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By Alexander L. Field

In the light of the experimental data on equilibrium for the reaction C + FeO = Fe + CO in molten steel recently obtained by Kinzel and Egan,l it is necessary to revise current theories regarding the nature of equilibrium between carbon and FeO in the basic open-hearth furnace. According to the measurements of these investigators the equilibrium constant m for the above reaction for a pressure of dissolved CO equal to 1 atm. is equal to 0.0005 at 1550" C., when concentrations of carbon and FeO are expressed in percentages by weight. Their work also shows that, with the pressure of CO fixed at 1 atm., not only is the product of carbon and FeO constant, but carbon and FeO are each independently constant—a circumstance which might have been predicted from theoretical considerations. At 1550" C., carbon is constant at about 0.025 per cent. and FeO at about 0.020 per cent., with the pressure of dissolved CO equal to 1 atm., the product of these two constants being equal to the originally mentioned constant of 0.0005. Available data on the dissolved FeO content of samples taken from the metal bath at practical slag-metal equilibrium prove that this FeO content is determined solely by temperature and the effective FeO content of the slag. The distribution constant r at 1550" C., as determined by Herty, Gaines, Larsen, Simkins, Geruso and Watkins2 is equal to 0.0086. A slag would have to contain 0.020 = 2.3 per cent. effective 0.0086 FeO or less in order to prevent the metal from containing more dissolved FeO than that required for equilibrium with CO at 1 atm. pressure. Such low percentages of FeO are never found in basic open-hearth slags at the completion of a heat when rate of carbon drop has become practi-

Jan 1, 1930

By Edward Keller

THE ASSAY FOR COPPER. SOMEONE some time ago remarked that some chemists still insist on telling us how to determine copper by the electrolytic method. The. writer must confess that he believes that everything is not known definitely as yet as to how the exact amount of copper is determined in such material as purest commercial electrolytic copper. Some of us are not yet convinced that the pure copper atom is at all times deposited from an acid solution and that no oxygen or hydrogen will, under certain conditions, accompany it. Difficulties with impurer material are frequent, but erroneous results are not always apparent, since these do not speak so readily for themselves as those in the first case. By this is meant that if a chemist finds 100 per cent. of copper in electrolytic copper it is pretty certain that he perceives the result to be wrong, while if he finds 0.1 per cent. of copper too much in a very impure material he is far more likely to be unconscious of his error. These, in a wide experience, are frequent happenings and the writer has always looked with interest to publications on this subject. In turn, he :feels justified in giving to others a few of his own observations. Up to a few years ago there were two methods of electrolytic copper assay in technical use, which had in common, that the amount of copper deposited on the cathode did not exceed 2 g., and they differed in that, for the one a large sample 1 (20 to 80 g.) was taken from the general sample by a splitting device, dissolved, and from the solution a small portion (to contain 1 or 2, g. of copper) measured out for the electrolytic deposition; in the other Method the copper was determined, generally in 1-g. portions of the separated coarse and fine portions of the sample, all of which passed -a 16 or 20-mesh screen, being accomplished by a 40-mesh screen,

