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By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.' and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By W. C. Smith, P. J. Hickey

After a short historical background of the process evolution, this article descvibes present-day plant facilities and operating techniques utilized for high-purity bismuth production. The plant is one of the world's largest, with an annual output of some one million pounds of refined bismutlz. PREVIOUS papers1 written by staff members of Cerro de Pasco Corp. have referred briefly to the production of refined bismuth. Since the Corporation is one of the world's foremost producers of high-purity bismuth, a detailed description of the process for extracting the metal may be of general interest. Following a short historical background of the development of the actual process, this presentation will trace the progress of bismuth from its entry into the primary smelting circuits to its concentration in electrolytic lead cell slimes. Our facilities for the treatment of anode muds will be described and the extractive methods given in some detail, with particular emphasis on the techniques which result in the production of refined metal. HISTORICAL BACKGROUND Shortly after Cerro de Pasco began smelting operations at Oroya, Peru in 1922, it became apparent that the dust carried by copper converter gas contained appreciable amounts of bismuth. Although dust collection efficiency was poor prior to building of the 550-ft stack and installation of the central cottrells in 1938, a large stock of dust was accumulated during the intervening years, having the following approximate composition: Oz. per ton Ag - 11.0 Pct Sn — 0.5 Pct Pb - 49.0 Pct Zn - 6.5 Pct Bi - 2.0 Pct Insol. - 1.5 Pct Cu - 0.7 Pct Fe - 2.3 Pct Sb - 3.0 Pct S - 10.0 Pct As - 7.5 In the mid-1920's, experimental crucible melts of this dust with carbon indicated that most of the bismuth and silver, and some of the lead, could be reduced to a fairly clean bullion. Other products were a small amount of leady copper matte and a slag high in zinc, arsenic, antimony, and lead; this slag contained some tin but only small quantities of silver, bismuth, and copper. After the laboratory results had been confirmed by operation of a small reverberatory, a dust reduction furnace was constructed. The ±10 pct Bi-Pb bullion produced from this operation was stocked until 1930, when an Oroya-designed converter type furnace3 was installed for the elimination of arsenic, antimony, and some lead from the bullion. This process concentrated the bismuth from 10 to about 60 pct. By means of the bismuth process developed4 by W. C. Smith at East Chicago (1909-1914) and the discovery of a method5 for separation of lead from bismuth with chlorine gas in 1929, it became possible to begin production of refined bismuth. Unfortunately, bismuth deleaded with chlorine always contained residual chlorides, and the removal of the chlorides by caustic soda left a lead content of 0.02 to 0.04 pct. This final problem was solved6 by substitution of air-blowing for the caustic treatment, which effectively removed all excess chlorine and gave bismuth which was practically lead-free. In 1934, a pilot electrolytic lead refinery began operations at Oroya. Lead smelting was resumed in 1935 and two years later a 100-ton-per-day lead refinery was put into service. In conjunction with the latter, the present-day Anode Residue Plant was constructed. Until 1940, the plant treated both lead anode slimes and dust reduction bullion. The dust reduction furnace was shut down in that year, and all cottrell dusts (with the exception of the product from the arsenic cottrell) were mixed with pyrite and treated in a Wedge roaster to eliminate all possible arsenic. Calcine from this operation joined the sinter plant feed; hence the bismuth from the copper and lead circuits was collected in the lead bullion and subsequently in lead anode slimes from the electrolytic lead refinery. The latter source has been the only bismuth-bearing material of any consequence entering the Anode Residue Plant from late 1940 to the present. A copper refinery began operating in 1948, and the cell mud from this plant is mixed with lead slimes and processed through the same circuit, though only a small quantity of bismuth is present in electrolytic copper cell residues. BISMUTH INTAKE Present-day routes which are followed by the new bismuth feed from its entry into the primary smelting circuits to its arrival at the Anode Residue Plant are traced schematically in Fig. 1. As illus-

