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By J. D. Meakin

J. D. Meakin (The Franklin Institute Laboratories)— In a recent paper Garofalo12 has shown that a number of experimental creep results can be represented by the empirical relation In this expression ? is the steady creep rate, s is the applied stress, and A is a constant at a given temperature; a and n are adjustable parameters. Garofalo has shown that Expression [6] approximates to a power function at low stresses and a simple exponential function at high stresses. Among the data used by Garofalo are the results we published for creep of copper." For these results we found that the best correlation was an exponential law with different parameters in the low-and high-stress region, respectively. That is, i = A exp qs where A and q have different values above and below a critical stress a,. In Ref. 13 are listed a variety of observations which support the proposal that different mechanisms are operative at stresses above and below a,, and it is not felt appropriate to repeat those observations here. The purpose of this note is to demonstrate that, although the representation used by Garofalo does fit the experimental data very well, this fit cannot be used to conclude that only one mechanism is rate-controlling. The argument is best made graphically and is illustrated in Fig. 9. The continuous curves 2 and 3 represent pairs of simple exponential functions which intersect at i = 10-5. The curve 2 closely resembles the copper results in that a change of slope of 2:1 occurs at i = 10-5; the two functions shown are in fact: e = 10-7 exp (1.150) and ? = 10-6&apos; exp (0.576s) For purposes of comparison, curve 3 represents two exponential functions with a change of exponent of 3:1 and curve 1 has the exponent 1.150 throughout. It is quite clear that a satisfactory straight-line fit is obtained on a Garofalo plot for all three curves. The curves represent processes which have either a single stress exponent or two ex- ponents in a ratio as high as 3:l. It must, therefore, be concluded that the ability to obtain a linear dependence between log i and log (sinh cyo) cannot be taken as evidence for a single activated process. In fact, to some extent the way the experimental points quoted by Garofalo lie about a best fit straight line on the log (sinh as) plot indicates that two processes are indeed occurring. This is seen in Figs. 7(c) and 8(c) of Ref. 12 where it is particularly evident that the experimental points deviate from the straight line in a manner similar to curves 2 and 3 of Fig. 9. It is, of course, recognized that the generally used exponential form is an approximation to the hyperbolic sine function which is not valid for exponents of less than 1.2, e.g., qs < 1.2. The only curve in Ref. 12 which is affected by this restriction is Fig. 6(b) where the deviation from a In ? vs s

Jan 1, 1964

By Ta M. Li

How do you convert a copper-zinc resource into a viable economic mining operation? This problem, unlike most, was complicated by the additional presence of a sub-arctic climate, highest labor costs in the world, low-grade copper-zinc values, depressed market prices, and a complex mineralization.

Jan 12, 1977

By F. D. Waltman

Under the hot, baking sun, engineers at the AEC&apos;s Nevada Test Site have been busy for several years in the sinking of 48-in. diam shafts to depths varying anywhere from 1800 to 4800 ft below the surface. In so doing these men have evolved several new techniques which should be of interest to the mining industry. Surface Facilities Designed For Speed: "Expediency plus efficiency" is a key phrase at the Site. Because of the relatively short duration of actual mining operations, all equipment has been packaged to decrease time and cost of "set up" and "take down". The headframe, designed specifically for use over 48-in. cased shafts, can be erected or dismantled within 48 hours. The back legs are pinned and hinged to the front legs for ease of installation and, when dismantled, for movement to another site with a minimum of delay.