Jan 8, 1913

By L. S. Birks

The bainite transformation in a 3.5 pct Ni-1.25 pct Cr steel was studied under various conditions of cooling and stress. Several characteristics may be specified: 1) transformation in the bainite region (925° to 575°F) is very little affected by the manner of cooling from the austenitizing temperature at 1600°F to 575°F)tothe upper limit of bainite transformation at 925°F; 2) starting time for the bainite transformation is the same order of magnitude for either isothermal transformation or continuous cooling, but the rate of transformation is somewhat greater for isothermal transformation; 3) tensile stress accelerates both isothermal and continuous cooling transformation, and 32,000 psi stress changes the form of the isothermal transformation diagram to correspond in appearance to the continuous cooling diagram; 4) transformation for nonlinear, continuous cooling may not be determined directly from the linear, continuous cooling transformation diagram, but may be predicted by assuming first that the fractional amount of austenite transformed in a given small temperature interval depends on the approximate linear cooling rate during that temperature interval and then by summing stepwise over the whole temperature range. IN a previous publication' an X-ray spectrometer was described with which the X-ray diffraction from a specimen could be observed continuously under controlled temperature and tensile stress. This instrument has now been applied to a study of the austenite-bainite transformation in a Ni-Cr steel for both isothermal and continuous cooling conditions, with and without stress. Certain characteristics of the transformation lead to a method of predicting the amount of transformation to be expected at a given temperature for any type of cooling curve. Material and Specimen Preparation The steel chosen for the investigation was a Ni-Cr steel having the composition in the following percentages: 0.30 C, 0.27 Mn, 0.019 P and S, 3.50 Ni, and 1.25 Cr. In order to fabricate specimens suitable for the X-ray spectrometer, a 1/4 in. plate was ground down to 0.060 in. and then cold rolled to about 0.035 in. Next it was heat treated by quenching in oil from 1650°F and tempering at 1200°F for 1 hr. Then it was etched in dilute nitric acid to reduce its thickness to 0.014 in. and cut into blanks in the shape of flat tensile specimens 3 1/4 Vi in. long, 7/16 in. wide, with a notch % in. long and 7/32 in. wide; see Fig. 1. X-Ray Technique Since the X-ray spectrometer has been described in detail elsewhere,' only a brief outline of the principles will be repeated here. A focusing, pow- der-diffraction arrangement' was used, as shown schematically in Fig. 1, and the specimen was mounted vertically in a vacuum furnace (not shown in the figure). The X-rays, moving in a horizontal plane, enter and leave the furnace through beryllium windows. As shown in the figure, X-rays diverging from the line source A are diffracted by the specimen B and converge at the detector slit C. The detector D and the slit C may be set at the proper angle in the horizontal plane to receive X-rays diffracted by either the face-centered phase (austenite) or the body-centered form (ferrite, bainite, martensite). The specimen is heated by electrical conduction between connectors E, and E,, and a Pt—Pt-10 pct Rh thermocouple spot-welded to the center of the notched region on the side away from the X-ray beam indicates the temperature continuously on a Brown recorder. Temperature control is exercised manually with a variable transformer on the input to E,-E,. Any desired time-temperature relationship is easily obtained by first drawing the desired curve on the temperature recorder chart and then adjusting the variable transformer during the run so that the thermocouple

Jan 1, 1957

By A. Gatti

A dispersion of AI2O3 was produced within chromium by the hydrogen reduction of a solid solution of Cr2U3-A1203. The yesulting powder. was compacted, extruded, and the material tested in tension at various temperatures and in creep at 1800°F. The material is ductile above 1200°F and is at least twice as strong as electrolytic chvomium at all temperatures. Its creep resistance, rupture strength, and ductility at 1800°F warrant further work to improve its Low -temperatutre properties. BECAUSE of its high melting point and excellent corrosion resistance, chromium has long been considered as a base for high-temperature alloys. Most chromium base alloys, however, are extremely brittle at low temperatures. Elements such as nickel and iron lower the melting point of chromium and thereby limit its high-temperature usefulness. Chromium-alumina materials made by othersl, 2 have shown good high-temperature creep resistance but poor ductility and thermal shock resistance. Pure ductile chromium3 is weak at high temperatures and reverts to a brittle state if exposed to nitrogenous atmospheres. In sintered aluminum powder (SAP)4 and internally oxidized alloys of silver, copper, and nickel, fine dispersions of oxide phases can control hardness, recrystallization, and yield stress. The possibility of formation of a ductile, high-strength material by precipitating dispersions of alumina in a chromium matrix appears worthy of investigation. MATERIAL Powder Production—Chromium oxide and alumina in amounts to produce a final alloy of Cr + 16 pct AI2O3 by weight were colloid milled, filtered, dried and high fired for 16 hr at 1600°C in air. The resulting solid solution of oxides was ball-milled to a fine powder and the chromium oxide reduced to chromium by heating in pure dry hydrogen for 64 hr at 1400°C. Final Materials Produced by Powder Metallurgy Techniques—-Chromium powder, containing a disper-sion of alumina, was pressed into 1 1/8-in. diam slugs at 25 tons per sq in. and sintered 16 hr at 1400° C in pure dry hydrogen. The sintered slugs were encased in a stainless steel can, 2 in. in diam, and extruded at 1200° C through a 1/2-in. die. The 16 to 1 extrusion ratio produced a final chromium-alumina rod 1/4 in. in diam about 30 in. long. Samples of the rod were plunge-ground to small rupture bars of 0.82-in. gage length with a 0.01-sq-in. cross section. RESULTS Microstructure Studies—Fig. 1 is the microstruc-ture of the material in the as-sintered condition while Fig. 2 is the microstructure of the material as-extruded. Comparison of the as-sintered and as-extruded micrographs show the redistribution and realignment of the alumina inclusions by the extrusion

