity was observed. This negative result of Baker's critical experiment appears to be substantiated by numerous observations, particularly the experiments by Lagowski and Meier8 on Mg-Zn alloys covering the range of zinc contents up to 30 pct Zn. These clearly reveal that the maxima for the incidence of hot tearing and layer porosity are well-separated, occurring at 1 and 6 pct Zn, respectively. Furthermore, the thermal contraction maximum occurred at 1 pct Zn, indicating that hot tearing is associated with contraction in the solid state, and not with porosity. These observations are further substantiated by the elementary consideration that the thermal contraction of the casting is likely to produce (if anything, since the temperature difference across casting of high thermal conductivity, such as aluminum and copper, is likely to be negligible) a compressive stress on the

Jan 1, 1969

By Fritz Wald, Martin Weinstein, Herbert E. Bates

ONE of the methods for preparing a fiber-reinforced composite is that of directional solidification of a eutectic melt. Its major drawback lies in the fact that the matrix in this case is a pure constituent (or a terminal solid solution of fixed concentration) and the ratio of fiber to matrix volume is fixed. Only very few, if any, pure metal matrices possess technically useful properties, and the necessity for alloying is the inevitable consequence of this fact. Nevertheless, structures similar to binary eutectic ones can be obtained in higher-order systems by pseudoeutectic reactions of a type where crystallites and a solid-solution matrix are simultaneously precipitated from a liquid.1"3 Trials to solidify such alloys directionally—the matrix consisting of a solid solution of chromium, nickel, and silicon and the reinforcing phase being Cr3C2— will be reported elsewhere.4 This note describes constitutional studies carried out primarily to determine -the position of the pseudoeutectic and further to insure that no undesirable reactions between the reinforcing phase and components of the matrix occur in the solid state at elevated temperatures. In the investigation it was specifically desired to reinforce a matrix which is as close as possible to the 80/20 Nichrome composition with Cr3C2 to insure good oxidation resistance and improve the strength at high temperatures. No konstitutional information on the quaternary C-Cr-Ni-Si svstem in the range of interest was found in the literature. Nevertheless, the two most important ternaries c-cr-Ni5 and have been completely investigated. On C-Cr-Si some investigations have been conducted,7"9 and C-Ni-Si was studied with a few alloys in the course of the present investination 9 Eight alloys were prepared to investigate the changes in the constitution of the ternary C-Cr3Ce-yNi eutectic5 with silicon contents up to 10 wt pct. Five alloys were made with varying chromium and carbon contents around compositions containing -60 to 70 wt pct Ni and 5 to 6 wt pct Si. The latter alloys were designed to locate the y(Ni-Cr-Si-C)-Cr3C2 pseudoeutectic reaction and to determine the maximum chromium content in solid solution compatible with a two-phase equilibrium between y and Cr3C2 only. The alloys were prepared from electrolyte nickel, semiconductor-grade silicon, high-purity chromium (99.999 pct pellets), and semiconductor-grade graphite. They were melted inductively in high-purity alumina crucibles under flowing argon. Twenty-gram charges were prepared and investigated by optical microscopy (including hot-stage investigations), X-ray powder methods, and electronmicroprobe analysis. The alloys were studied in the as-cast condition and also after a homogenization annealing treatment of 48 days at 900°C in evacuated quartz ampoules. The structures of all alloys based on the ternary eutectic plus silicon in the as-cast state consisted generally of an inhomogeneous solid solution and at least two other phases. Annealing of the alloys showed that the solid solution was homogenized but that an incomplete solid-state reaction had taken place in all alloys with silicon contents over 5 wt pct. This reaction is clearly visible in Fig. 1 around the large Cr3C2 crystals (gray areas). Below this concentration, the alloys consisted of a homogeneous matrix and precipitates of Cr3C2 plus graphite, Fig. 2. The Cr3C2 was entirely unreacted here. From these observations and subsequent X-ray and microprobe investigations, it was deduced that the

