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By Magnus Troilius

The method of using the bromine process of determining sulphur in steel, described below, is in successful use at the Midvale Steel Works. Ten grams of drillings are weighed out and put into the 1/2-liter flask A, with long neck. The flask is connected with a wide glass tube C', which, in its turn, is connected with the absorption bulbs B, containing HCI, 1.12 specific gravity, and ahout 5 C.C. of bromine. The wide tnbe C causes the vapor to condense and flow back into the flask A during boiling. The bulbs B connect with a long glass tnbe, which may be made to carry off the bromine fumes through a hole in a window, or, better still, through a flue with powerful draught. The connections being made, 100 C.C. of boiling water are run in through the thistle tube T. The air is thus completely driven out of the flask. 100 C.C. of HC1 (about 1.19 specific gravity) are then run in. When the gas begins to run rattler slowly through B, heat is applied until boiling gradually ensues. The steel being completely dissolved, the apparatus is disconnected, and the contents of B rinsed out into a beaker of 100 C.C. capacity, into which a few C.C. of a concentrated solution of BaCI, have been previously introduced. Heat is then applied (best by means of the hot iron plate) until the bromine is completely driven off and the BaSO, has settled nicely to the bottom. The BaSO4, is then filtered off on a small

Jan 1, 1884

By B. K. Larkin

Solutions to the diffusion equation for a line source located anywhere in a region bounded by a circular discontinuity are presented. Such solutions follow automatically from the Green&apos;s function presented by Jaeger.4 Petroleum industry applications of this problem would include transient compressible fluid flow in porous media bounded by a discontinuity. Since several recent papers have treated the subject in less general form, it would appear that many workers in this area of the petroleum industry are not aware of Jaeger&apos;s work. STATEMENT OF THE PROBLEM In several trearments1,2,3 of the transient flow of compressible fluids in porous media it was convenient to consider a region to be bounded by a circular discontinuity. In such a region (Fig. I), the properties in Region 1, r < a, are constant but different from the properties in Region 2, r > a. Hurst, l using the Laplace transform, obtained solutions for a line source located in the center of such a porous medium. The purpose of this work is to point out that a much earlier paper by Jaeger4 presents the solution for a line source located anywhere inside the discontinuity. The assumption is made that a line source may be used to approximate a well. In the following material it is convenient to use the terms source and well as being equivalent; however, the reader should remember the distinction in applications. SOLUTIONS Jaeger presented the Green&apos;s function for a line source, or well, in the composite region shown in Fig. 1. In the most general form, the solution for a system of j wells in Region 1, each producing at a time varying rate, qi (t), is

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 Frank Julian

The determination of manganese by precipitation with potassium chlorate from a solution in concentrated nitric acid, filtration through asbestos, and solution in a reducing agent whose excess is estimated, is open to the objections that the filtration and subsequent solution of the binoxide are apt to be very slow, and that the asbestos may (according to Troilius), unless perfectly purified, affect the titration. In the following modification, filtration is avoided. I give the method as I use it for Bessemer steel. In an 8-ounce Griffen beaker dissolve 1 gramme drillings in 15 c.c. nitric acid (1.2 sp. gr.). Evaporate to 5 c.c.; add 20 c.c. concentrated nitric acid and precipitate with chlorate as usual, avoiding a large excess; then add about 60 c.c. warm water, and 10 c.c. of the oxalic solution; stir until of a clear light yellow color, and titrate with permanganate while the solution is at about 80&apos; C. The binoxide should dissolve immediately when the oxalate isadded. The titration is rapid, and the end-reaction, though transient, easily caught after a little practice. The standard solutions used are: 15 grammes crystallized ammonium oxalate to a liter, and 1.6 grarnmes potassium permanganate to a liter. For standardizing the permanganate, to 10 c.c. of the oxalic solution is added 50 c.c. of hot water, and a solution of 1 gratnme of steel in concentrated nitric acid, from which the manganese has been removed by potassium chlorate and filtration through asbestos. I have made a large number of determinations in steel, pig-iron,

Jan 1, 1888

By J. C. McKinnell

The appraisal of an oil lease may often be mad,? through production decline analysis, which requires description of the functional relationship between the oil production rate and either cumulative production or time. Heretofore, attempts to define the function appropriate to a given set of production data have depended to some extent on subjective procedures. The purpose here is to introduce an objective solution, obtained by combining the principle of least squares with the theory of equations. MATHEMATICAL ANALYSIS The fundamental differential equation appropriate to a general class of decline curves may be written. Solution of Eq. 1 for general boundary conditions may be written in terms of either the cumulative oil production or time: These equations constitute the mathematical expression of the so-called hyperbolic decline. Their complete description for a given set of production data requires the numerical evaluation of the three parameters1.&apos;, n, D, and (go),. For the special case of n = 0, Eq. 2 becomes q. = (q.), - DiN with the corresponding expression in terms of time being q. = (qa),e...........(5) Similarly, for the special case of n = 1, Eq. 3 becomes with the corresponding expression in terms of cumula- tive oil production being q. = (q.),e " &apos;.......(7) Eqs. 4 and 5 constitute the mathematical description of the so-called exponential decline; Eqs. 6 and 7 are the mathematical description of the harmonic decline.&apos;,&apos; Returning to the hyperbolic expressions, Eqs. 2 and 3 may also be written, q: = sNp + b........ (8) and where a = 1 - n; s = (n— 1)D,(q0);"; b = (go):-"; a&apos;=-n;s/= nD,(qo);"; and b&apos; = (go);-. Note that both Eqs. 8 and 9 are linear in either time or cumulative production with respect to an exponential function of the production rate. In other words, a straight line relationship results for both variables when associated with the appropriate power of q,. This fact is of prime importance in the application of statistical analysis. . STATISTICAL ANALYSIS For a given oil lease, the time, production rate and cumulative production are recorded records. To establish predictive formulas from Eqs. 2 and 3, it remains to determine numerical values for the three parameters [n, D, and (q,) .] through an investigation of the past history. Upon interpreting a, s and b as parameters, Eq. 8 may be expressed for every time interval of interest, i, over the past history as follows. (q,): = s(Np), + b........(10) In general, Eq. 10 will not be satisfied exactly, because of the assumptions in the expression of Eq. 1, and the errors and anomalies universally associated with production data. It will instead define the residual, s(Np), + b- CO=d......(11) Squaring both sides and summing over all the data points, m, under consideration yields