Jan 1, 1961

By J. Kostuik, M. J. de Bastiani

The method of mining the uranium orebody at Denison mine in the Elliot Lake district of Ontario is discussed. Details of the development of haulage-ways and rooms are giuen, as well as methods of ore haulage. The milling and beneficiation stages are noted briefly. Located in the Elliot Lake mining district of Canada, the Denison mine lies between Sudbury to the east and Sault Ste. Marie to the west, Fig. 1. This area is overlain by Huronian sediments filling a basin in the Keewatin basement complex. Subsequent folding of these sediments developed a synclinal structure, known locally as the Quirke Lake Trough, which forms the northern portion of the now famous big Z structure, the geological trademark of this region. Plunging to the west and extending nine miles from the granite outcropping in the north to the Keewatin lava contact to the south, the syncline has dips of 10" to 45" on the north limb and 10" to 20" on the south limb, Fig. 2. The Denison orebody, located on the north limb of the syncline, lies between 800 and 3000 ft below the surface. The main ore zone is within 50 ft of the Missisagi-Keewatin contact (see Fig. 3), and it varies in thickness from 6 to 32 ft. This ore zone has a composite dip of 19" to the south and is composed primarily of two pyritized conglomerate beds separated by a band of pebbly quartzite stratum. The upper conglomerate bed of the main zone varies from 2 to 15 ft in thickness, while the lower conglomerate varies from 2 to 12 ft. Over extended areas, mining is carried out over the entire section comprising the two conglomerate layers and intercalated quartzite; in other areas, the conglomerates are selectively mined, depending on the thickness of the quartz-ite. The ore zone contains approximately 6 pct sulfides and 80 pct silica. The predominant uranium-bear ing minerals are brannerite, uraninite, and an unidentified mineral (probably thucolite). Some of the uneconomic metallic minerals identified to date are pyrite, pyrrhotite, and chalcopyrite. MINE LAYOUT Shafts: Underground exploration and development (Fig. 4) were performed through two shafts 1/2 mile apart. The No. 1 shaft, sunk to a depth of 1856 ft with the main station established at the 1600-ft ore level, is a 250-sq ft, 5-compartment shaft capable of handling 4500 tpd. Two 5x5-1/2-ft compartments serviced by a 12-ft diam double-drum hoist, are used for hoisting 190-cu-ft bottom-dump skips in balance. A 30-man cage, offset by a counterbalance, operates within a 5-1/2x11-1/2-ft compartment. The fifth compartment is used as a manway, pipe, and cable-way. This shaft is also provided with an intermediate pumping station used during the initial mining phase as well as loading-pocket and spill-pocket installations and pumping facilities. The 480-sq ft No. 2 shaft, located down-dip from No. 1 shaft, has a 2776-ft depth. Serving as the main hoisting shaft with a maximum capacity of 9000 tpd, it has eight compartments, four of which are used for hoisting ore in 10-ton capacity bottom-dump skips. These four compartments, measuring 5x6-ft in section, are serviced by two 12-ft diam double-drum semi-automatic hoists. A 50-man cage is operated in a 15x8-ft compartment, and it is counterbalanced by a 12-ton weight. Two compartments are used for ventilation, manway, electric cables, and pipes. A station was constructed at the 1325-ft horizon of the No. 2 shaft for relay pumping. The main sta-

Jan 1, 1961

By J. W. Downey, M. V. Nevitt

MUELLER and Knott' have reported that Ti2Cu has the Si2Mo-type (Cllb) structure. The lattice parameters of Ti2Cu and the positions of the titanium and copper atoms are given by them as follows: ao = 2.944A; co = 10.786A 6 atoms per unit cell: 2 Cu (a) 000; 1/2: 1/2, 1/2 4 Ti (e) 002; 1/2, 1/2, 1/2 + z 00 -2 ; 1/2. 1/2. 1/2- z where z = 0.341 We have found eight other binary compounds which appear to be isostructural with Ti2Cu. All of them involve the combination of a titanium group element with a copper group element or a titanium group element with palladium. The compounds and their lattice parameters are given in Table I. The alloy samples were prepared by arc melting metals having a purity of 99.9 pct or better. They were homogenized for 72 hr at 900°C in evacuated capsules and quenched in tap water. Filings were prepared, and these were reannealed for 4 hr at 700°C, also in evacuated tubes. The lattice parameters were determined by a least squares Bnalysis of the back reflection lines of patterns made with cobalt radiation. It was not possible to make a precise determination of the lattice parameters of Zr2Au because the filings underwent rapid oxidation at room temperature. The evidence supporting the large tetragonal cell containing 6 atoms involves the presence of the reflections 002, 101, 004, 112, 114, 202, and other reflections with higher indices for which I = 3n. Three or more reflections corresponding to these indices, which cannot be indexed on the basis of a small body-centered tetragonal cell containing 2 atoms, are observed in the patterns of all of the compounds listed in Table I. They are strongest and most numerous when the components have large differences in their atomic scattering factors, as is the case in Ti2Pd, Zr2Cu, and Hf2Cu. The values of the z parameter should be regarded as approximate They were selected on the basis of the best agreement between the observed intensities of two pairs of closely spaced powder pattern lines (004): (112) and (114): (202) and the corresponding intensities calculated for several values of z. An ordering scheme was assumed in which titanium, zirconium, or hafnium atoms occupy the titanium positions of Ti2Cu, and copper, silver, palladium, or gold atoms occupy the copper positions. Calculated and observed intensities of the aforementioned lines and the other lines of the patterns are in satisfactory agreement, but a refinement of the z parameters and a final confirmation of the ordering arrangement must await a more detailed study. It is interesting to note that in transition metal systems at A2B stoichiometry the Si2Mo-type structure competes for stability with two other fre-