Jan 1, 1962

By N. A. Gokcen, J. Chipman

A revised treatment of the authors' published data eliminates the complex relation previously proposed between concentration of silicon and activity coefficient of oxygen in liquid iron. Revised values of the thermodynamic properties of the liquid solution are presented. IN a recent experimental study of the reaction SiO2 (s) = Si+ 2O; Kf, = [% Si] [% O]² [1] the authors' found a substantially constant equilibrium product in liquid iron at 1600°C of 2.8x10-5 They also reported extensive data on the reactions: SiO2 (s) + 2H2 (8) = Si- + 2H2O (g); K'2= [% Si] (H2O/H2 [2] and H, (g) + 0 = H2O (g); K'3 =( H2 O [31 (H2) [%O] From the results on reaction 3 and earlier data of Dastur² on this same reaction in the absence of silicon, they determined the activity coefficient of oxygen, f0, on the basis of the definition K3 = (H2O)/ (H2)f0 [% 0] where K, is the equilibrium constant and f0, is taken as unity in the pure Fe-0 system. Similarly values of fsi were deduced from results on reaction 2. In a more recent study" of analogous reactions in the system Fe-A1-0, it was found impossible to reconcile the results on reaction 3 with Dastur's data; accordingly the latter were ignored and the equilibrium results were extrapolated to find a value of K, at zero concentration of aluminum. This procedure failed to locate the cause of the discrepancy but it did yield reasonable values of activity coefficients. It also avoided introduction of the complex empirical relation between the oxygen activity coefficient and the concentration of the added element. The same type of discrepancy exists for system Fe-Si-0.' In the earlier paper an attempt was made to fit both sets of data by a single curved line (Fig. 6 of ref. l), the form of which is contrary to the theoretical requirement of a finite slope at infinite dilution. In the light of experience on the Fe-A1-0 system the discrepancy must be recognized as one which can be resolved only by more refined measurements. Accordingly Figs. 6 and 10 are retracted. It is pointed out also that until the discrepancy is resolved Figs. 7, 8, and 11 are subject to some uncertainty. Qualitatively the following conclusions still appear valid: 1—The activity coefficient of oxygen is reduced by addition of silicon. 2—In dilute solutions the activity coefficient of silicon increases with its concentration. 3—With respect to equilibrium in reaction 1, the above effects are approximately compensating. The discussion of K'1 in the previous paper requires no revision. It was pointed out that the constancy of the product [% Si] [% 0]² ndicated a compensating effect of the activity coefficients of silicon and oxygen. Therefore, as a very good approximation, K1 = K'1 and the following average values are suggested both for K, and K', at the temperatures 1550°, 1600°, and 1650", respectively, 1.0x10-", 2.8~10-" and 5.5 ~lo-'. Revision of the thermodynamic treatment is necessitated by the recent appearance of new data, based on a combination of combustion and solution calorimetry,' which yields for the heat of formation of low-cristobalite from the elements, the value —209,330 ±250 cal per mol at 25°C. This is about 4000 cal larger than the value previously accepted. The new value for cristobalite is used, together with Kelley's tables of high-temperature heat contents" and entropies and with Korber and Oelsen's' heat of fusion of silicon to obtain the following equation for the standard free energy of cristobalite in the temperature range 1700" to 2000°K: Si (1) + 02 (g) = Si02 (crist.); ?F° = -217,700 + 47.OT [4] The free energy of solution of 0, in liquid iron is:8 O2 (g) = 20 (in Fe); AF° = -55,860 - 1.14T [5] and these two equations are combined to give: Si (1) + 20 = SiO, (crist.); AF° = -161,840 + 48.14T [6] ?F°1873 = -71,700 cal. From the experimental value of K, = 2.8x10-5, Si + 20 = SiO2 (crist.); ?F°1873 = -39,000 cal. [7] The combination of Eqs. 6 and 7 yields the free energy change when liquid silicon dissolves in iron to form the dilute solution of unit activity (1 pct). Si (1) = Si; ?F°1873 = -32,700 cal. [8] The heat effect in this process according to Korber and Oelsen' is an evolution of 28,500 cal per gram

Jan 1, 1954

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By E. S. Moore

ALTHOUGH nickel was in use in alloys long before the Christian era, the metal was not discovered until 1751, when Cronstedt recognized it in niccolite from Sweden. The Chinese apparently used a nickel alloy, known as "pahfong" thousands of years ago and Persian coins dating farther back than 200 B.C. consist of a copper-nickel alloy similar to some of those now in use in coins. The pure metal was first prepared about 1775 and the metal was refined for commercial purposes some years later. The nickel industry did not attain much prominence until the ores in New Caledonia were discovered. Exports of ore from that country began in 1875 and since that date there has been an ever-increasing world output of nickel and a great expansion in the uses of the metal except during short periods of commercial and industrial depression. Previous to 1875, for a number of years, Norway was the chief producer, although the metal was mined also in Sweden, Finland, Italy, Germany, Austria, France, China, the United States and other countries. With the dis-covery of nickel deposits in the Sudbury district, Ontario, a new factor was introduced into the nickel industry and Sudbury has since become the overwhelmingly dominant feature in the world&apos;s nickel markets. Although nickel was first discovered in Canada as early as 1848 near the north shore of Lake Huron and nickel-copper sulfides were found in 1856 by surveyors working close to the present location of the important mine at Creighton, in the Sudbury field, it was not until 188.3 that any importance was attached to this field. In that year copper sulfide attracted attention where the main line of the Canadian Pacific railroad was being projected across Canada to the Pacific coast. Mining began near this discovery in 1889 but in the meantime operations had begun in 1886 in other parts of the field and by 1890 about 100,000 tons of ore had been raised. In the Sudbury field, as in Norway and at the old Lancaster Gap mine in Pennsylvania, the ore was first mined for its copper content and difficulty in the refining of the copper led to the discovery of the important proportions of nickel in the ore. No. 3 property of the Inter-national Nickel Co., now known as the Frood, the greatest deposit in the