Jan 1, 1969

By J. C. McDonald

A DDITIONAL experimental data are presented in this note on a phenomenon which has been touched on but lightly in the literature. The common magnesium base rolling alloy (AZ31B) contains about 3 pet A1 and 1 pet Zn. When cold rolled, it hardens until it starts to break up in the rolls at 30 to 50 pet reduction. When it is heated after rolling to full hardness, it softens. However, other magnesium alloys have shown themselves capable of being cold rolled indefinitely, provided the ratio of roll diameter to starting gage is sufficiently high. As measured by the tensile test, these alloys actually soften when the reduction becomes large (60 to 90 pct). A subsequent heating at 300' to 500°F can produce hardening of this metal. Heating at higher temperatures (600' to 800°F) causes recrystalliza-tion and softening. Menzen' has shown that a magnesium base alloy can be cold rolled without intermediate anneals as much as 90 pet. The alloy studied, Mg-1.5 pet Mn, softened considerably between 20 and 90 pet reduction, as measured by tensile properties; a decrease in yield strength of 30 pet, and an increase in elongation from 3.2 to 16.7 pet (longitudinal direction of the sheet). However, Menzen gives no data on the reaction of this metal. to heating. Ansel and Betterton2 and Hurst and Hatch3 report a similar effect in Mg-1.5 pet Mn-0.1 pet Ca. Their data show an initial hardening, followed by softening. The former authors also show that the alloy softened by cold rolling will harden when heated at low temperatures, and that these effects are absent in Mg-3 pet Al-1 pet Zn. In the course of work4, 5 some years ago, the author observed similar effects with alloys containing cerium, thorium, or zirconium; but not with elements like aluminum, silver, or zinc. Table IA contains the results of an experiment which shows these effects rather well. A binary alloy with 0.3 pet total rare earths (Mischmetal* added) was rolled hot to 1/16 in. and then annealed to full softness by heating 30 min at 800°F. Rolling was continued at 1.5 pet per pass to 80 pet total reduction on 8 in. diam rolls. The metal was harder after 20 pet work than initially but, at 80 pet reduction, properties were back to their original values. Heating for 1 hr at 450°F produced about the same hardness whether the reduction was 20 or 80 pet. At intermediate reductions, the metal hardened, but not to as high values. Extensive cold rolling may also be carried out on metal hot rolled at temperatures sufficiently low to produce a semihard temper. Mg-0.6 pet Zr was rolled to 0.1 in. at 700° to 800°F, 30 pet per pass. As shown in Table IB, a further cold reduction of 85 pet, at 1.5 pet per pass, definitely softened the metal.

Jan 1, 1959

By A. W. Schlechten, W. J. Kroll

As this paper is written, the only method for the commercial production of lithium metal is by the fusion electrolysis of LiCl-KCl mixtures, as first proposed by Guntz.2 The details of the industrial process have not been made public but Osborg8 stated that an efficiency of more than go pct is obtained with a lithium metal recovery above 95 pct and that the metal is 99.5 pct pure. Pletenev9 gave a power consumption of 66 kw-hr per kilogram of lithium metal produced with a salt consumption of 9 kg of LiCl and 0.4 kg of KCI. Pletenev's figures indicate a somewhat lower recovery than that given by Osborg. In a recent report on German lithium plants, Motock7 gives figures that are also less favorable than those reported by Osborg. At the German plants the lithium recovery in electrolysis was only 83.4 pct, with a power consumption of too kw-hr per kilogram of lithium. The metal averaged only 97 pct pure, with sodium and potassium as the chief impurities. The presence of SO2, SO3, Si02, Ba, Ca, and appreciable amounts of Na and Fe2O3 were especially disturbing in the electrolysis, and it was necessary to run the cell for some time to eliminate most of these impurities and condition the bath. It may be noted here that most of these impurities do not interfere with a thermal reduction process. These facts show that the present method of producing lithium is fairly efficient and would suggest that other methods could not compete. However, fusion electrolysis has certain drawbacks, such as the necessity of supplying costly, low-voltage direct current and of collecting and processing the anodic chlorine if it is not to be wasted. An even greater disadvantage is that lithium chloride must be used for an electrolyte. It is one of the most expensive salts of lithium, since it cannot be produced in anhydrous form by precipitation from aqueous solution, as is done with LiF or Li2CO3. The reduction of lithium by a vacuum process similar to the ferrosilicon method for the production of magnesium would have certain advantages. Small units, such as Pidgeon retorts, would give flexibility of production to meet demand, and a small plant would require moderate capital outlay. There is a possibility of using idle Government-owned magnesium plants for such purposes. The raw materials needed for vacuum thermal reduction would not have to be extremely pure, especially with respect to the iron and calcium content. This paper describes a series of experiments to determine the effectiveness of various agents for the reduction of lithium compounds. The investigation is part of a program of vacuum metallurgy con-