Jan 6, 1966

By MORTON WEBB

Discussion of the paper of Max Boehmer, presented at the Pittsburg meeting, March, 1910, and printed in Bulletin. No. 38, February, 1910, pp. 119 to 122. W. MORTON WEBB, Germiston, Transvaal, South Africa (communication to the Secretary*):-The experience of Mr. Boehmer in the Leadville district and his reputation as an engineer assure the interest of anything he may write on the ore-bodies of that district; and all engineers who have operated in Leadville will agree that the theory of the origin of the Leadville deposits, as given by Mr. Emmons in his famous monograph, does not adequately explain the genesis of all the deposits. The solution of the problem does not, however, appear to be quite so simple as Mr. Boehmer would make it; and the advance pamphlet issued by the U. S. Geological Survey, pending the completion of the main report, shows that there is still much ground for controversy. No doubt the later eruptives had a greater influence on the deposition of the ore-bodies than was thought at the time of the first investigation by the Survey; but it has always appeared to me that the influence exerted by these dikes was more in the nature of a physical than a chemical one. The weight of evidence in recent years is mostly in the direction of ascension rather than lateral secretion; and one of the strongest evidences is the fact that most of the ore-bodies lie under one of the comparatively impervious layers which help to make up the structure of these hills. On Iron hill I have found a very persistent white porphyry sheet, split off from the overlying porphyry and lying from 30 to 60 ft. below the main white porphyry and blue limestone contact. This sheet varies from a few to 50 ft. in thickness, and where found adds another "contact" to that region ; some of the largest ore-bodies on Iron hill lie immediately under this sheet. Above this is the main white porphyry and * Received Mar. 3, 1910.

Feb 1, 1911

By E. S. Bardwell, R. J. Lapee

Twenty years ago, W. T. Burns, in his paper presented at the Butte Meeting of the Institute,&apos; discussed the general scheme then in use in the electrolytic copper refinery of the Anaconda Copper Mining Co. at Great Falls, Mont., for removing impurities from tank-room electrolyte and controlling its acid content. Since then marked changes have taken place in copper-refinery practice at Great Falls. The electrolytic copper refinery in use in 1913 has been replaced by a new and entirely modern plant capable of producing up to 27,000,000 Ib. of cathode copper per month. With the building of the new plant in 1916, the treatment of converter anodes was discontinued. At first the substitution of refined anodes for converter anodes resulted in a decrease in the impurity content of the anodes, but as time went on, changes in metallurgical practices at the smelter resulted in substantial increases in the impurity content of the anodes. The leaching of the silver slime to remove copper before shipment to Raritan for treatment further added to the purification problem. The fact that the scheme of purifying electrolyte which Mr. Burns described in his paper has proved adequate for our needs under a wide variation of conditions speaks well for its essential soundness. Method of Purification Briefly, the method adopted for purifying tank-room electrolyte at Great Falls has been as follows: Each day a certain volume of tank-room electrolyte is run off and sent to the purification plant, where it is boiled down to approximately 46&apos; 136. The concentrated electrolyte is then sent to crystallizing tanks where the bulk of the copper is crystallized out as copper sulfate. The mother liquor is then passed through insoluble anode tanks to remove the last of the copper and most of the arsenic and antimony. It is then either returned to the tank room direct or boiled down to 55&apos; Bé, the iron and nickel salts crystallized out and the mother liquor returned to the tank-room circuit as restored acid. Prior to 1930 all of the evaporating was done in lead-lined tanks 13 ft. in diameter by 4.5 ft. deep, provided with lead heating coils through which steam at 30 lb. gage pressure was circulated.