Jan 1, 1932

By C. R. Whitney, G. N. Maniar, D. R. Muzyka

Previous results have shown that Pyromet 860, an Fe-Ni-base heat-resistant alloy, is stable at temperatures as high as 1500°F for aging times as long as 100 hr. This Paper describes the results of long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Times as long as 37,660 hr were employed. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffraction, and microprobe techniques. phase, containing cobalt, nickel, and molybdenum, was detected after extended exposures from 1200" to 1400°F and careful study was performed to describe the kinetics of its formation in this alloy. µ phase formation apparently has little effect on the elevated-tem-perature properties of Pyromet 860. For times as long as 500 hr at 1300°F and below, with µ phase present, m significant effects on ambient temperature properties were noted. For longer times at 1300°F and after 1400°F exposure, the effects of u phase on ambient temperature tensile strength properties are not clear due to y&apos; effects and grain boundary reactions. Electron-vacancy, N,, numbers were calculated using different methods described in literature and correlated with the present findings. In the selection of alloys for use in gas turbine applications, structural stability ranks as a primary criterion. High-temperature strength and cost are also of major concern. With these factors in mind, Pyromet 860 alloy, an Fe-Ni-base superalloy was designed. This alloy combines the cost advantages of Fe-Ni-base alloys such as A-286, 901, and V-57 with improved strength and structural stability&apos;1,2 and no tendency to form the embrittling cellular 77 phase. A previous study3 reported on the stability of Pyro-met 860 at temperatures from 1375" to 157 5°F and times up to 100 hr. That study showed that the y&apos; precipitates increased in size and separation and decreased in number with an increase in time or aging temperature. No deleterious phases were found to occur. In the present work, samples from four production heats were subjected to long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Various heat treatments were used on the starting samples and tests were run up to 37,660 hr. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffrac- tion, and microprobe techniques. Electron vacancy numbers, Nv , calculations were made by TRW.4 Experimental results are correlated with the Nv data used to predict occurrence of intermetallic phases such as a phase. EXPERIMENTAL PROCEDURE Mechanical Tests. Material for the present study came from four production size heats of Pyromet 860 alloy, weighing from about 3000 to about 10,000 lb. All of these heats were made by vacuum induction melting plus consumable electrode vacuum remelting. The nominal analysis for this alloy is compared with the actual analysis of the four heats in Table I. Sections of these heats were forged to 9/16-in. round bar,3/4-in. square bar, 3-in. round bar, 4-in. square bar, and a gas turbine blade forging about 16 in, long, about 6 in. wide, and weighing about 20 lb. In general, all forging of this alloy is done from a 2050°F furnace temperature. Longitudinal test blanks were cut from the centers of the smaller bars, from mid-radius positions for the 3- and 4-in. bars, and from the air foil of the gas turbine blade and heat-treated according to the procedures outlined in Table 11. Heat treatment A is the "standard treatment" recommended for this alloy for best all-around strength and ductility. Heat treatment B is a modification of treatment A for improved tensile strength at moderate temperatures. The treatment coded C was designed for treating large sections according to a procedure previously described.&apos; Heat treatment D was developed to yield optimum stress relaxation characteristics at 1050°F for a steam turbine bolting application. After heat treatment, the test blanks were machined either to plain bar creep specimens with a gage diameter of 0.252 in., to combination smooth-notched stress-rupture bars with a plain bar diameter of 0.178 in. and a concentration factor of Kt 3.8&apos; at the notched section, or to notch-only specimens. All specimens conformed to ASTM requirements. Metallography. Most of the creep-rupture tests were continued to failure. A few bars were fractured as smooth or notch tensiles after creep-rupture exposures. After fracturing, ordinary metallographic sections were made primarily in gage areas adjacent to fractures to represent a "high-stress" region and through specimen threads to represent a "low-stress" region. All metallographic sections were made in a longitudinal direction with respect to the test specimen axes. For optical microscopy, the samples were etched in glyceregia (15 ml HC1, 5 ml HNO,, 10 ml glycerol). For XRD analysis, the phases were extracted electrolytically in two media: 20 pct &Po4 in H20 for selective extraction of y&apos; and 10 pct HC1 in methanol for carbides and other phases.