By James K. Stanley

WHEN a plastically deformed metal is heated to a certain temperature, it undergoes a complete change in microstructure, the consequence of which is a marked alteration of mechanical properties such as hardness, strength and ductility. This change in microstructure occurs by recrystallization and is a process involving the formation and growth of strain-free nuclei in the deformed matrix. These nuclei continue to form with time and grow until a new grain structure replaces the cold-worked structure. The formation of the nuclei in the deformed sheet of 1 per cent silicon ferrite is illustrated in Fig. 1. If a recrystallization is conducted isothermally, a measurement of the fraction of the matrix recrystallized plotted against time leads to an isothermal recrystallization curve, first established in 1942.1 Such recrystallization curves are shown in Fig. 4. These curves show that the recrystallization of a cold-worked metal is best considered as a rate process rather than a time independent process such as is suggested by the improperly named and misleading recrystallization diagrams involving deformation, temperature, and grain size. 2-5 Any study of the rate of recrystallization resolves itself into a study of the component rates of nucleation and growth. The previous paper&apos; provided an account of the determination of the rates of nucleation; N, the number of nuclei formed per unit time per unit of unrecrystallized area, and growth, G, the radial growth in unit time, in the recrystallization of silicon ferrite (1 per cent Si). A method was developed to furnish experimental data for evaluating the effect of the recrystallization variables on N and G. The mathematical analysis for the derivation of the isothermal recrystallization curve was developed for a two-dimensional case (in thin sheets where the diameter of the recrystallized grain is greater than the sheet thickness). The present paper is a continuation of the study of recrystallization of 1 per cent silicon ferrite begun in 1942.1 In this work the effect of the factors deformation, temperature, grain size, composition, and recovery is studied with respect to the rates of nucleation and growth. At the same time it is shown how the cooperation of N and G affects the isothermal recrystallization curve. The study of these variables on N and G has a definite bearing on the mechanism of recrystallization and should lay a foundation for a rational theory on the subject. PROCEDURE The procedure used in these experiments was essentially the same as that described previously but in certain details some changes were made in the interests of speed. With few exceptions, the procedure is the same for the study of all the variables. Where the procedure is different from standard manipulations attention is called to this fact.

Jan 1, 1945

By R. W. Smith, T. J. Smolik

Recent work indicates that fluosilicate ions and or fluosilicate amine complex ions play important roles in fluoride activation of bery and feldspars in cationic flotation systems. In an attempt to further confirm conclusions reached in this earlier work, an infrared and X-ray diffraction study of the action of fluorides in cationic flotation of silicates was undertaken. It should be noted that in recent years considerable use has been made of infrared spectroscopy in studies of surface phenomena,2-4 and these studies have established the excellence of the technique. In the present study infrared spectra were obtained for various products of the reaction of HF and dode-cyclamine hydrochloride with quartz, microcline and beryl. These spectra were compared with one another and spectra of several inorganic and organic substances. In addition to infrared spectra, X-ray diffraction patterns were run on many of the reaction products obtained. A model 137 B Perkin Elmer Infracord double beam spectrophotometer containing sodium chloride optics was used to obtain the spectra. Infrared samples, except for the dodecylamine sample, were prepared by thoroughly mixing the substance to be analyzed with purified KBr in steel vessels on a Wig-L-Bug amalgamator. One-half in. pellets weighing 100 mg were than pressed under vacuum. Details concerning percentage of the substance to be analyzed in the pellets are indicated on the spectra. In all cases except for dodecylamine a KBr pellet was placed in the reference beam of the spectrophotometer to cancel bands due to possible impurities in the KBr. The dodecylamine sample on which an infrared spectrum was obtained was prepared by placing pure dodecylamine between two salt plates. X-ray diffraction patterns were obtained with a Norelco instrument, using a copper target tube, nickel filter and Geiger tube detector. The samples were ground into powders and either placed on glass slides with glue or placed into regular powder sample holders for diffraction studies. Goniometer scanning speed varied from 1°/min to 1/8°/min. EXPERIMENTAL RESULTS AND DISCUSSION Infrared spectra of microcline, beryl and quartz were obtained first and are shown in Fig. 1. These spectra agree reasonably well with previously reported spectra.5,6 The microcline (Fig. 1 a) and beryl (Fig. 1 b) were from good Black Hills crystals. The quartz (Fig. 1 c) was from a large, clear Brazilian crystal. It is not clear whether absorption bands of minerals are due to molecular vibrations, lattice vibrations or both. Fig. 2 shows infrared spectra of dodecylamine (Fig. 2 a) and dodecylamine hydrochloride (Fig. 2 b). The dodecylamine spectrum checks quite closely with that reported in Sadtler.8 Little is known of the spectra of hydrochloride salts of amines,9 and a spectrum of dodecylamine hydrochloride could not be