Jan 1, 1947

ROESLER MAX-Geology of the Iron-Ore Deposits of the Firmeza District, Oriente Province, Cuba. Discussed by William Kelly, J. T. Singewald, Jr., B. L. Miller, J. D. Irving, L. C. Graton, C. P. Berkey 439 SINGEWALD, J. T., JR., AND MILLER, B. L.-The Manganese Ores of the Lafayette District, Minas Geraes, Brazil. Discussed by L. C. Graton, J. T. Singewald, Jr., F. Lynwood Garrison HARDER, E. C.-Manganese Ores of Russia, India, Brazil, and Chile. Discussed by J. T. Singewald, Jr., E. C. Harder 454 SCHRADER, FRANK C.-Geology and Ore Deposits of Mohave County, Arizona. Discussed by J. C. Anderson McDOWELL, J. SPOTTS-A Study of the Silica Refractories. Discussed by J. W. Richards, H. D. Hibbard, W. F. Rochow, J. B. Umpleby-: 460 PHALEN, W. C.-The Conservation of Phosphate Rock in the United States. Discussed by E. G. Spilsbury 462 NORTON, S., AND LEFEVRE, S.-The Magnetic Concentration of Low-Grade Iron Ores. Discussed by G. C. Foote, J. L. W. Birkinbine, F. L. Nason 462

Jan 4, 1917

By J. Chipman, N. J. Grant, R. Rocca

D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—With reference to eqs 7 and 8, at what temperature do they apply John Chipman (authors' reply)—That was 1600°C. Dr. Babcock—You have l x 10-4 as the component for the lime and 1 or 4x10-. Now, is it by dividing one into the other you get the 400? That is assuming equivalent activity on the part of oxygen, sulphur, and magnesia. Dr. Chipman—Yes, they are calculated for 1600. Now, the first one for CaO was calculated before we had a glimpse of Dr. Rosenqvist's paper." If you take his calculation you get 14,000 cal which is very good agreement, but our calculation would be superseded by Dr. Rosenqvist's new data. Dr. Babcock—The state you assume those to be in is the liquid state, as near as you can measure? Dr. Chipman—Naturally it is based on the solid CaS, but if you add the effect of fusion on both sides it just about balances out, so the ratio would be about the same. B. M. Larsen (U. S. Steel Co., Kearny, N. J.)—If we knew the activity of sulphur in the slag instead of merely the percentage, we might be able to find some conflicting factors that balance one another out, and find that the FeO or oxygen pressure effect is really present over the whole range. Dr. Chipman—I am fairly sure we would. The activity of sulphur in the slag and the activity of CaO in the slag, if we just knew those quantities, would enable us to save a lot of this computation and assumption and all the approximations we are doing now. Mr. Larsen—Two other points perhaps should be included: 1—an independent effect of manganese in helping the desulphurization; and 2—the number of mols of constituents or number of mols of ions or whatever there is in the slag could vary with these compositions in such a way that you get dilution effects. Dr. Chipman—You can figure all that in if you want to and it might improve the degree of approximation a little bit. Maybe enough to justify the labor of calculation, inaybe not, but we did not do it. L. S. Darken (U. S. Steel Co., Kearny, N. J.)—The authors have tackled a very complicated problem in trying to tie together in one picture the desulphurizing problem over the wide range of basicity and oxidation level from that of the open hearth to that of the blast furnace. At the present state of our knowledge of slags such an ambitious undertaking necessarily involves the adoption of numerous hypotheses. Their formulation (eq 11) for the higher FeO range