Jan 1, 1970

By J. E. Campbell, G. D. Calkins, N. M. Ewbank, M. Pobereskin, A. Wesner

GRINDING for size reduction affects the economics of many processes and products. It is essential as the first step in many industrial processes and is also a finishing step for materials with properties depending on particle size, such as talc, cement, and silica sand. Intermediate and fine grinding are vital operations in the U. S. cement industry, which is producing more than 250 million bbl of cement per year.&apos; Wear of the grinding media is a large part of the grinding operation cost. Problems encountered in grinding cement are so complex that evaluation of efficiency and economy of grinding media is difficult.2 It has been especially difficult to evaluate the relative effectiveness of different types of balls because there are no good testing techniques. Many other industrial operations can be evaluated on a laboratory scale with reasonable accuracy. This does not hold true for evaluation of grinding balls. The consistent results obtained in a laboratory test under a given set of conditions are not always borne out in field application. Rough evaluations of the effectiveness of various compositions and types of grinding balls have been made in the field by using a full charge of one type in a mill and comparing the production record with another run using another type of ball. This method is time-consuming and not very precise, as the second run may not have been carried out under identical conditions. Laboratory-scale tests, on the other hand, have yielded inconclusive results, and many investigators have turned their attention to the development of a field testing technique. Field testing small sample lots of grinding balls has been impractical because it is difficult to identify and recover the test specimens from the grinding mill, and individual groups of balls that have undergone different heat treatments can not be separated.".4 To overcome these difficulties, previous investigators have identified the balls by distinctive marks, notches, and drilled holes, but this procedure has three serious drawbacks: 1) Grinding characteristics and quality of the steel balls may be affected. 2) Physical markings may be worn away in the grinding process, especially during a prolonged run. 3) Recovery from the bulk of the charge will be extremely difficult because the markings are hard to see and may be masked by a coating of the product. To circumvent these difficulties, a radioactive-tracer technique was proposed for recovery and separation of steel grinding balls and subsequent evaluation of the various compositions of the balls. The proposed technique involved five basic operations: 1) Thermal-neutron irradiation activation5 of each group of test grinding balls to a different level of specific radioactivity. 2) Addition of groups of radioactive steel-ball specimens into a ball tube mill. 3) Recovery of radioactive steel-ball specimens from the bulk of the mill charge. 4) Separation of the various groups by their specific radioactivity. 5) Evaluation of actual grinding ball wear. Before any physical tests were performed, required neutron irradiation intensity and time were calculated. Probable composition of the steels to be used was ascertained. An examination was made of the radioactive nuclides8 to be formed which would contribute measurably to the radiation level immediately after irradiation and during the test operation. The radioisotopes formed, their types of radiation, and their half lives are listed in Table I. Of these radioisotopes only iron-59 and chromium-51 were significant for the actual wear test. The intensity of radiation that could be detected by a Geiger counter when the test was completed was the basis for the minimum activation level established. The intensity of radiaton that could be safely handled at the beginning of the test was the basis for the maximum activation level, although this was not considered a major problem. Ten groups of grinding balls of various composition and/or surface or heat treatment were to be tested. One group was designated for the minimum irradiation time. The remaining groups were designated for irradiation periods that increased by increments of 33 pct from that of each preceding group. This difference was considered enough for separation and identification of the groups by comparison of specific activity. Potential Hazards: Possible radiation hazards that might be encountered during this experiment were evaluated for the three important phases: 1) the radiation hazard of placing balls and removing them from the mill, 2) contamination of the product cement by radioactive material worn from the balls, and 3) contamination of the steel by the radioactive balls left in the mill. The radiation intensity expected from the whole group of radioactive balls was calculated to be 250 milliroentgen per hr at 1 ft. This meant the balls would require special shielded packaging and warning labels on the shipping containers. In a radiation field of 250 mr per hr a man can work for 1 hr without exceeding maximum permissible weekly exposure. Since the balls could be dumped into the mill in a matter of seconds, relatively little radiation exposure was anticipated at this stage of the operation. If the weight loss in the balls was 7.7 pct per month and the cement feed through the mill was

Jan 1, 1958

By R. B. Adamson

The fatigue behauior of irradiated copper single crystals is compared to that of unirradiated crystals. Proton or electron irradiation did not substantially change the fatigue-lzj.e, fatigue-hardening-, or slip-line characteristics, while neutron irradiation did appear to alter these parameters. Postfatigue transrrzission electron microscopy did not reveal any marked structural differazces between irradiated and unirradiated specimens. Possible dislocatio~a mechanisnzs to explain the observed behavior are discussed. A LTHOUGH considerable work has been done to ascertain the effects of radiation on the tensile properties of metals (e.g., Refs. 1 and 2), little work of a basic nature has been reported on the effect of radiation on fatigue properties. Since it is known that fatigue properties are sensitive to conditions at the surface of the metal, it was felt that charged particle irradiation, whose penetration into metals is very small, might influence the fatigue behavior. To investigate this surface effect, irradiations with 10 mev protons and 1.5 mev electrons were conducted. The range of 10 mev protons in copper is about 0.236 mm; which is very small compared with the thickness of the specimens used (1.53 mm). The range of 1.5 mev electrons is somewhat larger, on the order of 0.665 mm.4 On the other hand, irradiation with reactor neutrons produces damage throughout the entire specimen, so neutron irradiation can be used to study the effects of bulk damage. The damage introduced by proton and neutron irradiation is expected to con!ist of large interstitial dislocation loops,5 tiny (<25A) vacancy loops," and/or various vacancy-rich regions called depleted zones.&apos; In the case of electron irradiation at about -173°C the damage is expected to consist of isolated Frenkel pairs.&apos; The effect of radiation damage on the fatigue properties of some engineering materials has been reported,g,10 but the results are not clear-cut or consistent. SPECIMEN PREPARATION Zone-refined copper was used to grow single crystals by a modified Bridgeman technique in an inert helium atmosphere. Using a seeding method, single crystals were obtained as bars about 6 in. long with a cross section of 3 by $ in. Immediately upon removal from the split-mold graphite boat in which they were grown, the very soft bars were embedded in a room-temperature setting plastic. They could then be cut into specimen lengths without introducing any long-range damage. Generally, four or five specimens plus one seed were obtained from each bar. The plastic material was dissolved away in acetone and the orientation of each sample was checked by the standard Laue X-ray