Jan 1, 1962

By Newell Alford

FORECASTS of future timber consumption in soft-coal mining are handicapped by; the lack of adequate experience records for estimating properly the timber requirements of the industry. Data were obtained from plants where records are kept or from operators who collected the information and to these were added FIG. 1.-GROWTH OF POPULATION IN UNITED STATES, FROM PEARL'S ?BIOLOGY OF DEATH." composite figures for the continental United States in 1905 and 1919 1 and for central and. Western Pennsylvania and for Illinois in 1922.2 The result, representing slightly over 928;000,000 net tons, is shown in Table 1. Some of the companies furnishing data were unable to segregate the timber into classes of use but for those who did, Table 2 shows the board feet of posts and cross bars used per ton of coal mined and the, percentage of the total timber consumed that was used in roof support. The wide variation in amounts of timber per ton of coal mined is the result of

Jan 5, 1924

By George W. Sheary

Situated 45 miles west of Philadelphia and 50 miles southwest of Bethlehem Steel Company's Bethlehem plant, the integrated Grace mine facilities produce 4000 tpd of high-quality iron ore pellets. Startup of the Grace mill was in November 1958, and iron concentrates were shipped until March 1960, when the pellet plant went into operation. The underground mine, when fully developed, will hoist about 9000 tpd, including development rock. The crude ore, which has an iron content of approximately 42%, is magnetically cobbed and crushed in closed circuit with 3/4-in. slotted vibrating screens. The ore is washed and screened in the mill and the plus 1/4 in. screen product is again cobbed prior to feeding to the rod mills. Grinding is done in rod mills, and in ball mills that are in closed circuit with 30 in, cyclones, to 1% on 100 mesh and 65% minus 325 mesh. The ground ore is magnetically concentrated by three-drum permanent type finisher magnets to 67% Fe. The magnetite concentrate is pumped from the mill to a 50 ft thickener in the pellet plant. The thickened magnetite concentrate is relayed to the filters through a two-stage pump arrangement. The filter cake is fed by belt from filter concentrate bins to mixer-muller belts where it is intimately mixed with bentonite and a slight amount of water for moisture control. The fluffed concentrate then drops into balling cones. The green pellets from the balling cones are fed in a prescribed feed pattern to shaft furnaces through the use of shuttle car mechanisms. The green pellets are dried, heated to 2500°F and cooled to 1200°F as they descend through the furnace and into pellet coolers where the pellets are further reduced in temperature to 250°F. Heat is recovered in the cooling process through the use of air-to-air heat exchangers. The cooled pellets discharge on a rubber conveyor belt and are transferred to 6000-ton pellet railroad loading bin. The final pellet product consists of 90% plus 1/4 in. material (after tumble testing1) and contains 66% Fe plus 3% silica.