Jan 1, 1952

By B. C. Allen

The interface energies of chronzium, molybdenunz. hugsten, and their solid-solution alloys Cv-35Re, MO-33Re, and UJ-25Re were studied at 0.6 to 1.0 of the absolllte liquidus ter)zpe,vature using fiz&apos;e )izethods. Liquid surface tension, yv , was deter mined clsing the pendant-drop and drop-weight methods. Results are, respectizlely, 1700, 2370, and 2480 +100 dynes per ct for the rhernium -containing alloys and essentially the same as tlwse reported for liquid chro)riln, trolybdenum, and tungsten. Average solid slrjace energy, rsv< xias ))zeasured using tlre fiber-extetlsion method. The ratio of ysS, the acerage high-angle grain-boundary energy, to ySV cclas jolnd fronz grain-bolzdary grooue angles fort)zed at the surface in an inert atrfizosphere. Absolllte iute?:face energies were deterawined using ?nultip/rase equilibria involzing suitable liquids of known surface tension (tin, silver). Interpretation of the experimented results in view of pvobable tenzperatzcre, orientation, and purity effects giz,e the follouling approximations in ergs per sq ctn: ysv (i2lo. Mo-33Re) - 2100, ySS (Mo, Mo-33Re) - 800, rr (defornzation twins in MO-33Re at 1200"C) - 800. ysV (Cr. Cr-35Re) - 2400. YSS (CY, Cr-35Re) - 1000. Probably Ylv- YSV- 2500 for tungsten and W-25Re, giving yss (It&apos;, W-25Re) - 900. The interface energies of solid and liqid ch?&apos;omiu?.z, nolybdenu?rr, and tungsten are not geatly aff&apos;ected by rhenium and therefore are not a ttlajor factor in the ductili zing rhenium effect in Croup VI-A metals. THE interface energies of the refractory Group VI-A metals, chromium, molybdenum, and tungsten, are not well-established. The objective of this investigation was to study the liquid surface tension, solid surface energy, and grain-boundary energy of these metals and compare them to those found for the bcc solid-solution alloys, Cr-35e,&apos; 0-33e,&apos; and -25e. Five techniques were used to measure interface energies in high-purity polycrystal rod, wire, and sheet at 0.6 to 1.0 of the absolute liquidus temperature. The alloys were chosen to see if there was any connection between interface-energy behavior and the ductilizing rhenium effecL4j5 EXPERIMENTAL WORK Materials. A description of the materials used is presented in Table I. Chromium rod was prepared by arc melting iodide process crystals supplied by Chromallo Cor., hot extruding, and warm swaging to 0.63-cm-diam rod.6 The sheet was prepared by rolling as-extruded rod to 95 pct reduction in area from a hydrogen furnace at 800" to 900°C and surface grinding off 0.02 cm from each face. Cr-35Re rod was prepared by arc melting sintered rhenium powder and iodide chromium crystals, warm rod rolling to 50 pct reduction in area in cans, and swaging to 60 pct reduction in area at 1100" to 1200°C. Some of the rod was warm-rolled to sheet and then surface-ground. Portions of swaged chromium and Cr-35Re were further reduced by swaging and drawing to 0.013-cm-diam wire by the General Electric Co. Mo-33Re and W-25Re rod, sheet, and wire were provided by Chase Brass and Copper Co. The molybdenum sheet consisted of two lots, both essentially the same except for the carbon content. Liquid Surface Tension. The liquid surface tension of Cr-35Re, Mo-33Re, and W-25Re was measured by a combination of pendant-drop and drop-weight methods using techniques already decribed." Following out-gassing, molten drops were formed on the ends of centerless-ground Mo-33Re and W-25Re rods by electron bombardment at 5 x 106 mm. Similar drops were formed on outgassed Cr-35Re rods by induction heating under 1 atm of 99.995 pct Ar. Solid Surface Energy. Solid surface energy was measured by conducting microcreep experiments on molybdenum, Mo-33Re, chromium, and Cr-35Re wires at 2350°, 2306, 1550°, and 180O°C, respectively. In preparation, gage marks -2.5 cm apart and -0.001 cm deep were circumferentially scribed on the wire with a razor blade. Weights of the wire material were then attached. Five to seven reasonably straight wires were hung in a container made out of the wire material. The free end was placed through a small hole in the removable top and secured by bending a small portion 90 deg. The containers not only tended to provide vapor-solid equilibrium for the wires but also protected them from gaseous impurities. They were nominally 2.5 cm in diam by 5 cm high and were made from extruded chromium rod, Cr-35Re arc casting, molybdenum bar stock, or welded Mo-33Re sheet. After deg re as ing, the assembly was outgassed at a relatively low temperature to 2 x 10"5 mm and then recrystallized 2 to 8 hr at the creep temperature in a rhenium-element resistance furnace. The static argon atmosphere was gettered by tantalum radiation shielding. Specimen temperature was measured optically to 25"C using calibration with known melting points and blackbody conditions. The wires generally developed a stable bamboo-type structure according to Fig, l(b), (c), and (d) and retained their gage marks [upper portion of Fig. l(d)]. One or two of the weights were clipped off to provide a low load for the creep anneal. To minimize the possibility of bending or breakage, the wires remained attached to the top of the annealing container which was held to keep the wires vertical. The distance between gage marks was