Jan 1, 1968

By D. E. Peacock, B. Harris

The mechanical behavior of a niobium (columbium)TUNG alloy containing 20 wt pet Ta. 15 wt pet W, and 5 wt pct Mo has been studied in the temperature range 77° to 423°K. All specitrzens tested, apart from those into which oxygen was introduced deliberately, were fully recrystallized at 1500°C, had an average grain diameter of approximately 0.03 mm, and a combined carbon, ox-vgen. nitrogen, and hydrogen content of not not more than 250 ppm The meckatnical behavior of this alloy was found to be similar in seine respects to that of unalloyed bcc transilion metals. Both yield and flow stresses were sensililae to changes in deformation rate and both increased rapidly as the temperature was lowered below 150°C. A detailed examination revealed, however, that most of the temperature dependencc of the yield stress could be accounted for by the temperature dependence of the elaslic, modulus, whish is not true of the unualloyed metals. In lension at moderate strain rates, the trunsition fvom ducfile to hvittle behavior occurred just belour room teunperature bur incveasing the oxygen content from 190 to 200 pptn raised the transition temperature to about 4000K. TUNGSTEN and molybdenum have been found to be very effective high-temperature solid-solution strengtheners of niobium, but the amounts of these elements that can be added are limited if the alloy is to retain useful room-temperature ductility. It has been shown, however, that partial replacement of niobium with tantalum lowers the ductile-to-brittle transition temperature of such alloys and allows larger additions of molybdenum and tungsten to be made. Some of the high-temperature properties of niobium alloys containing these elements have been reported by Bartlett et al.,&apos; and the work presented here describes the low-temperature behavior of one of these, a solid-solution alloy containing, by weight, 20 pct Ta, 15 pct W, and 5 pct Mo. The elastic modulus, the temperature and strain-rate dependence of the yield and ultimate tensile stresses, and strain-hardening effects are discussed and compared with those of unalloyed niobium. EXPERIMENTAL MATERIAL AND PROCEDURE The material used in this investigation was produced from a 6-in.-diameter, double arc-melted ingot. This was can-extruded at about 1150°C to a 3-in.-diameter billet, and after annealing for 1 hr at 1345°C the billet was heated to 1315OC and part rolled and part forged to 0.5-in.-thick plate. The resulting material exhibited a cold-worked structure

Jan 1, 1965

By A. H. Daane, J. J. Hanak, F. H. Spedding

IN the study of the rare earths at the authors&apos; laboratory, methods have been devised for preparing pure rare earths and many of their properties&apos;- have been determined. Very little information is found in the literature on the properties of europium metal, which is the scarcest of the naturally occurring rare earths. Since we have recently prepared europium in appreciable quantities, we are in a position to describe the method of preparation and some of the properties of this metal. Metallic europium was first prepared by Klemm and Bommera who heated a mixture of potassium and EuC1, in vacuo, and obtained a mixture of europium metal and KC1. Trombe4 electrolyzed a molten salt bath containing NaC1, KC1 and EuC1, and collected the europium in a molten cadmium electrode as a cadmium alloy. The cadmium was subsequently removed by distillation but the properties of the residue indicate that pure europium was not obtained. McCoy attempted to prepare europium by distilling mercury from europium amalgam, but the stability of the Eu-Hg intermetallic compounds prevented a complete separation of the two elements. The preparation of very pure europium was suggested by previous work in this laboratory1,4 in which ytterbium and samarium were prepared by heating the respective sesquioxides with lanthanum metal turnings to 1450°C in vacuo and distilling ytterbium and samarium from the mixtures. Subsequently, small test experiments showed that europium also could be prepared by this method. A more detailed version of this method was used in the work described in this paper. Klemm and Bommer3 found by X-ray analysis that the metal had a body-centered cubic (bcc) structure with a lattice constant a, = 4.582 ± 0.00A (converted from kX units), with a bulk density of 5.30 g per cu cm. They found europium to be weakly ferromagnetic. Spedding, et al,7 found a,, to be 4.606 ± 0.001A. Barrett&apos; showed that the bcc structure persists throughout the temperature range 5 to 3000K with a, at 5, 78, and 300°K being 4.551 ± 0.003, 4.551 ± 0.004 and 4.577 ± 0.001A, respectively. Trombe1 described europium as being iron gray, malleable, about as hard as neodymium and not attacked by cold water. He estimated the melting point to be between 1100 and 1200°C. Previous work in this laboratory indicated that the pure metal corrodes rapidly in air and reacts with cold