Jan 1, 1965

The Cuajone and Toquepala copper projects are located in the extreme southern area of Peru. Since 1960, Southern Peru Copper Company has operated the Toquepala open -pit mine, flotation mill, 110 smelter, townsites, power plants, and railroad. Toquepala and 10, the smelter and port location, are connected by a 110-mile-long (176 lun) railroad. Much of Toquepala&apos;s infrastructure has been used for the Cuajone project. Cuajone, at an elevation of 11,400 ft (3475 m), required five standard-guage railroad tunnels with a combined length of 17 miles (27.2 km) to connect with Toquepala so concentrates could be shipped to the no smelter. The total cost of Cuajone is estimated at $726 million for a designed annual capacity of 180,000 tons of copper, equivalent to about $4,000 per ton of installed production capacity. This relatively low cost per ton, by today&apos;s standards, has been made possible through the use of the 110-to Toquepala railroad, the ability to expand the 110 copper smelter, and other favorable factors. To mine the 468 million tons of copper sulfide or e at a grade of 1.0% copper, approximately 24 1 million tons of waste were stripped- before mining of ore to supply the new Botiflaca 45, 000 ton per day concentrator. The mining rate must exceed 300,000 tons of waste plus ore per day to maintain the 45, 0 00 tpd sulfide ore milling rate which was to be reached at the end of 1976. Waste stripping is done with 15 cu yd electric shovels and 120 -ton trucks. Ore mining is done with 8 and 9 yd shovels. A railroad connects the pit with the 60 in. by 89 in. Allis-Chalmers gyratory crusher. Side-dump railroad cars of 50.cu yd capacity dump onto a 0 16 ft 9 in. long (5. 1 m) grizzly inclined at 40º with 7 to 8 in. (178 to 203 rnrn) bar spacings. The grizzly is divided into two 22 ft 4 in. (6.8 m) wide sections and two side -dump railroad cars discharge simultaneously into the 150-ton capacity dump pocket. A Barco rock manipulator is used for breaking or removing oversize from the dump pocket. The bin receiving the grizzly undersize has a capacity of 5,000 tons, and the pocket beneath the crusher holds 900 tons. Each is equipped with an 84 in. apron feeder, which feeds a 60 in. (1.52 m) conveyor belt to the 150,000 ton coarse ore stockpile, where the ore is distributed by a 72 in. (1. 83 m) tripper conveyor. The 45, 000 live tons in the coarse ore stockpile are reclaimed by twelve 48 in. (1. 22 m) apron feeders. Maintenance on the crusher eccentric is made easy by an eccentric

Jan 1, 1978

By W. A. Backofen, D. Lee, F. S. Jabara

THE empirical character of plasticity analysis insures a continuing need for measurements of the yield surfaces of anisotropic materials. Recently, Wheeler and Ireland (W-I) proposed that an octahedral yield locus could be constructed on the basis of six Knoop hardness indentations. Such simplicity would have obvious appeal, if it led to consistently dependable results. In other recent work, a much more straightforward (and more tedious) method of measurement was used to establish all quadrants of the plane-stress yield loci for two substantially anisotropic titanium alloys.2,3 The same materials have since been reex-amined by the W-I method with results being reported here. A full description of the stress state under a Knoop indentor would be complex. In principle, however, this can be avoided in relating the hardness number to a plane-stress yield locus, by the expedient of superimposing the appropriate hydrostatic component on that state of stress. Six possible orientations of in-dentor on orthogonal (symmetry) planes, along (principal) coordinate directions, are illustrated in Fig. 1(0). Pictured in Fig. l(b) are normal-stress components nominally associated with indentation n: o2(H), directly proportional to the Khn in this case, together with By overlaying a hydrostatic tension, ah, that in general is equal to the stress state around the indentation is reduced to one of plane stress in the x-y plane for which the stress ratio is a The key step in the W-I yield-locus construction is to represent the Khn for any indentor orientation as a vector quantity on the octahedral plane. In the plotting, the vector is given as deviatoric stress components along the principal axes in the ratio , where represents the direction of the minor (width) diagonal and 1 that of the major (length) diagonal. There is no attempt by W-I to justify the 7/1, although it might be supposed that the value originates in the usual ratio of major to minor diagonals in a Knoop indentation of about 7/1. If that were its origin, the link to the deviatoric stress ratio would presumably be made by first taking 7/1 and then turning to the Levy-Mises equation for isotropic material: Interpreted in this way, the W-1 approach seems arbitrary and even contradictory. Yet it would still be favored by two circumstances: the deformation under a Knoop indentor approaches plane strain: when dcw/del =a; and the shape of the locus where plane strain is represented is not overly sensitive either to the exact value of dc,/dcl or to the degree of anisotropy, within a rather wide range of both variables. The second point is illustrated below, after a few additional comments on applying hardness