Jan 5, 1962

By Ernest Klepetko

A NOTABLE amount of fossil resin exists in many of the bituminous coal beds of Utah. The upper part of these show a marked concentration of resin, which occurs primarily in the fracture seams. In general, these seams are less than 1/8 in. thick, but it is not uncommon to find coal with areas as thick as 3/8inches. The resin is of the hard kauri variety, with coloration varying from deep blood red to lemon yellow and almost colorless. There is also an almost black variety, which is not readily soluble in the same solvents as the lighter colored resins. These resins are valuable for many industrial purposes. When refined, they are suitable for uses similar to those for which lac resins are usually employed. They are particularly desirable for preparing dielectric varnishes. They are also desirable in preparing printing inks, waterproofing agents, special synthetic rubbers and rubber cements. They are especially suitable as an admixture in synthetic rubbers and cements, as they supply the essential tackiness the synthetics lack. The following chemical trade characteristics have been found by Inter-Chemical Co. research chemists in the refined resins: [Specific gravity (melted) 1.03 -1. o6 Acid number6-8 Softening point, mercury method 160 -165°C Iodine value (Wijs)140-1.50 Refractive index1.544 Color (Hellige, 25 pct toluol) ...14 Molecular weight, average732 Purity, 99 + pct pure hydrocar Bon] "Unaffected by alkalies and resistant to one hour fusion with solid potassium hydroxide. Completely soluble in aliphatic and aromatic hydrocarbons. Insoluble in alcohols, ethyl acetate and other commonly used alcohols and esters. Compatible with natural and synthetic rubbers, chlorinated and cyclized rubbers, waxes, vegetable oils, mineral oils, rosin, ester gum, phenolic and modified phenolic resins and other natural and synthetic resins of like solvent solubility. The recovery and refining of these fossil resins has been the subject of much research work and has intrigued many investigators. Broadly speaking, the problem involves separation of the resin from the coal into a very high-grade concentrate, and subsequent treatment of this concentrate to produce an acceptable refined resin for its various usages. Obviously it is also desirable to recover the residual coal without excessive size degradation. The late W. D. Green, concentration engineer for Combined Metals Reduction Co., obtained U. S. Patent No. 1773997 for the recovery of resin from coal through

Jan 1, 1947

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate of oxidation of ferrous iron to ferric iron in pure molten iron oxide by carbon dioxide + carbon moloxide mixtures at 1550°C. It is shown that the rate-controlling process is the interdiffusion of iron and oxygen atoms within the melt. The inter-diffusivity of iron and oxygen in the melt is obtained from the results and the value of (5.0 * 1.0) x 10-5sq cm per sec is recommended for the temperature of 1550°C. Similarly, it is also found that the rate of reduction of molten iron oxide is con -trolled by diffusion in the melt; however, apparent interdiffusivity values from these experiments are 10 to 20 pct higher than those obtained in the oxidation experiments, by virtue of convection arising from density difference. The results of the oxidation experintents are used to calculate an estimated self-diffusivity of iron in molten iron oxide of (1.5 * 0.5) x sq cm per sec. BECAUSE of the industrial importance of iron oxides, the study of the kinetics of both the reduction and oxidation of the solid oxides has received a great deal of attention. However, knowledge of the kinetics of similar reactions in the liquid state is very meager. Dancy 1 studied the kinetics of reduction of molten iron oxide by carbon in pig iron and found that the reaction is very fast. It was concluded from the results that the reduction of molten ferrous oxide is a first-order reaction up to 80 pct reduction, while

Jan 1, 1964

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".' The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley's publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1' for ?H°, and the entropy function.

Jan 1, 1952

A. L. BLOMFIELD, ? Colorado Springs, Colo. (written discussion?).¬I congratulate the author on bringing out a paper of real service to the profession. His contention of uniform size in balls is borne out by my own experience; in coarse crushing at the Golden Cycle in 6 by 6-ft. (1.8 by 1.8-m.) ball-mills we unquestionably gain by screening out the small balls once or twice a month. The point of gaging the ball size to be used by the uniformity of screen sizing is of particular interest. The necessity of sufficient return feed from classifier to the ball-mill is sound and clearly shown. In connection with this, I wish two further points had been gone into as thoroughly: (1) The effect of the quality of classification. In general, it is true that the smaller the per cent. of undersize in the feed the more effective is the mill's work. This is true on a bucking board, in tube-mills, ball-mills, and grinding pans. Given the possibility of returning. a full-feed load to any mill, it has been my experience that the effective work in the grinder is almost proportional to the quality of the return feed. (2) Again speaking generally, the shorter the tube-mill the greater is the quantity of return feed necessary to keep it loaded. The classification thus keeps the oversize in the mill more free from finished product and thus the crushing more efficient. It is very easy to overload any long mill with too much return