Jan 1, 1934

By H. H. Podgurski, H. E. Knechtel

Annealed Fe-Al alloys do not react readily to form AlN when held at 500ºC in NH3-H2 gas mixtures, but do so upon the introduction of dislocatims. Nuclea-tion of the nitride phase occurs on dislocation sites. In turn, the growth of the aluminum nitride particles causes the ferrite phase to yield plastically, generating more dislocations for the nucleation process. The nitride phase extracted from an Fe-2 pct A1 alloy nitrogenated at 500°C was identified as stoichio-metric aluminum nitride with a hexagonal crystal lattice. THIS investigation reveals the role that dislocations play in initiating and sustaining the nitriding reaction in Fe-A1 alloys. As early as 1931 the work of Meyer and Hobrock1 suggested that the initiation of the nitriding reaction could involve a nucleation controlled process. Recently Bohnenka2 depicted the gas-phase nitriding process below 600°C as one of mixed control limited by nitrogen penetration through the surface, by nitrogen diffusion, by aluminum diffusion, and by nucleation of the nitride phase, Fig. l(a). In our research in a comparable alloy (0.57 pct Al) at 575ºC, we have observed a nitrogenation which we feel is better described by Fig. l(b). In the case of a 2 pct-A1 alloy partially nitrided at 500°C we propose the profiles shown in Fig. l(c). For a complete and accurate description of the process, a concentration profile of the dislocation density in the test specimen would be needed. EXPERIMENTAL Nitrogenization was conducted between 500" and 575°C in a variety of NH3-H2 gas mixtures on three Fe-A1 alloys: 1) zone-refined iron + 0.16 i 0.2 pct Al—levita-tion melt, 2) zone-refined iron + 0.57 0.02 pct Al— levitation melt, 3) plastiron + 2 pct Al—melted by induction heating. To demonstrate the effect of dislocations on reactivity, both cold-worked and annealed samples were investigated. All nitrogenation rate studies were conducted gravimetrically with a gold-plated invar balance4 contained in a gas-flow system. To avoid contamination of the specimens in the reaction zone of the system, the reaction chamber was constructed of high-purity dense alumina. The activity of nitrogen was fixed by specific NH3-H2 gas mixtures whose compositions were continually monitored by calibrated thermal conductivity gages and checked by chemical analysis. Variations of ± 0.1 pct NH3 could easily be detected by both methods. Throughout this paper the activity of nitrogen is defined as PN3 /PH23/2 , where PNH3, and Ph2 are partial pressures in atmospheres. Electron transmission, density measurements, and chemical analyses were made on specimens before and after nitrogenating in order to reveal structural and chemical changes. Similar studies as well as X-ray diffraction studies were conducted on nitride extractions from the nitrogenated 2 pct-A1 alloy. These extractions were obtained by the use of an anhydrous bromine-methyl acetate solution which dissolves the iron and leaves the insoluble nitrides as a residue. Hardness profiles were obtained on cross-sections of partially nitrided specimens to demonstrate the extent of nitriding through the thickness of the specimens. RESULTS AND DISCUSSION The nitrogen activity in the NH3-H2, atmospheres was never allowed to reach a level capable of producing iron nitride (Fe4N). Hence, the term nitriding as used in this paper refers only to the formation of aluminum nitride whereas nitrogenation refers to the total uptake of nitrogen regardless of how it is distributed throughout the alloy. The weight increases observed during the initial stage of a nitrogenating treatment are due primarily to the solution of nitrogen in the ferrite phase, particularly when starting with annealed specimens. Because this initial nitrogenation rate in the case of the 0.57 pct A1 alloy, see Figs. 2 and 3(a), was most rapid the weight change that occurred thereafter might be attributed to the nitriding reaction with the exception of a small weight increment due to the irreversible pickup of oxygen by aluminum. The oxygen (<70 ppm) came from traces of H2O and 0, in the hydrogen and ammonia gases. On the basis of discrepancies between total weight increase and the increase in the nitrogen content of the sample as determined by chemical analysis, it was estimated and later established by activation analysis, that as much as 200 ppm of oxygen were taken up by a fully nitrided Fe-0.57 pct A1 specimen at 575°C. Most of the oxygen could have been picked up from the nitriding atmosphere on the surface of the samples during cooling to room temperature. Even 50 ppm of water in the gas phase will become oxidizing to iron before the sample has cooled to room temperature. The lack of reactivity* of these alloys in the annealed