Jan 1, 1968

By Arthur F. Taggart

Tins paper proposes two units (believed to be new) for designating, respectively, capacity and efficiency for primary and intermediate crushers. CAPACITY Operators know that the tonnage of rock that can be put through a particular crusher in a give time depends primarily upon the crusher setting (open setting for jaw and primary gyratory types; closed setting for cones and rolls), and secondarily on the lithological character of the feed, its maximum size, the amount of fines that it carries, its moisture content, and the method of feeding. The proposed capacity formula states a relationship between all of these factors in one empirical equation, as follows: TR = TR80KK&apos;K" [I] in which Ts, called "reduction tons per hour" is the new capacity unit; T = tons of feed per hour requiring crushing; R80 = "80-per cent reduction ratio"; and K, K&apos;, and K" are constants that approximate quantitatively lithological character, moisture content and method of feeding, respectively. T is the hourly weight of material in the feed that is coarser than the coarsest discharge of the crusher. (For marked departures from the normal specific gravity range - 2.5 to 2.7 - T should. be adjusted to corresponding volumes.) In the crushers under consideration, discharge from the crushing zone is limited by the minimum dimension of a particle. Passage of the particle through a square-mesh screen is limited by its intermediate dimension. Sheppard1 has shown that the ratio of maximum: intermediate: minimum average dimensions of broken rock fragments may be taken as about 1.5 : 1 : 0.6 for nonslabby rocks such as are normally crushed, while for slabby rocks, such as thin-bedded sedimentaries, foliated schists and gneisses, and the blocky metamorphics, the ratio is of the average order I.3:I:0.3, with the possibility of an even smaller relative value for the thickness. Gaudin2 finds the corresponding ratio for 150 + 200-mesh pyrite to be 1.4: 1 : 0.6. The hourly tonnage of crusher-plant feed, therefore, should be diminished by the amount thereof that would pass a square-mesh screen of which the aperture is S times the crusher setting, where S is a shape factor with the value 1.7 for rocks that break exceptionally cubic; 2 for ores and rocks that exhibit no appreciable tendency to slabbiness; and 2.5 to 3, or, in exceptional cases, even larger, when the tendency to slabbiness is marked. R80 is the quotient of the theoretical square-mesh aperture that would pass 80 per cent of the feed, divided by the aperture that would pass 80 per cent of the product. It is best determined from screen tests.

Jan 1, 1941

By Donald T. Hawkins, Ralph Hultgren

The lorsion effusion method has been used to measure the vapor pressure of lead over pure lead and eight Pb-Sn alloys ranging from 9.1 to 87.9 at. pct Pb in the temperature range 950° to 1125°K. The resulting ?H°y 298 = 46,630 ± 200 cal per g-atow for pure lead is in excellent agreement with previous work. Deriued ?Gph values for the alloys were smoothed and correlated with previous heat of formation data to obtain entropies for the liquid alloys. values for the tin component were calculated by Gibbs-Duhem integmtion. Surfhce depletion of these liquid alloys was found to be absent, as shown by the fact that the measured pressure remained substantially constant with time in contrast with previous measurements on iron-rich solid Fe-Mn alloys. The activities and Gibbs (free) energies of the liquid Pb-Sn system are not well known although the heats of formation have been accurately determined by K1eppa.l Vapor pressure determinations of the activity of lead by Voronin and Evseev2 disagree with those of Predel.3 Elliott and chipman4 measured activities by the electromotive -force technique in the ternary Pb-Sn-Cd system. From the resulting values of the activity of cadmium, they were able to calculate the activities of lead and tin for the binary Pb-Sn system at the compositions xsn = 0.33 and 0.67. Atarashiya, Uta, Shimoji, and Niwa5 determined the activity of tin from Hz-H2O equilibrium measurements, but their results are subject to question due to uncertainty in the final state of their samples. To resolve these differences, measurements of the activity of lead were made using a torsion-effusion apparatus. Among other advantages, this apparatus rapidly detects errors caused by surface depletion, which tends to reduce the apparent vapor pressure of the more volatile component. If the measured torques remain nearly constant with time, only bulk depletion is occurring. This contrasts with the rapid decrease in torque found in solid Fe-Mn alloys at high temperatures and low manganese contents.6 EXPERIMENTAL 99.999+ pct Pb was obtained from the American Smelting and Refining Co. and 99.999 pct Sn from Vulcan Detinning Co. Eight Pb-Sn alloys were prepared by melting together weighed amounts of the pure metals in evacuated Pyrex tubes and quenching the melts in water. Loss of weight in preparation was less than 0.02 pct in all cases. The effusion cells were made from high-purity, nonporous graphite. Graphite was chosen because of its resistance to reaction with lead and tin and because it can be accurately machined with precision orifices. Two cells were used with overall dimensions as shown in Fig. 1. The orifices of cells 1 and 2 were, respectively, 1 and 1.5 mm in diam.