Jan 1, 1959

By E. M. Cox, T. Rosenqvist

IN a recent investigation, carried out at the Institute for the Study of Metals, the affinity of sul-phur for iron, copper, and manganese was studied over the temperature range 700" to 1300°C.&apos; It was found that copper exhibits a rather high affinity for sulphur, especially at higher temperatures; and attention was called to the possibility that copper when present together with sulphur in liquid steel would tend to lower the chemical activity of sulphur and thus interfere with the desulphurization process. It was clear, however, that the data for the equilibrium between pure copper and pure copper sulphide (Cu2S) could not give any quantitative information about the effect of copper when dissolved in liquid steel. The present work is concerned with the activity of sulphur in the diluted range of the binary iron-sulphur system, and with the influence of small amounts of copper on this sulphur activity. This investigation is in principle based on the same method previously described for the binary metal-sulphur studies;1,2 namely, reaction with hydrogen to form hydrogen sulphide. The equilibrium ratio PH2s/Ph2 in the equilibrium gas mixture is, for a given temperature, directly proportional to the sulphur activity. The activity of sulphur in liquid iron has previously been studied by Chipman and Ta Li,3 White and Skelly,4 and recently by Sherman, Elvander, and Chipman.5 Morris and Williams6 have studied the effect of added silicon, and Kitchener, Bockris and Liberman,7 and recently Morris and Buehl,8 the effect of added carbon on the sulphur activity. In present day steelmaking processes the steel bath contains between 0.01 and 0.1 pct sulphur, and the copper content may be as high as 0.5 pct. The equi-librium gas ratio (H2S/H2) would, for such a low-sulphur content, be too low to be measured with the experimental technique we use. It has been shown by previous investigators that the H2S/H2 ratio is closely proportional to the sulphur content up to about 1 pct sulphur. The sulphur activity at very low-sulphur content can therefore be calculated by linear interpolation between 0 and 1 pct sulphur. In order to show the general trend with increasing sulphur content, the present work has been carried out to about 3.5 pct sulphur. As the effect of copper was assumed to be more a function of the Cu/S ratio than of the absolute copper content, the runs with copper were made for certain constant values for this ratio.

Jan 1, 1951

By J. Rogers, H. F. A. Hergt, K. L. Sutherland

IN 1938 Ralston4 reviewed the many attempts to find a satisfactory collector for the separation of cassiterite from its ores and in 1944 Dean and Ambrose2 summarized some further attempts. Generally, soaps and amines are effective but nonselective collectors. We have discovered that reagents containing either the polar group -SO4- or _S03- are excellent collectors for cassiterite and promise to be selective.1 The response to these reagents of cassiterite and of minerals commonly associated with it was studied, using the captive-bubble technique. Using these fundamental data, the practicability of separation and concentration of tin was investigated by flotation tests in a 2000gram Denver cell. EXPERIMENTAL METHODS Reagents All inorganic reagents were of Analar grade. The preparation and purification of sodium cetyl sulphate, cetyl trimethyl-ammonium bromide, laurylamine and cetylamine have been previously described.5 The other collectors were commercial surface-active agents, which were used without purification. Tests Captive-bubble Tests and Cylinder Flotation Tests have been previously described.5-10 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±0.2 pH units and ± 5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible, by a cross, and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, and the experimental results are indicated by a square. The curves show the limits of composition of solutions in which flotation in a cell would be possible but many factors other than those considered in these tests determine recovery and grade of a given mineral in practice. Flotation Tests in 500 and 2000-gram Denver Submachines.--Melbourne tap water, containing 12 parts calcium, 6 parts

Jan 1, 1947

By Howland Bancroft

This article is not presented as a treatise on tin mines and mining in Bolivia. It deals primarily with the tin situation, and but fragmentary information is given regarding individual properties, generalizations being necessary in so short an article. Data on general subjects related to tin mining in Bolivia are necessarily abbreviated and very incomplete. It is believed that the references to be found in this article will help those interested to a more thorough under-&apos; standing of the general conditions extant in Bolivia. Bolivia produces from one-fifth to one-fourth of the world&apos;s supply of tin. The United States consumes about one-half of the world&apos;s supply and produces practically none. Tin ore is not reduced in the United States. These facts are not generally appreciated by American mining men. Many conflicting data have been published regarding tin in Bolivia. The Transactions of the Institute contain practically no mention of this subject.1 I have made a study of mines and mining conditions in the west coast republics of South America and have been particularly impressed by the possibilities of the Bolivian field.2 In consequence the thought seems justified that the present meeting would, present a fitting occasion to bring the tin situation in Bolivia to the attention of American mining men.

Jan 9, 1913

By C. A. Stetefeldt

IK the dry-crushing of ores, either by stamps, rolls, or other machinery, it is essential that the material should be free from moisture. Hence a contrivance which effects this with economy, and is of durable and compact construction, is a great desideratum. It is claimed for the below-described shelf dry-kiln, that it possesses these qualifications in a high degree. The construction of the shelf dry-kiln is based on the Hasenclever principle. That is to say, a number of inclined shelves are arranged zig-zag above each other in a vertical shaft, having openings or slits where they meet, on which the ore rests in a stratum, the thickness of which is governed by the width of the slits and the inclination of the shelves. If a portion of the charge is removed at the end of the bottom shelf, a sliding motion of the ore takes place on all shelves above, and the top shelf is replenished from a hopper set over it. It will be seen that the shaft is divided by the shelves into a number of triangular prismatic spaces. Through these the hot gases from a fireplace are made to circulate, each space communicating with the next one by a flue arranged in the sidewall of the shaft. These flues being located on alternate sides of the shaft, a continuous passage is formed through the whole structure. After thus stating the principle of the construction, its details will be easily understood by reference to the drawings, Fig. 1 to Fig. 5. The drawings, Fig. 1 to Fig. 4, represent two kilns united into one structure. The cast iron shelves(a) are 2 feet 4 inches wide and 5 feet long, with sides and a back 4 inches high, and are cast a full halfinch thick. How they rest on the brackets(d), and interlock each other, is shown in Fig. 5. Three such shelves, with an inclination of 38&apos;) are placed in one row in a brick shaft 7 feet 1/2 inch wide and 4 feet deep. The ore hoppers(g) rest on the iron bems(f). At the end of the bottom shelves are the discharge-doors(b), with shoots projecting beyond the front wall. A swinging apron(e) keeps the ore in place. By dropping it a car below the shoot is filled with dry ore. A number of extra-large pieces of ore may cause a stoppage in the slits ; for such an emergency the openings(e) are provided, through