Jan 1, 1970

By M. L. Rudee, R. A. Huggins

Samples of iron containing nitrogen or carbon have been given treatments similar to those used in cold-work peak (CWP) measurements and examined by transmission electron microscopy. It was observed that the unusual and nonreproducible behavior of the carbon CWP can be explained by a strong tendency for carbon to form grain boundary precipitates at temperatures below those used for CWP measurements. These precipitates dissolved at the temperatures used in the CWP measurements. There was no evidence for nitrogen precipitation at grain boundaries. There was no indication of precipitation along dislocations in either carburized or nitrided samples given treatments similar to those of CWP measurements. Although it is possible that subelectron-microscopic clustering had occurred, this observation supports the theories of the CWP that are based on continuous atmospheres rather than on individual precipitates. In an earlier paper,&apos; the present authors developed a new distribution function to predict the occupation of sites for interstitial impurity atoms around a dislocation. When this distribution was applied to the case of carbon and nitrogen in iron, it predicted that, if the temperature dependence of the concentration of solute atoms in the matrix was controlled by the presence of equilibrium carbide or nitride precipitates, the tendency for nitrogen to segregate to dislocations would be greater than that for carbon even though their binding energies to dislocations are identical. The cold-work internal-friction peak (CWP) is considered by most authors to be produced by the interaction of interstitial impurities with dislocations. Many investigators have studied the CWP in iron containing carbon and nitrogen and have observed a significant difference between its behavior in the two cases. In this paper a series of experiments will be reported that were initiated to determine whether the application of the new distribution function would explain the observed differences between the carbon and nitrogen CWP. Although it was found that the distribution function, pev se, did not explain the differences, the differences became clear, and some insight into the mechanism of the CWP was realized. Before reporting the present experiments, the literature pertaining to the differences between the carbon and nitrogen CWP in iron and the various mechanisms proposed for the CWP will be reviewed. LITERATURE REVIEW Snoek2 first observed the CWP in iron specimens containing nitrogen, but also reported a weak and unreliable peak in carburized samples. Later, Ke3 established that the CWP height was proportional to the degree of deformation. The presence of nitrogen alone would produce a peak of the same size as found in a sample containing both nitrogen and carbon, and KG concluded that the CWP was caused by nitrogen. In a discussion of G&apos;s paper it was reported that Dijkstra had investigated the CWP in samples that contained only carbon. He found it to be much smaller than the nitrogen peak and "unstable". KG et al.4 charged specimens of iron with both carbon and nitrogen. They observed that the carbon CWP was much smaller than that observed in nitrided samples, but that aging at 300°C caused the carbon peak to increase. A similar treatment produced no change in a nitrogen peak. Annealing at higher temperatures caused the height of the CWP in both the nitrogen and carbon samples to decrease. This behavior was also observed by Kamber et al. 5 who found that the activation energy for the annealing of the CWP was identical with the activation energy for the self-diffusion of iron. They concluded that the annihilation of dislocations by climb caused the reduction in the CWP height. Kamber et al. studied the "unstable" carbon peak in detail. They measured both the Snoek and CWP during various aging treatments. In carburized samples, aging at 100°C caused the Snoek peak to disappear, although the CWP peak remained small. However, a subsequent treatment for 5 hr at 240°C caused the CWP to reach a maximum. They proposed that an additional location for the carbon, other than whatever site produced the CWP, is present. In nitrided samples the CWP was completely developed as soon as a measurement was made; additional sites are not present. No explanation of either the additional site or the difference in the behavior of carbon and nitrogen was offered. petarra5 performed a systematic study of the effect of composition on the CWP. Using three kinds of "pure" iron, he showed that there was a residual CWP when the carbon and nitrogen concentrations had been reduced to less than that detectable by Snoek-peak measurements. He observed the same general annealing behavior and composition dependence as previous investigators, with the following exceptions. On first measuring the carbon CWP, it was found to be identical with the residual peak, and essentially independent of the carbon content. If the CWP was measured a second time in the same sample, it increased in size, but was still only about one-fourth the size of a CWP in a sample of the same iron nitrided to the same composition. On the other hand, a series of annealing experiments showed that the nitrogen CWP was not al-

Jan 1, 1967

By L. S. Darken

In the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be represented satisfactorily by the simple equilibrium expression where (P) denotes the concentration of a product and (R) the concentration of a reactant in the reaction r1R1 + r2R2 + • • • D P lP1 + P 2P2 + • • • Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a component is not proportional to its true mol fraction. But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple components and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satisfactorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature— as ionization or the occurrence of polar and nonpolar molecules—are presumably less effective in inetal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By L. S. Darken

In the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be represented satisfactorily by the simple equilibrium expression where (P) denotes the concentration of a product and (R) the concentration of a reactant in the reaction r1R1 + r2R2 + • • • D P lP1 + P 2P2 + • • • Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a component is not proportional to its true mol fraction. But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple components and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satisfactorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature— as ionization or the occurrence of polar and nonpolar molecules—are presumably less effective in inetal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By M. Dubrovsky, J. W. Evans

A laboratory scale cell (approximately 50 amps current) equipped with a fluidized bed cathode was used in a study of the electrodeposition of cobalt from acidified aqueous sulfate solutions The effect of current density (in the range 0.1 to 1 amp/cm2 of diaphragm), cobalt concentration (4 8 to 100 glliter) and catholyte pH (1 35 to 6 2) on current efficiency and energy consumption were determined. Generally the current efficiency increased with increasing current density and cobalt concentration Current efficiencies were comparable to those reported in the literature for conventional electrowinning