Jan 4, 1919

By I. R. Kramer

In his technical note entitled "Specimen Temperature During Electropolishing of Aluminum Crystals" Dr. Nakada 1 reported that the temperature of his aluminum specimen increased 65°C when it was polished electrolytically; he therefore concluded that the temperature of the specimens used in our work (Nakada's Refs. 4 and 5) similarly increased by this amount. From this he further concluded that the change in plastic-flow characteristics associated with the removal of the surface by electropolishing during deformation were due solely to a temperature effect. We believe that these conclusions are not justified. It is, of course, realized that the amount of the temperature increase is associated with the total heat transfer of the entire system, including the efficiency of the stirring action, heat flow through the grip on the specimen, and so forth. Of great importance is the type of electrolyte used for polishing. For example, in Dr. Nakada's experiment a methanol-perchloric acid solution was used. This solution has a relatively low conductivity and for the current densities of 0.3 amp per sq cm the electrical input appears to be 30 to 40 w. In our research a methanol-nitric acid solution was employed and for the size of specimen employed by Dr. Nakada the power never exceeded 7 w. There are major differences in his test apparatus which also appear to affect the temperature rise. In our case a steel specimen holder was used in order to provide a good heat sink and conduction path. The cathode was a coiled aluminum tube through which a coolant was passed to provide additional cooling capacity near the specimen. The stirrer was placed in a position to obtain maximum cooling efficiency. On the other hand Dr. Nakada used a teflon grip to support the specimen at one end only and a flat copper cathode, thus providing a much less efficient heat sink as compared with the metal grips used in our studies. The relationship between current density and the temperature increase for two sizes of aluminum crystals tested in our tensile apparatus is shown in Fig. 1. The temperature measurements were determined from a thermocouple spot-welded to the surface of the specimen. The thermocouple was protected from the acid by means of a thin film of stop-off lacquer which covered just the outer surface of the thermocouple junction. Whereas Dr. Nakada reported a time delay of 8 min to obtain thermal equilibrium, our temperature change occurred in less than 15 sec. This emphasizes the importance of the heat transfer in the entire system. However, readings were taken over a period in excess of 5 min to assure thermal equilibrium. The data given in Fig. 1 were also confirmed by determining the thermal expansion of the specimen in a sensitive creep apparatus. As may be seen, for the smaller specimen the increase in temperature is 8°C for a current density of 1.5 amp per sq in. The majority of our data on the effects of surface removal on the plastic behavior of aluminum were obtained at current-density values at or below this value. Above 1.5 amp per sq in. the temperature rise is uncertain; for under certain conditions, especially in the vicinity of 2 amp per sq in., the anode can become polarized and the current flow is erratic. This condition is easily recognized because wide fluctuations in the creep and stress-strain data make it virtually impossible to obtain reliable results, a condition which was always avoided in our work. The temperature increase for the larger specimen is less than that of the smaller specimens below a current density of 1.5 amp per sq in. At a current density of 2 amp per sq in. the temperature increased 13°C. The above temperature data are in accord with observations made during creep experiments. Using a transducer capable of detecting strain in the order of 10 -6, temperature changes in excess of 8°C were not detected when the current density was increased to as high a value as 1.5 amp per sq in. Finally we wish to point out that our experimental data cannot be explained solely in terms of a heat effect. For example in Fig. 1 of Ref. 2, the change in slope of Stage II as a function of the rate of re-

Jan 1, 1965

By Harold M. Feder, Irving Johnson

Tkermodynamic functions for dilute solutions of uranium in liquid cadmium were obtained from galvanic cell measurements. Deviations from Henvy's law were observed at concentvations down to 2 x 10-3 atom fraction. Unusually large negative values of the pavtial molal relative enthalpy and excess entvopy of uranium, suggestive of the occu,vvenctwe of partial ovdering of cadmium around uranium in these solutions, were found. The negative relative partial molal enthalpy of uranium at the liquidus accounts for the observed retrogvade solubility of metallic uranium between 473" and about 630°C. The standard free enevgy of formation of UCd,, from a-uranium and liquid cadmium is given by F,° THE constitutional diagram of the U-Cd system,' Fig. 1, is unusual in several respects. The near equality of the Goldschmidt atomic radii2 (Cd, 1.52A U, 1.56A) might be expected to give rise to extensive mutual solubility of the elements except for the restrictions imposed by differences in valence and electronegativity.3 The latter factors must be strongly influential because mutual solubilities in the terminal solid phases are probably negligible, and the solubility of uranium in liquid cadmium in the readily accessible range is only about 1 at. pct. Interestingly, the solubility of uranium in liquid cadmium actually decveases slightly with increasing temperature from 473" to about 630°C. Such a retrograde solubility in a liquid phase is a rare phenomenon in metallic systems; no other authenticated examples were found among the nearly 700 binary phase diagrams compiled by Hansen and Anderko.2 These observations suggested the existence of some unusual interaction between uranium and cadmium. Greater insight into the nature of this interaction was sought by measurement of the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE The emf of cells denoted by the scheme was measured. Each cell consisted of two uranium and two alloy electrodes immersed in a molten lithium chloride-potassium chloride eutectic mixture containing uranium trichloride. The physical arrangement is shown in Fig. 2. The potential between any pair of electrodes could be measured with a Leeds and Northrup Type K-3 potentiometer. The measurements were made at points marked in Fig. 1. It should be noted that points on the phase boundaries represent the concentrations of uranium in the saturated liquid phases of heterogeneous alloys. Uranium Electrodes. Uranium, which is not a particularly soft metal, is capable of retaining residual stresses, and its potential may depend upon its physical condition. Electrodes were prepared from 3-mm diam rods of hot-rolled high-purity4

Jan 1, 1962

By E. J. Rapperport, J. P. Pemsler

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4'5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.'-' EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) 'Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.