Jan 1, 1967

By W. J. Heck

The need for a better understanding of the effect of fluid pressure on the strength of intact and jointed rock has long been recognized. The behavior of pore fluid pressure was first pointed out by Terzaghi 1 who suggested the application of the effective stress concept to rock and concrete. While the effective stress concept has been used for some time in the design of mass concrete dams, it only recently has been applied to rock. Robinson 2 and Handin et al.3 evaluated the effects of pore pressure on a variety of sedimentary rocks and demonstrated the validity of the concept. Work using pore fluids other than water has been done by Boozer, et al.4 who considered strain rate and temperature as additional variables. According to the effective stress theory, the effective stress, [a], is the difference between the total stress, [a], and the pore pressure, u, and is the controlling factor influencing frictional strength of rock, other parameters remaining constant. Assuming the Mohr-Coulomb failure criteria applies, the shear strength, T, is given by the equation [r=d+ (a-u)tan ¢](1) where [~F], the angle of internal friction, and c, the cohesion intercept of "no load" shear strength, are the effective stress parameters.* Robinson,2 Handin,3 and others have demonstrated that moderately porous sand-

Jan 1, 1972

While the production of this state has not realized the early hopes that this coal would replace eastern coal on the Pacific Coast, it has been steady though small. Nearly all of the tonnages given are from Goodyear&apos;s, The Coal Mines of the Western Coast of the U. s., a carefully com- piled and accurate account of the development of the industry along the Pacific. [ ]