Jan 1, 1981

By Charles C. Towle, Irving Rapaport

URANIUM mineralization along the north flank of the Zuni Uplift, in the vicinity of Haystack Butte, was discovered by Paddy Martinez, a Navajo Indian, in the spring of 1950. The find was reported to the Santa Fe Railway Co., which initiated a program of exploration upon its holdings in the district in December of 1950. The Anaconda Copper Mining Co. secured numerous leases in January and February, 1951, and began an intensive exploration and development program in March 1951. The district was extended into the Lucero Uplift in August of 1951 by the discovery of uranium mineralization in Todilto limestone by Joy Sinyella, a Supai Indian living on the Laguna Reservation. Initial reconnaissance was performed in the district by the Atomic Energy Commission in November 1950. A field office under the direction of the Denver Exploration Branch of the AEC was established at Prewitt, N. Mex. in January 1951 to study regional and detailed guides to ore, to evaluate the ore deposits, and to promote the development of the district by providing geologic services for the companies and individuals engaged in exploration. With the development of sufficient ore to warrant construction of a mill, the Grants area of New Mexico has come of age as a full fledged uranium mining district. The carnotite-type deposits of Grants, the first of major economic importance found in limestone, have extended the Colorado Plateau carnotite field into the more complex structure of the Basin and Range Province. General Geology The Grants uranium district is in northwestern New Mexico, along the southern flank of the San Juan Basin, between the cities of Gallup and Albuquerque. The region is at a mean altitude of about 6800 ft, vegetation is sparse, and outcrops are excellent. Mt. Taylor volcanic peak, at an elevation of 11,400 ft dominates the surrounding area. The overlying cliff-forming Dakota sandstone is the most resistant formation in the Grants District and characteristically erodes into dissected mesas as much as five miles wide. The principle uranium ore-bearing horizons are found in the underlying Morrison formation, and the Todilto limestone of the San Rafael group. The Morrison weathers into. a series of steep slopes and precipitous cliffs near the lower part of the Dakota-capped rims, while in contrast, the relatively resistant underlying. Todilto [ ] limestone forms broad benches extending out from the base of these Dakota rims as much as five miles wide. The Todilto benches are covered with overburden to an average depth of about 5 ft in the first thousand ft away from the Dakota rim, but increases to about 200 ft at the base of the rim. In many places however, a thick mantle of upper Cretaceous sediments and Tertiary volcanics "obscures the ore-bearing Jurassic, and precludes exploration. . The known uranium deposits of the Grants District are distributed throughout a zone 85 miles long and about 10 miles wide. Stratigraphy Rocks from pre-Cambrian through Tertiary are exposed in the uplifted areas, but uranium appears to be restricted chiefly to two zones in Jurassic sediments. The Jurassic sediments of the Colorado Plateau have been subdivided into three units, in ascending order: (1) Glen Canyon group, (2) San Rafael group, (3) Morrison formation. The Todilto limestone zone within the San Rafael group has produced the bulk of ore to date, but the promise of the Morrison zone is rapidly increasing. The Todilto formation extends about 300 miles east-west and about 100 miles in a north-south direction. It is composed of a lower, extensive, limestone member and a central, more restricted, thick, pure gypsum member. The Todilto is believed to be of lacustrine origin. The Morrison formation in this area is subdivided, rather arbitrarily, into three members: Recapture Creek, Westwater Canyon, and Brushy Basin. Ore

Jan 1, 1952

By AIME AIME

DESPITE the meetings and discussions on over- production the situation still continues to grow worse instead of better. The demand for oil has dropped to 2,700,000 bbl. per day. On the other hand domestic production has risen to 2,700,000 bbl. with prospects of further increases, and if imports and natural gas-gasoline be added to this the current supply is about 3,100,000 bbl. per day. Though during the summer and early fall the demand may exceed this figure for a few months the prospects are that &apos;the average demand during 1929 will be at least 200,000 bbl. per day less than the present current supply, meaning additions to stocks over the year of about 75,000,000 bbl.