Jan 1, 1970

By Garth M. Crosby

Seven mines with important production records in the Coeur d'Alene lie adjacent to the Gem stocks -the Frisco (Gem), Hercules, Interstate, Rex (Sixteen to One), Success (Granite), Sunset, and Tamarack. Old records are incomplete, but avail- able data given in Table I show these mines have produced 10,550,721 tons of ore containing more than 50 million oz of silver, more than 1.5 billion lb of lead, and about 1 billion lb of zinc (approximately 1.25 million tons of lead and zinc combined). Average ore grade is 4.8 oz of silver per ton, 7.2 pct Pb, and 4.6 pct Zn. This impressive production represents about 12 pct of the District's yield. At present metal prices, with modern beneficiation, the gross value would be more than $400 million.

Jan 7, 1959

By M. G. F. Söhnlein

In a Bolivian tin concentrator an appliance was needed to furnish a suitable product for fine jigging from a pulp of the following composition: Mesh Per Cent. + 20 8.0 40 36.5 + 60 9.0 + 80 10.5 + loo 5.5 4-150 1 4.5 -150 25.0 99.0 Loss 1.0 In the jigging process, particles of cassiterite as small as 0.1 mm. can be recovered, provided they are not present in excess, that is if the material treated on the jigs contains sufficient coarser sands to keep the interstices between the grains open. Removing the fine material from the pulp by screening, to prepare the jig feed, is impractical, because that means the use of an 80-mesh screen or finer, and is not as effective as hydraulic classification. A screen would eliminate mineral grains from the feed which can be recovered by jigging, and in addition would throw more gangue and low-grade middling on to the jig. Formerly a one-spigot Richards vortex classifier had been used to accomplish this separation, but the tangential openings through which the hydraulic water enters became clogged by fine vegetal matter with which the water was contaminated, and which it was impossible to remove from the water. Consequently the work of the classifier was imperfect and a good deal of slime was sent to the jig. When designing the plant referred to in this paper it was decided to use a hydraulic classifier as shown in Fig. 1. The essential features had been copied from the Anaconda classifier.' This remodeled classifier consists of a truncated pyramidal wooden hopper A with an attachment of cast iron

Jan 1, 1917

By F. R. Hensel

THE alloy under discussion is a nickel-silicon bronze and is one of many age-hardening or precipitation-hardening FIG. I.-EFFECT OF QUENCHING AND AGING TEMPERATURES ON HARDNESS OF TWO TYPICAL NICKEL-SILICON BRONZES, NO. 2351 AND No. 2362. copper-base alloys. The hardening con-stituent is a nickel-silicon compound.1 The quenching temperature necessary to pro-duce hardening by a subsequent aging treatment is a function of the composition and extends from about 700'C. to ()50'C.; the aging temperature range extends from 400° to 600°C. The work carried out by the authors of this paper was confined to cast alloys having compositions within the ranges of 1.5 to 3.00 per cent Ni; 0.4 to 0.75 per cent Si; balance, copper.

Jan 1, 1940

By Edward Keller

In a paper, " A Study of the Elimination of Impurities from Copper-Mattes, etc.," presented to the Institute at the Atlantic City meeting, February, 1898, I gave certain figures which I called the relative slaggability in refining copper. In that paper* will be found the following pertaining to this subject: Relative Slaggability in Refining Converter-Copper. Cu. Pb. Bi. Sb. As. Se, Te. 1 129.5 1.13 7.30 5.22 0.81 and Relative Slaggability in Refining Electrolytic Copper. Cu. Pb. Sb. As. 1 41 9.97 7.13 Since there is a, possibility of misinterpretation of the above values, the following supplementary information may seem justified in explanation. As the contents of impurities in the unrefined or crude copper were unknown, the contents of the refined copper were substituted therefor, merely in order to obtain the two series of figures for comparison. These figures are higher than they would be had I been able to take the correct ones for the unrefined copper. The high figure, 129.5, for lead, in the case of converter-copper, means simply that more lead was slagged from the crude copper than remained in the refined copper; or, in definite values, that to 1 per cent. of copper slagged, the ratio of the lead gone into the slag and the lead remaining in the refined copper is 129.5 : 100. It is possible to approximate the true slaggability much more closely by adding the quantities of impurities in the refined copper to those in the slag, thus obtaining values for the crude copper in which the amounts volatilized are ignored (the latter