Jan 1, 1968

By G. Sachs, G. Espey

IT is well known that high residual stresses are created in tubing by the sinking process, in which no internal tool or mandrel is used.1-4 In this process, the wall thickness is usually slightly increased.4,5 In tube drawing with a plug, the residual stresses are gradually reduced with increasing reduction of wall, and, by the conventional approximation methods of stress measurement, no stress is detected in tubing in which the wall reduction is over 50 per cent of the total reduction in cross-sectional area.1-6, It has also been observed that higher stresses are set up by the use of wide-angle dies than by the use of acute dies.2 The actual stress distribution in drawn .tubing has been investigated by a few workers,7-9 but has not been related to the conditions of the drawing process: Some attempts have been made to correlate accelerated cracking tests for stresses in brass products with the magnitude of the circumferential stresses and the condition of the metal.1-10 MATERIALS AND PREPARATION The material used in this experiment was commercial cartridge-brass (70 per cent Cu, 30 per cent Zn) tubing in the straightened and annealed condition.‡ This tubing was of various outside diameters and had a wall thickness of 0.032 in. It was sunk to 1/2-in. outside diameter by means of an experimental 10,000-lb. hydraulic draw-bench, with a maximum drawing speed of 8 ft. per minute. All dies were of 1/2 -in. diameter. Various die materials and contours were used in order to study the effect of die design on residual stresses in the tubing; the specifications for the dies are given in Fig. I. Castor oil was used throughout as lubricant. Chattering occurred in sinking some of the tubing, particularly when dies having the more acute angles were used, but the tubes showing chatter marks did not differ markedly from those with a smooth surface regarding the magnitude of residual stress. The source of the chattering has not yet been revealed. The wall of the tubing becomes thicker during sinking, as previously observed 4,5 The increases in wall thickness were 3, 7 and 9.5 per cent on the average for 6, 20 and 33 per cent reductions in diameter, no effect of the contour being noticeable. The reductions mentioned throughout this investigation do not consider this fact, but are reductions of the outside diameter. For the evaluation of the residual stress two fundamentally different methods were used. The approximation method1,11 of splitting a certain length of tubing was employed to obtain a bird&apos;s-eye view of the effect of various drawing conditions on the circumferential stress measured by the diameter change occurring on splitting. For the determination of the complete stress

Jan 1, 1941

By W. Rosotoker

Using an expression for the free energy of a homogeneous phase as a function of composition, a relationship is derived which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. Comparisons between observed and calculated phase boundaries in the systems Fe-Ni, Fe-Mn, Fe-W, Ti-Mo, and Ti-Cb are presented. IT is the purpose of this paper to illustrate how the general free energy equations for two phases in equilibrium may be used to derive an expression which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. The free energy per gram atom of a disordered solid solution may, for many purposes, be represented by the equation:&apos; F = ½NZ [C-V,, + (1-C) VbB + 2C (l-C)V] + K(T) +RT[C-lnC+ (l-C)ln(l-C) ] [1] where N is Avogadro&apos;s number; Z, the coordination number; C, the concentration of the solute element in atomic percent; the subscripts refer to concentrations at phase mixture boundaries; VAA, VBB, and V,, are the bond energies between like and unlike adjacent atoms, respectively, at the interatomic spacing characteristic of the phase. The bond energies are usually assumed to be independent of small changes in the lattice parameter occasioned by solute additions and variations in temperature; V = VAB ---------------—— ; K(T) is the sum of the heat con- tent and heat entropy; R, the molar gas constant; and T, the temperature in degrees Kelvin. The free energy of a homogeneous phase is there- fore the sum of an internal energy, a specific heat, and a configurational entropy term, respectively. The compositions of two phases in equilibrium at a given temperature are governed by the minimum total free energy principle. Graphically, this is represented by the points of tangency of the tangent common to the free energy vs. concentration curves of the two phases. Analytically, this may be expressed as: ( df) = (df) [2] dc dc Expanding both sides using eq 1, the following equation is obtained after convenient readjustment of the terms: RT In[(ca)(1-c)]-½N (Vaa-Vbb)(Za-Zb) +NV [Za(l-2Ca)-Z,(l-2C,)] [3] The following assumptions have been made at this point: 1—The specific heats of the two phases are independent of composition variations within the range under consideration. Accordingly, the K(T) terms disappear on differentiation. 2— (Vaa)o = (VAA); (VBB). = (VBB); Va = V, Theyjustification for these assumptions can lie only in the successful application of the resultant equation. It may be noted that Zener2 has used assumption 1 in the calculation of the boundaries limiting the (a+j3) phase mixture in the Cu-Zn system.

Jan 1, 1952

By R. E. Miner, J. K. Jackson, T. L. Wilson

THE nature of the decomposition reactions producing hardening in aluminum-rich A1-Ag alloys is now fairly well understood. The silver is not uniformly dispersed even at temperatures above the solvus line: rather, it is clustered into zones and associated with dislocations.&apos; During quenching, nearly all of the silver segregates into zones&apos; and some is attracted to dislocations, producing stacking faults. Growth of these faults produces the semicoherent y precipitate.1 During aging, the larger zones and the y precipitates grow at the expense of the smaller zones. The large zones persist up to about 350°C; where they redissolve in favor of the y&apos; and y precipitates.&apos; The equilibrium hcp y precipitate occurs both by a cellular reaction at the grain boundaries1 and by growth of the Y&apos; plates to a critical size where incoherency results. Damask and Nowick 4 observed an internal friction peak in an A1-6 at. pct Ag alloy at about 140°C (0.25 cps). The peak was found to exhibit a systematic instability. After aging at successively higher temperatures between 155&apos; and 23Z°C, the peak first migrated to higher temperatures while increasing in height, then returned to lower temperatures and decreased in height. After aging at temperatures above about 200°C, the peak position remained constant while the height decreased very slowly. In quenched specimens, elastic after-effect measurements inhcated a rapid initial transient in peak position from low temperatures up to 155°C. The authors concluded that a stress induced growth and resolution of the clusters and the 7&apos; was the most reasonable mechanism to account for the behavior. It would seem, however, very unlikely that both the clusters and the y&apos; precipitate would provide damping contributions whose relaxation time and activation energies were identical, which is required for them to produce the same internal friction peak. The present investigation was motivated by this apparent anomaly and the development of a very low thermal inertia torsion pendulum5 capable of monitoring transient behavior. Low frequency internal friction measurements were made on four binary A1-Ag alloys nominally containing 5, 10: 15, and 20 at. pct Ag. The results of measurements made on a 10 at. pct Ag alloy in the quenched condition are shown in Fig. 1. There are two peaks apparent in the spectrum, one centered at about 160°C, the second at about 210°C. The two peak spectrum was observed in each alloy, but it was best resolved in the 10 pct Ag specimens. Because of the instability in the internal friction, 4 it seemed possible that the second peak was not a peak at all, but simply a manifestation of a single, sharply transient, peak. This effect has been observed in Au-Ni alloys.6 The existence of the higher tempera-