Jan 1, 1942

By H. Tabachnick, N. Hedley

The extraction of gold and silver from ores with alkaline cyanide solutions is well known. Cyanide solutions are also good solvents for many base metal minerals, particularly most of the copper minerals. Leaver and Woolf,1 who determined the solubilities of copper minerals in 0.10 pct sodium cyanide solution, showed that malachite, cuprite, chalcocite, and bornite are readily soluble in cyanide; least soluble are chalcopyrite and chrysocolla. The Mining Chemicals Laboratory of American Cyanamid Co. has studied the possibilities of using cyanide solutions for leaching base metals. In this article the authors present the results of their experiments with cyanide leaching to reduce the copper content of a zinc concentrate from 0.050 pct to the desired specification of less than 0.02 pct. Zinc Ore Sample: The sample of commercial zinc ore used in this investigation to produce zinc concentrates was ball mill feed ranging from 1/2 in. to fines. The ore was crushed to —10 mesh and riffled into 600-g charges for zinc flotation. Analysis revealed 4.54 pct Zn and 0.005 pct Cu. Examined microscopically, the ore consisted essentially of cream-colored sphalerite and carbonate gangue. It contained a small amount of pyrite, partly tarnished. The only copper mineral identified was chalcopyrite, mostly smaller than 20µ, some of which occurred as attachments on sphalerite. Flotation Procedure: Batches of zinc concentrates were made as required according to the following general procedure. A 600-g charge of —10 mesh ore was ground for 4 min at 60 pct solids in a laboratory steel rod mill. Screen sizing showed it to be all —35 mesh with 42 pct —200 mesh. The pulp was transferred to a Fagergren laboratory flotation machine, diluted to 25 pct solids and conditioned for 5 min with 0.6 lb per ton CuSO4, . -5H2O. It was then conditioned with 0.10 lb per ton Sodium Aerofloat promoter and floated for 5 min with pine oil as frother and creosote as froth stiff-ener. The pH during flotation was 8.5. A typical analysis of zinc concentrate subjected to leaching is 44.41 pct Zn and 0.051 pct Cu. The ratio of concentration was close to 10 to 1. Leaching Procedure: Aero Brand cyanide, technical calcium cyanide analyzing 49.5 pet NaCN equivalent, was used for all cyanide leaching tests. For each test three rougher concentrates floated as described were combined (total weight close to 180 g) and the water content adjusted to 150 ml. The percent solids in the pulp was thus 55. After a weighed amount of cyanide flakes had been added, the pulp was agitated on rolls for a given period, then filtered and washed. Filtrate and washed concentrate were assayed for copper content. The procedure for ammonia leaching was similar to the cyanide process. A series of tests was run in which the effects of ammonia as a solvent for copper in the zinc rougher concentrate were investigated. In each test 180 g of zinc rougher concentrate was leached with 150 ml of ammonia solution. Various strengths of ammonia and times of leaching were investigated. The results are shown in Table I. It is apparent that ammonia was a poor solvent for copper in the zinc concentrate; 60 min of agitation with a relatively strong NH:, solution extracted only 2 pct of the copper. CYANIDE LEACHING TESTS Effect of Solution Strength: The solvent effects of 0.125, 0.187, and 0.250 pct NaCN equivalent solutions were compared for leaching periods of 15 min. Residue and filtrate were assayed for copper content. The copper content of the filtrate plus wash was calculated back to the original volume of cyanide solution (150 ml). The effects of cyanide strength are given in Table II, It will be noted that 15 min leaching with 0.25 pct NaCN equivalent solution extracted 74.6 pct of the copper in the zinc concentrate. The leached product assayed 0.013 pct Cu, appreciably below the required specification of 0.020 pct. Effect of Leaching Time: Portions of zinc concentrate were leached with 0.25 pct NaCN equivalent

Jan 1, 1961

By C. G. Dunn, F. W. Daniels, M. J. Bolton

Recent observations on grain boundary movements in sihcon iron have indicated the possibility of studying grain growth phenomena in two-grain specimens in which several variables affecting growth are readily controlled. These variables are (1) the energy per unit area (?) in the grain boundary, (2) the orientation relationship of the two grains, and (3) the radius of curvature (7) of the moving boundary. Ideally, one grain A should be a narrow rectangular parallelepiped adjacent to a second grain ß as shown two dimensionally in Fig 1. Such a two-grain group becomes unstable when one end of grain A is shaped according to the dotted line. Since the width w of grain A remains constant during growth of grain B, T should also remain constant. The other vari- ables mentioned above can be controlled in the preparation of each two-grain specimen.l,2,3 For a parLicular orientation of each grain, is not necessarily fixed; ? may also depend on the orientation of the grain boundary, but this may be controlled to some degree. The energy relationships for the gowth of grain ß may be derived from the more simple arrangement of two grains A&apos; and B&apos; shown schematically in Fig 2. Here B&apos; largely surrounds A&apos;. Assume these grains are oriented with a common plane parallel with the flat