Jan 1, 1884

ROBERT PEELE, New York, N. Y. (written discussion *).-This excellent paper is one of a number of recent detailed descriptions of the, methods and plant in use at prominent mines of the country. The publication of such papers cannot be too highly praised. In the past, the interchange of inside information has often been hampered by the disinclination of some mining companies to permit publication of details of their work. These companies apparently have not realized fully that free discussion is of mutual benefit; that members of mine staffs are aided in. keeping up to date, in improving old methods and devising new ones to meet changes in conditions, and, by a wholesome feeling of rivalry, are stimulated to introduce economies and do better work. In writing this paper, Messrs. Haight and Tillson have packed a large amount of information into a relatively small space, and the numerous illustrations, chiefly reductions of working drawings, are valuable. The authors are also to be commended for their highly detailed Table of Contents, which adds to the usefulness of the, subject matter. The method of mining at Franklin does not fall readily into any of the accepted classifications. It is a combination of shrinkage stoping and mining of the pillars by a modified top-slicing method. Attention may be called to the fact that, in the wider parts of the orebody, the stopes, 17 to 18 ft. (5.2 to 5.5 m.) wide are transverse; in the narrower parts, they are longitudinal, that is, in the direction of the&apos; strike. This varia-tion is made necessary by the shape and character of the deposit, and distinguishes practice at Franklin from that in some of the western mines. The direction of the stops is changed from transverse to longitudinal when the orebody narrows sufficiently to make the length of a transverse stope approximately equal to its width. Some of the longitudinal stopes exceed 120 ft. (36 m.) in length, and when the hanging wall is bad, requiring prompt filling, three operations&apos; proceed simul-taneously in the same stope, viz., ore is broken at one end, while drawing down goes on in the middle, and filling at the other end. Each transverse stope or chamber is begun by a crosscut from foot to hanging wall, which is afterward enlarged to the stone width and to a height of 12 or 15 ft. (3.7 or 4.6 m.). This preliminary work is done only once for each stope, because the stope is carried up far enough to continue stoping

Jan 1, 1918

By A. U. Seybolt

RECENTLY, cases of coexisting ordered and disordered phase equilibria have been reported among face-centered cubic metals,1"3 but not on body-centered cubic systems.4 McQueen and Kuczynski5 showed a single line as the boundary between ordered solid solution of Fe3Al type and corresponding disordered solution in the Fe-A1 phase diagram based mainly on dilatometric and magnetic measurements. Such a single line would indicate a second or higher order transition. or an absence of coexisting order and disorder. The writer found previously a two-phase equilibrium region at 800°C consisting of ordered and disordered solid solutions of Fe3Si in a matrix of approximately 1-6 wt pct Si (Fe3Si is of 14.3 wt pct Si). A similar two-phase region of ordered and disordered Fe3Al solid solutions might be expected if the similarity between Fe3Si and Fe3Si structures hold true. In the present investigation, a wire of 22 at. pct Al, balance Fe and 0.0513 cm in diameter was subjected to electrical resistivity measurement in vacuum as a function of temperature between 300 and 800°C, see Fig. 1. There was excellent agreement between data taken on heating and on cooling: no hysteresis was observed. The Curie temperature was determined to be 640 °C which agrees with the finding by McQueen and Kuczynski.5 But in addition, there were two transitional points in the resistance-temperature plot at 510oC and 400 "C. The former is thought to be a connection with the transition from disordered state to a coexisting order and disordered equilibrium state; while the latter, from such coexisting state to ordered state. Fig. 2 shows a phase diagram where the suggested two-phase region lies between dotted lines. The solid lines are those of McQueen and Kuczynski.5 Since these authors found only a single-phase boundary between ordered and disordered Fe3 Al, it would seem likely that the dilatometric method used by these authors was not sufficiently sensitive to resolve the ordering reaction into the two-phase boundaries. In addition, their phase diagram conflicts with the statement they make on P. 1 of their paper: "The sharpness of the peaks indicates that ordering to Fe3A1 is a first order reaction." The suggestion of coexisting order plus disorder in Fe3A1 must be considered tentative until confirmed by high-temperature X-ray examination. If