Jan 1, 1970

By E. H. Crabtree

THE heavy-media separation plant at the Central mill of the Eagle-Picher Mining and Smelting Co., near Picher, Okla., was started in February 1939. Since that time twenty-four million tons of lead-zinc ore has been treated in the mill, of which approximately 70 pct has been treated by heavy-media separation. Until January 1945, galena concentrate from the flotation plant was used as the sink-float medium. At that time minus 100-mesh ferrosilicon was substituted for the galena, and its use has been continued. The purpose of this paper is to compare the operating results and the costs of operation of the two media. For the purpose of this comparison the period Jan. 1, 1943, to Jan. 29, 1945, has been taken to represent the operation using galena medium; the period Jan. 29, 1945, to Sept. 1, 1946, to represent the ferrosilicon medium. During the first of &apos;these periods about seven and one-half million tons was milled; during the latter, or ferrosilicon period, more than five million tons was milled. It is believed that these tonnages are large enough to give representative data. FLOWSHEET The Central mill has a capacity of 15,000 tons per day. Briefly, the treatment used consists of crushing the ore through 11/2-in. and wet-screening out the minus 3/16in. portion. The minus 1 1/2 plus 3/16in. washed product is treated by the heavy medium; the minus 3/16-in. product is deslimed and jigged. The heavy-media cone tailing is discarded and the cone .concentrate is recrushed and jigged for the production of a coarse lead concentrate. The cone concentrate, impoverished of lead, is then ground in ball mills and treated by differential flotation. The minus 3/16-in. jig product is similarly treated. HEAVY-MEDIA PLANT The heavy-media cone plant treating the minus 1 ½ plus 3/16-in. product consists of one open-top cone 20 ft in diameter by 20 ft deep, equipped with a central airlift. Concentrate is discharged from the top of the airlift to a 3 by 14-ft low-head Allis-Chalmers drainage screen. Medium drains back into the cone, from the first half of this screen. The last half of the screen is provided with washing sprays for further removal of medium. Cone tailing is similarly drained and washed. Undersize from the washing screen is thickened and then cleaned in the medium-cleaning plant. When galena was used as a medium, cleaning was done in Fagergren and Denver flotation machines. The ferrosilicon is cleaned in three 36-in. and one 24-in. Crockett magnetic separators. A flowsheet of the cone plant is shown in Fig 1.

Jan 1, 1947

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 W. D. Robertson, D. A. Koss, A. J. Goldman

THE significance of the hcp (E) structure, which appears when Fe-Cr-Ni alloys (stainless steels) are transformed martensitically, has been the subject of considerable study and speculation.&apos;-7 It has been proposed that the hcp structure is an intermediate phase in the transformation: fcc (austenite) — hcp (E) -bcc (0, martensite). However, recent studies by transmission electron microscopy6,7 have indicated that the hcp structure may be a consequence of the large shear strain (10 deg) associated with the fcc to bcc transformation. That is, the transformation to a bcc structure is accompanied by extensive dissociation of dislocations in the parent austenite, which has a low stacking-fault energy.&apos;-&apos;&apos; X-ray diffraction analysis of the transformed alloy reveals a pattern of lines corresponding to an hcp structure, together with the parent austenite and the bcc product. The fact that the hcp structure is observed only in association with the bcc product in these alloys1&apos;4&apos;6&apos;7 lends support to the conclusion that the hcp structure is a secondary product of the transformation. But, the evidence is circumstantial and more definite resolution of the two possibilities mains to be obtained. If the hcp structure is an intermediate product of the transformation, as in 1) above, then two distinct Ms temperatures should be observed, Ms and To evaluate this possibility, three different techniques that are particularly sensitive to the structural changes accompanying such transformations have been used in an attempt to detect two transformation temperatures in an Fe-15.1 Cr-11.7 Ni alloy: 1) high-sensitivity differential thermal analysis, 2) the temperature dependence of resonant frequency (elastic moduli), and 3) internal friction of cylindrical specimens vibrating in either longitudinal or torsional modes. To obtain the necessary sensitivity, a differential thermal analysis technique was developed for the purpose, Fig. 1. The differential temperature between a nickel standard and the specimen was amplified to produce a sensitivity of 0.02OC (0.7 v) in temperature difference. The specimen and the standard were surrounded by a copper block and the entire assembly was immersed in a solution of methyl and ethyl alcohol, freezing point, - 140OC, which provided the necessary thermal stability to reduce temperature fluctuations to negligible proportions. A cooling rate of about 1.5OC per min was obtained by bubbling liquid nitrogen through the liquid bath. In order to calibrate the experiment with respect to the evolution of heat in the transformation from fcc to hcp structures, differential cooling curves were obtained for an Fe-19.8 Mn alloy, which transforms martensitically to E.&apos;"-&apos; a Ms(e) temperature of 145°C was clearly defined by a temperature