Jan 1, 1950

By A. L. Foell

THE development of the modern blast furnace began more than one hundred years ago, with the abandonment of the small hillside furnaces. Its development, especially during the past 50 years, has been accomplished through a rapid succession of enlargements and improvements. The remarkable growth in furnace output during this period is a tribute to the engineers and operators who have constantly endeavored to build larger and more efficient blast furnaces. The blast-furnace operators and their mechanical and electrical maintenance staffs have originated most of the furnace improvements as a result of their practical operating experience. FURNACE LINES About 50 years ago furnaces consisted of hearths about 11 ft. in diameter, which merged into rather high flat boshes, with no cylindrical section between the bosh and inwall and no cylindrical section at the stock line. Since then the lines of the furnace invariably have included a cylindrical section above the bosh and a cylindrical section at the stock line. Notable increases have been made in both hearth diameters and furnace heights. During the past 10 years hearth diameters in new and replaced furnace stacks have rather consistently fallen within the range of 25 to 28 ft. while their heights have varied between 100 and 106 ft. The lines of most large furnaces using Mesabi ores have followed a fairly uniform pattern (Fig. I) in which the principal dimensions for 25-ft. hearth furnaces are as follows: [Hearth diameter 25 ft. o in. Height of bosh 10 ft. o in. Bosh angle 8 1 ½° Diameter top of bosh 28 ft. o in. Inwall batter per foot 15/16 Stock-line diameter 19 ft. 6 in. Large-bell diameter 14 ft. 6 in. Height from iron notch to top ring casting 100 ft. o in.] In determining the size of a new furnace for the replacement of an existing stack or for an addition to productive capacity, it is not possible to formulate a procedure that can always be followed. Local conditions, requirements as to capacity, available raw materials and prospects for future expansion dictate the size of such proposed improvements or additions. However, where the immediate requirements indicate a stack or furnace of a certain productive capacity, and the future prospects indicate that more capacity can be utilized, it is well to consider building the furnace for the ultimate capacity rather than to install a smaller hearth with provision for future enlargement. The decision to build the larger hearth and stack for the ultimate capacity probably will require no greater initial investment, since the saving in the cost of brickwork will about offset the greater cost of the hearth jacket, tuyere breast and bosh bands. In the meantime, the furnace of larger hearth dimensions, while operating below its ultimate output, will yield a better coke rate and

Jan 1, 1942

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

By Frank R. Corwin, Selden S. Rodgers

PAGE I. Introduction,........... 383 11. Brief History of Present MacDoUgall Plant,.... 384 III. First Experimental Work on Increasing Capacity of Furnaces, 385 IV. Effect On MacDouRall Plant of IncreaBed Draft from New Smelter Stack,,.......... V. Increasing the Capacity of the MacDouGall FurnaceS,.. 391 (A). Test of Arthur Crowfoot on Increasing Capacity,.... (a). Description of Test,........ (6). Discussion of Results Obtained from Test,... 393 (B). Investigation Carried Out by John A. Church, Jr.,... 395 (a). Advantages of High Speed,......398 (C). Effect on Regular Operation of Department by Applying Results Obtained from Experimental Work ..... 399 (D). Fundamental Principles Involved in Increasing the Tonnage, . 400 VI. Treatment of an INcreased Amount of Ore Screenings,.. 401 VII. Maximum Percentage oF Ore Screenings in a MacDoUGall Feed, 403 VIII. Tests to Further Increase Capacity of Furnaces,... 406 IX. Tests to Decrease PercentaGe of Flue Dust made by MacDouGall Furnaces,............. (A). Repath-Marcy Furnace......... 408 (B). Modified Hepath-Marcy Furnace,....... (C). Crouse Furnace Designed for Dust Prevention,.... 413 (a). Tests on Crouse Furnace,....... X. Concrete Hearths,.......... 419 XI. Conclusion,............ I. Introduction. Since the first installation of MacDougall roasters at the Great Falls smelter of the Anaconda Copper Mining Co., the capacity of the furnaces.has been more than doubled. During the first nine or ten years of the operation of the MacDougall department the tonnage treated by the furnaces remained practically unchanged. Experimental work carried out in 1906, however, showed that increasing the draft of the furnaces would bring about an increase in capacity. In 1909 the MacDougall department was connected to the new smelter stack and