Jan 1, 1901

By Y. A. Chang

Phase relationships in the system Cr-Si have been established based on the melting point, X-ray, metallo-graphic, and DTA studies. The three intermediate phases, Cr3Si, Cr5Si,, and CrSi,, melt congruently at 177V ± I@,Cr3Si, 1680"i 20°, and 1490" *20°C, respectively, while the fourth intermediate phase CrSi, melts peritectically at 1413" i 5°C to Cr5Si3 and a melt containing 51 at. pct Si. The temperatures and compositions of the four eutectic isotherms occurring in this system are given below: DTA and metallographic evidences indicate that Cr5Si, undergoes a phase transformation at 1505" i20°C. The high-temperature form of this phase could not be retained by the quenching techniques used in this study. TECHNOLOGICAL interest in the developing of composite systems, consisting of Sic on the one hand as a fiber-reinforced material and metallic substances such as chromium, nickel, or Cr-Ni alloys as a binding agent on the other hand, stimulated the present investigation of phase relationships in the binary system Cr-Si. Earlier works concerning this system have been evaluated and summarized by ansen and Anderko.' Their phase diagram was based mainly on the works of Kieffer, Benesovsky, and schroth2 and Kurnakov.~ According to these authors, the three intermediate phases Cr3Si, CrSi, and CrSi, all melt congruently at approximately 1730°, 1600°, and 1550°C. However, they did not agree on the compositional stability of the fourth intermediate phase between Cr3Si and CrSi. Later Parthe, Nowotny, and schmid4 determined the structure of this phase to be tetragonal T-1 type using the single-crystal method, and concluded that this phase had a formula of Cr5Si3. Since the compilation of Hansen and Anderko,' a new phase diagram for the system Cr-Si has been proposed by Elliott5 based on the works of Goldschmidt and rand,' Guseva and ~vechkin,~ and Trusova, Kuzev, and Ormont8 and the earlier works quoted by Hansen and Anderko.' According to this proposed phase diagram, all four intermediate phases have large ranges of homogeneity and all melt congruently. More recently, Svechnikov, Kocherzhinskii, and yupkog studied the system Cr-Si by the DTA-method. According to their findings, the three intermediate phases, Cr3Si, Cr5Si3, and CrSi,, melt congruently at 1700°, 1720°, and 1475"C, respectively, while the fourth intermediate phase, CrSi, melts peritectically at 1475°C to Cr5Si3 and a melt containing 50 at. pct Si. The temperatures and compositions of the four eutectic isotherms were found to be: In view of the discrepancies existing in the literature concerning the system Cr-Si, it was decided to rein-vestigate the phase relationships in this system. EXPERIMENTAL a) Starting Materials. Chromium disilicide and chromium or silicon powders were used in the present study to prepare the melting point and DTA samples. CrSi, was obtained by directly reacting cold-pressed elemental powders in an atmosphere of Hz at a temperature of about 1250°C. Chromium powder, purchased from Stark Chemical Co., had the following impurities in ppm: Fe, 200; Mg, 1000; and 0, 250; while silicon powder, purchased from the Welded Carbide Co., had the following impurities in ppm: Ca, 700; and Fe, 3500. b) Melting-Point Determination and Differential Thermal Analysis. Cylindrical melting-point samples of approximately 13 mm in diam and 30 mm in length with a rectangular groove in the center were prepared by hot-pressing of well-mixed powder mixtures in graphite dies. Before the melting-point determination, the hot-pressed samples were ground on a sand paper to remove any minute surface contamination of graphite. A small hole of 1 mm in diam, drilled on the center portion of the samples, served as a blackbody cavity for the temperature measurements. DTA samples approximately 13 mm in diam and 15 mm in length were prepared in a manner similar to the melting-point samples. Melting points were determined using the Pirani technique under a helium atmosphere of 40 psi. The design, performance, and operation of this apparatus have been described in detail by Rudy and ~ro~ulski.'~ The temperature measurements were carried out with a calibrated disappearing-filament-type micro-pyrometer. The measured temperature was corrected for losses from the quartz window of the melting-point furnace and for deviations from blackbody conditions of the observation hole. The procedure for temperature correction has also been previously described." The DTA method of Heetderks, Rudy and Eckertl' was also used to check any phase transformations of selected alloys in the system Cr-Si. It was not possible to make remated runs on the same sample once melt-

Jan 1, 1969