Jan 1, 1964

The Gooseberry Mine is located 38 krn (24 miles) by road east of Reno, 13 km (8 miles) south of Interstate 80. The mine was originally discovered in 1906 and remained in the control of the Martin family of Fresno, who worked the-property with Mexican ranch hands for 68 years. Westcoast took over the property in 1976 from Apco Oil Corporation. During the time the Martins operated the mine, a 305 m (1,000 ft) inclined shaft was sunk with drifts developed on eight levels exceeding a total of 3,000 m (9,000 ft) in length. It is interesting to note that for over one -half century all development ore was stockpiled. West- coast, the United States mining subsidiary of Home Oil Company Ltd., Calgary, Alberta, completed sinking another vertical shaft to the 396 m (1,300 ft) level. Development work between 122 m and 305 m (400 ft and 1,000 ft) levels has proved the existence of a fine ore body over 300 m (1,000 ft) long. The silver-gold ore grade is fairly consistent in the vertical section, but copper, lead and zinc may show slight increases with depth. Average width of the ore bearing portion of the vein is 2.5 m (8.3 ft). Stoping is by cut-and-fill method. Average silver values within the ore zone have increased from the 152 m (500 ft) level to the 305 m (1,000 ft) level, although the gold values do show some decrease. It is not possible for the geological staff to predict the depth of the ore. However, several years of ore reserves have been proved in the existing mining areas. Important ore minerals are argentite, native gold, and electrum. Trace amounts of galena, chalcopyrite, and sphalerite are associated with the precious metal mineralization. The vein is mainly composed of calcite and quartz. Mine-run underground ore is dumped from the hoisting skip into a coarse ore bin followed by a jaw crusher, an impact crusher, and a 600 mt (650 st) fine ore bin. The mill has a capacity of 317 mt per day (350 st per day). Two-stage grinding is done by a rod mill followed by cyclones with the underflow sent to a ball mill in closed circuit with the cyclones. Cyclone overflow after conditioning receives a primary float in four 1.7 cu m (30 cu ft) cells and a second stage of conditioning ahead of 24 0.8 cu m (30 cu ft) secondary flotation cells. No cleaning stages are used. Flotation tailings are cycloned for a sand-slime separation with the sands used as underground stope fill and the slime portion to tailing dam storage.

Jan 1, 1981

By W. H. Porter, M. E. Wadsworth, J. R. Lewis, K. L. Leiter

The oxidation of Cu2S in oxygen and the sulfating of Cu2O in oxygen-sulfur dioxide atmospheres was carried out under a variety of conditions. The oxidation of Cu2S was found to be retarded by entrapment of SO, and O2, which stabilized internal sulfates for long periods of time. The course of the reaction was followed by measuring weight changes and also by SO, evolution. Sulfating of Cu2O was a maximum at ratios of SO, to O2 approximating maximum SO, production. At elevated temperatures SO, was found to increase the rate of oxidation of Cu2 O to CuO even though sulfates did not form. All sulfating reactions followed the parabolic rate law indicating diffusion. MANY studies of the roasting of copper sulfides have been reported in recent years. Diev et al.1 investigated the roasting of chalcocite (Cu2S) in air, and oxygen enriched air. Lewis et al.2 also studied the oxidation of natural and synthetic chalcocite in air and oxygen atmospheres and their studies indicated that the maximum formation of water soluble sulfates occurred at approximately 450oC. Ashcroft3 reported that oxide production during the roasting of chalcocite resulted only from secondary decomposition of sulfates which were formed as primary products. peretti4 refuted this claim by showing that a layer of Cu2O appeared directly adjacent to the Cu2S during roasting of cylindrical briquettes of cupric sulfide, CuS. The linear advance of the Cu2S-Cu2O interface was used as a measure of the kinetics of the roasting reaction. The reactions proposed were: 2 CuS—Cu2S + 1/2 S2 [4-1] 1/2 S2 + O24 SO2 [4-2] cuzs +3/2 O2 4 Cu2O + SO2 [4-3] cu2o + 1/2 O2—2 cuo [4-4] At temperatures above 663oC, CuO was the only final solid phase reported. Below 663" C increasing amounts of sulfate were found mixed with the CuO. McCabe and Morgan5 investigated the roasting of discs of synthetic chalcocite and reported the following sequence of products beginning at the sulfide surface: Cu2O, a mixture of Cu2O and CuSO4, Cum,, CuO . CuSO4, and CuO. The principal reactions were reported to be: Cu2S + 3/2 O2-Cu2O + SO2 [5-1] CU2O + 2 SO2 + 3/2 O2—2 CUSO4 [5-21 2 CUSO4— CUO . cum, + SO3 [ 5-31 cuo . cuso4—-2 cuo + SO, [ 5-41 Eq.15-11 supports the claim of Peretti, Eq. [4-31, that CuzO is formed directly from Cu2S rather than as a secondary product from a sulfate as suggested by Ashcroft. On the other hand CuO was found to form as a secondary product from the decomposition of copper sulfate and basic copper sulfate, Eqs. [5-31 and [5-41. The formation of sulfates was explained by McCabe and morgan5 to be a direct reaction of Cu2O with 0, and SO, or SO, at distinct regions in which the partial pressures of each were such as to form the sulfate. Thornhill and pidgeon6 roasted both natural and synthetic chalcocite grains in air at temperatures between 420" and 550° C. They found a dense primary oxidation layer in contact with the sulfide. A secondary layer of porous oxidation products was found to expand with roasting time. The oxide products were leached away and the remaining core was studied by X-ray diffraction. The X-ray patterns showed an increased conversion of chalcocite to digenite with time. Digenite,7 a defect structure of cuprous sulfide, occurs naturally as Cu,-,S where x = 0.12 to 0.45, with an average analysis of Cu, ,S. The mechanism of digenite formation was proposed as: Cu2S + oxygen—Cu1-8S + 0.1 Cu2O [6-1] Cuj.eS + oxygen—0.9 Cu2S + SO2 [6-2] It is apparent from the above studies that the oxidation of Cu2S, ultimately ending in CuO, may be divided into ihree general stages (all of which may occur simultaneously): 1) primary oxidation to Cu2O; 2) secondary sulfate formation; and 3) sulfate decomposition. Consequently reactions of O2 and SO, with Cu20 constitute important aspects of the roasting of chalcocite. Virtually no studies have been made regarding sulfating reactions involving Cu,O. Mills and Evans8 noted the effect of sulfur dioxide on the oxidation of copper at low temperatures and low SO, partial pressures. They reported a measurable increase in the oxidation rate of copper when SO2, was present. Interest in the Cu2O-CuO-0, system has been limited predominantly to misciblllty studies and determinations of heats of formation by