Jan 1, 1914

By J. D. Braun, C. W. Powell

Diffusion between gold and indium at two temperatures below the melting point of indium (155.4oC) was investigated. The major, component of the diffusion zone was determined to be AuIn2; the other, intermediate phases in the system occur in much narrower layers In order of decreasing layer width these are: Au9In4, AuIn, Au4In. Inter diffusion coefficients of the four intermediate phases and the terminal solid solutions lie in the range of 2.4 x 10-l3 to 1.8 x 10-11 sq cm per sec. WHEN two metals which do not form a continuous series of solid solutions interdiffuse, each phase in equilibrium at the diffusion temperature should appear as a separate layer in the diffusion zone. In the Au-In system, diffusion plays a significant part in many commercial applications, particularly where indium alloys are used as solders for electrical contacts with very fine gold wire, for estab- lishing electrical contact to thin metallic films, and for mounting metal-coated piezoelectric crystals. A knowledge of the number, extent, and type of phases which form at diffusion temperatures below the melting point of indium, 155.4oC,1 and the diffusion constants for the system would be useful for these practical applications. Of more basic significance, additional information on polyphase diffusion in a system not previously investigated would be gained. The phase relationships in the Au-In system were determined primarily by Kubaschewski and Weibke1 and are based on thermal, microscopic, and X-ray analysis, Fig. 1. There are five intermediate phases in the system having approximate compositions corresponding to the formulas: Au4ln (ß)—80.0 at. pet Au; Au3In (?)— 75.0 at. pet Au; Au9In4 (d)—69.2 at. pet Au; AuIn—50.0 at. pet Au; AuIn2—33.3 at. pet Au. Solid solubility of indium in gold at 700°C is reported as 12.64 at. pet and at 406°C as 10.36 at. pet. No solid solubility of gold in indium is reported.

Jan 1, 1964

By F. B. Eiseman

IT is desired -to determine the effect of the extent of bank repairs on the final slag volume in acid electric steel-melting practice. It is understood that the repairs stud- TABLE I-Summary of Effect of Bank Repairs on Slag Volume [ ] ied here are necessary and the amount of sand added is that needed to maintain hearth and banks in a satisfactory condition. In this way the effect of repair materials on the amount of slag tapped would be found with a reasonable degree of accuracy. Ten heats were made for this study with careful attention to a uniform charge. The steel was the usual grade B and melting was carried out in a 3 1/2-ton top-charge Lectromelt furnace. Melting practice in all cases was the same-complete oxidation, with recarbonization by means of low-silicon pig iron.

Jan 1, 1947

By N. A. Zeigler, T. D. Yensen

Aging is a term that connotes a slow change in properties under ordinary operating conditions. It can be accelerated by increasing the temperature and by mechanical straining. The magnetic properties of iron and some of its alloys have for many years been known to be subject to such a change. But the cause of the change was not recognized until a few years ago after mechanical age-hardening in non-ferrous alloys of the "duralumin" type had been definitely shown, by means of solid solubility curves, changes in electrical resistance and microanalysis, to be caused by slow precipitation of one or more constituents from the solid solution. The similarity between the solid solubility curves of such alloys (Fig. 1) and those for iron-nitrogen (Fig. 2) and iron-carbon alloys (Fig. 3) below the A1 transformation point suggested at once that magnetic aging of iron might be caused by a similar process; namely, by the slow precipitation of carbon and nitrogen in the form of Fe4N and Fe3C at ordinary temperatures because of a cooling rate that had been too rapid to permit complete precipitation according to equilibrium conditions. This suggestion has since been amply confirmed, particularly by the comprehensive work of Köster1 on the effect of nitrogen and carbon. Typical curves are shown in Fig. 4 for the relationship between aging temperature and coercive force. Previous to the establishment of the precipitation-hardening theory it was thought that the effect of nonmetallic elements like C, N, O, etc., on the magnetic properties of iron was greatest when these elements were retained in solid solution, atomically dispersed throughout the interstitial spaces of the iron lattice2. Based on the theory that magnetic properties are intimately connected with the regularity of the lattice, it now follows quite logically that a greater effect on this regularity may be obtained when the above impurities are precipitated as very fine particles of Fe3C, Fe4N, FeO, etc., more or less uniformly dispersed within the grains. But if this is the case, it follows also that there must exist a relationship between the size

Jan 1, 1935