Jan 1, 1961

By Alfonso W. Ovalle, Héctor R. Albornoz

INTRODUCTION The El Teniente Mine of Codelco-Chi le has extracted 588 mil lion tons of ore in its 77 year history for a total copper output of 8.800.000 tons. The mine production has been obtained mainly by traditional block-caving where grizzlemen using a hand held lever send ore through long-raises to load trains. At present the mine is about to introduce mechanized block-caving using LHD equipment to extract the primary rock. This paper describes this method which will be tested starting next month by caving an 11.000 square meter block. THE PRIMARY ROCK PROBLEM The secondary enrichment sulfides of the El Teniente ore body have characteristics which makes a standard unmechanized block-caving practice very successful. In the 60&apos;s parts of blocks encountered primary ow in the Teniente 1 and Sub-13 levels which proved to be extremely hard to extract. These foretold the obstacles that arised in the central part of the Teniente 4 level. Preparation of a completely primary 8.100 square meter block started in 1970. Its undercutting was completed by the end of 1972 and by 1973 the problem of mining the primary rock was clearly visualized. The numbers below describe the difficulties in mining this block: -Long-hole drilling rate is 90 m (270 ft) per shift in secondary rock and 37 m (110 ft) in primary. - Undercutting which is completed in 9 shifts in secondary took 180 shifts in the primary block. - Average grizzlymen productivity in secondary is 250 tons per shift while in primary it is only 25-30 tons, both at 343 mm (13 1/2 in. ) grizzly opening. - Powder consumption for secondary blasting increased from 8 grams per ton in secondary to 84 in primary. - The protection pillar between the under- cutting and the production levels was 60% broken in primary while 20% is usual for secondary. - Extraction advanced 5 cm per day in primary while a 50 cm per day rate is the aver- age in secondary. This is the main reason that after 8 years this primary block has a 20% extraction. Secondary blocks take 1.5 to 3 years to complete their extraction. - 80% of the boulders in primary rock are larger than 343 m (13 1/2 in.) with 10-20 % of them larger than 3 meters. -Direct cost of production (preparation, undercutting, extraction and haulage), using the traditional block-caving design for secondary rock, increased 3.5 to 4 times when used in primary rock. The following indicators of Table 1 show the rock characteristics differences.

Jan 1, 1981

The Pinson Mining Co., which will start production in very early 1981, is the fourth Carbon-In-Pulp plant to be put into operation in the United States. The property is located in Humbolt County, Nevada, 38 km (24 miles) northeast of the town of Golconda. The famous Getchell Mine was also near Golconda and was the site of one of the early Carbon-In-Pulp plants in the 1940s. The deposit was discovered in 1971 by Reno based Cordilleran Explorations, which is founded by a consortium of Canadian mining companies. Cordilleran is a partnership consisting of John Livermore and Peter Galli. In 1972 a second but smaller deposit, called "Preble", was discovered at a location 15 miles south of Pinson. During 1980, a decision was made to place the Pinson deposit into production and Pinson Mining Company was formed. Ownership of Pinson is vested in Lacana Mining Inc. , Rayrock Mines, Inc. , Siscoe Metals, Inc., John S. Livermore, Peter E. Galli and Donald M. Duncan. Three distinct but connected ore zones occur at Pinson. Combined reserves of milling ore total 3, 200, 000 tons at an average (undiluted) grade of 4. 12 g per mt (0. 12 oz per st) Au. Initial mining will be from "A" zone which contains 1, 500, 000 tons with an average (undiluted) grade of 5. 8 g per mt (0. 17 oz per st) Au. An additional 5, 500, 000 tons of low grade ore will be mined from the Pinson deposit and processed by heap leaching. Mining reserves at Preble total at least 1, 500, 000 tons grading 2. 7 g per mt (0. 08 oz per st) Au. Production plans for the Preble deposit have not been formulated at the date of writing. Gold mineralization at both deposits is finely disseminated as sub micron sized particles. The ore at Pinson is structurally controlled and occurs in an Ordovician limestone-siltstone unit. Much of the ore has been silicified to a jasperoid. The ore zones have been entirely oxidized. Preble ore occurs in the Cambrian formation in a carbonaceous, limey shale. Only the upper part of the Preble is oxidized and amenable to conventional cyanide leaching. The Pinson ore body is adjacent to the mouth of Granite Creek in the Osgood Mountains at an elevation of 1, 615 m (5, 300 ft) with the mill being 1. 2 km (3/4 mile) from the mine at an elevation of 1, 495 m (4, 900 ft). Mine development work began in May of 1980 with ore being stockpiled for later processing. Pertinent factors affecting

Jan 1, 1981

By F. Galasso, A. Paton

ThE recent emphasis on producing boron fibers by reacting boron trichloride and hydrogen on a hot tungsten wire has brought about a renewed interest in the tungsten boride phase diagram. The reaction of the boron with the tungsten core results in the formation of 6 WB, W2B5, and another tungsten boride phase, which was suspected of being the WB4 phase reported by Chrbtien and Helgorsky.1 While the powder-diffraction data for the boride in the fiber and those reported

Jan 1, 1967

By John V. Beall

When a mine has ore averaging 5% lead, 7% zinc, 0.60% copper, 1/4 oz gold, and 6 oz of silver, adequate reserves, power and water, easy access to market, and is situated in beautiful natural surroundings with the advantages of a big city within a few hours drive, there is little left to be desired. Such a mine is the Mayflower mine of the New Park Mining Co. situated 30 miles from Salt Lake City in the Wasatch Mountains near Keetley, Utah.

Jan 1, 1949