Jan 1, 1961

By Emerson F. Heald

A systematic study was made of new and old data on chemical activities in Fe-Pt alloys at elevated ternperatuves. Experimental results may be expressed in terms of the excess free energy using Least-squares analysis of the data gave the following values for the constants: for the temperature range 1130° to 1350°C, and tentatively to 155O°C, B = -3.326564 and C = 0.221051; for the temperature range 650" to 850°C, B = -2.555690, C = 1.762735, and D =0.097196. In the study of iron-containing silicate systems, it is sometimes desirable to have a direct experimental measure of the activity of iron in the system. The well-known solubility of iron in platinum, often a headache in experimental work on iron compounds under reducing conditions, can be used to advantage in this respect. If the activity of iron in an Fe-Pt alloy in equilibrium with the silicate is known as a function of the composition of the alloy, chemical analysis of the alloy will give a knowledge of the activity of iron in all of the phases in the system. The present study was undertaken in order to elucidate the characteristics of Fe-Pt alloys as iron activity indicators. This work is intended to tie together some previous work, which may be summarized as follows. Larson and Chipman1 determined the activity of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with calcium oxide-iron oxide-silica melts of known iron activity. Compositions of the resulting alloys were determined by chemical analysis. A similar study was carried out by Taylor and ~uan,&apos; who worked at 1300°C. They brought the Fe-Pt alloys into equilibrium with iron oxide under conditions of known partial pressure of oxygen, and thus, from the work of Darken and ~urr~,~ conditions of known iron activity. Compositions were determined indirectly, by following the change in weight of the sample. Sundaresen et el* used the electromotive force of cells in which the alloy formed one electrode in order to measure the activity of iron in the alloy at 650" and 850°C. These temperatures were chosen to be above and below the first-order phase transition which takes place upon the ordering of Fe3Pt and the second-order transition which occurs upon the ordering of FePt3. EXPERIMENTAL 1) High Temperatures. The starting materials used were thin platinum foil, about 0.002 mm thick, and Fisher Certified reagent ferric oxide, Fez03, which had been heated for 24 hr at 1000°C. An intimate mixture of 80-mesh Fez03 and platinum platelets was placed in a thin platinum foil envelope. The latter was suspended from thin platinum wires in the hot zone of a vertical-tube, platinum-wound furnace of the type described by Muan and ~sborn.~ A capillary gas mixer similar to that used by Darken and Gurry3 was used to prepare a precisely known mixture of carbon dioxide and hydrogen, which was allowed to flow upward through the furnace tube. The partial pressure of oxygen in contact with the sample was thereby fixed at a value which was calculated from the charts prepared by porter? Temperatures were measured with a Pt-10 pct Rh-in-platinum thermocouple, which was calibrated using the melting points of gold (1062 .@C) and diopside, CaMgSizOB (1391.5"C). Temperature control was maintained to within i3"C with a Geophysical Laboratory proportional controller, using the furnace resistance as the sensing element. Samples were quenched by passing a small current through the platinum suspension wires, allowing the sample to drop into a bath of dibutyl phthalate at the bottom of the furnace tube. Prior to chemical analysis the samples were washed with acetone and dried. 2) Chemical Analysis. It proved possible, in almost all cases, to separate the Pt-Fe platelets physically from particles of iron oxide. The platelets were dissolved in a small volume of aqua regia, evaporated to dryness, and redissolved to 0.1 M HC1. In order to determine iron in the platinum alloy potentiometrically, it is necessary first to remove the platinum. A 10-cm column of Amberlite IR-120 cation exchange resin in the hydrogen form provided separation quickly and quantitatively: The mixture of iron and platinum in 0.1 M HC1 was added to the top of the column, and washed with about 100 ml of 0.1 M HC1. Under these conditions, the iron, principally in the form of cations such as FeC1" and FeCl;, is held quantitatively in the uppermost centimeter of the column. The platinum, in the form of anions such as PtC&- , is washed through without being adsorbed. After a qualitative test with stannous chloride indicated all of the platinum was removed, the iron was

Jan 1, 1968