Jan 1, 1929

By F. F. Frick, Frederick Laist

In a leaching process, having obtained the copper in solution, the choice of the precipitation method is influenced by the following factors: 1. Availability of precipitant. 2. Adaptability to the leaching process. 3. Final product desired. 4. Regeneration of leaching solutions. 5. Fouling of solutions. There are three general classes of precipitation methods: 1. The use of iron, scrap or sponge. 2. Electrolytic deposition. 3. The use of some gas or reagent by which the copper is obtained, usually in the form of an intermediate precipitate which requires further treatment. For example, the precipitation of, the copper as Cu2Cl2 from chloride solutions; with SO2 gas. The use of iron is adapted to almost any process. It has the great advantage of extreme simplicity, and the recovery of the copper and any values present in a highly concentrated, easily treatable form. The disadvantages are the cost in isolated places, the uncertainty of the scrap-iron market, and the fouling of the leaching solutions. The latter is a serious factor, when a reagent such as salt is used in them, which makes necessary their re-use. Where applicable, electrolytic deposition is very attractive. The copper is obtained in a form directly marketable, there is a regeneration of acid and no fouling of solutions. Unfortunately, chloride solutions do not lend themselves to electrolysis. An entirely satisfactory anode material has not yet been discovered, although magnetite, apart from being rather brittle, seems to answer the requirements fairly well. The use of a method of the. third class is involved in many special

Jan 1, 1915

By Y. Jeannin, C. Mannerskantz, F. D. Richardson

Measurements have been made between 1040o and 1300°C of the equilibrium between chromium metal, chromic oxide, hydrogen, and water. The results are in closer agreement with those deduced from recent thermal data than with previous equilibrium values. They lead to the equation ?G°1300°-1600°k = -266,700 + 59.95T ± 300 cal for the formzation of a mole of Cr2O3 from chromium and oxygen. This same equilibrium has been studied with the chromium dissolved in solid iron, and in this way chromium activities in Fe + Cr alloys have been established. The measuremenis show that there are substantial positive deviations from ideality in the a, and b phases, and support the results obtained by Heymer and Kubaschewski against those of other investigators. There is considerable disagreement between existing data,1"4 which is referred to in the Discussion, concerning the equilibrium Cr2O3 + 3H2 = 2Cr + 3H2O [l] There is also substantial disagreement between the results obtained by various investigators5-&apos; who have measured the activities of chromium in its alloys with iron by the Knudsen effusion vapor pressure method. In view of the importance in metallurgical processes of chromium and its oxide and of Fe-Cr alloys, an attempt has been made to study equilib- rium [I] both with pure chormium metal and with chromium alloyed with iron, at temperatures between 1040o and 1300oC. From the work with the alloys it is possible to derive the chromium activities from the relationship

Jan 1, 1963

By D. W. Fuerstenau

THE object of this article is to point out the experimental relationship which exists among contact angle, adsorption density, zeta potential, and flotation rate data. In each of the experiments discussed in this article, the surface properties of quartz, as a function of pH, were measured in solutions to which constant quantities of dodecylam-monium acetate were added. Morrow1 and deBruyn2 worked with solutions containing 4.08x10-5 moles per liter, whereas Fuerstenau3 and Seele worked with solutions containing exactly 4x105 moles per liter, but this difference is not significant. The pH of the solutions was regulated with HCI or NaOH in all cases. In each case, the addition of collector was constant, but the concentration of dodecylammonium ions decreased because of the formation of dodecylamine at higher pH values.2 Contact Angles: Gaudin and Morrow1 presented data for the contact angle of quartz in solutions containing 4.08x10-5 moles of dodecylammonium acetate per liter between pH 2 and pH 10.15. Using the same captive bubble techniques, the writer measured contact angles on quartz in solutions containing 4x105 moles of dodecylammonium acetate per liter at pH values ranging from 9.9 to 13.2. Both sets of data are presented in Fig. 1, in which the contact angle in degrees is plotted as a function of the pH of the solution. From pH 2 to about 8, the contact angle

Jan 1, 1958

By W. O. Philbrook, K. M. Goldman, G. Derge

T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer

Jan 1, 1951

By Milton E. Wadsworth, W. Martin Fassell, William H. Dresher

A study of the rate of dissolution of molybdenite (MoS2) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process. HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.&apos; The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.&apos; National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 phalerite,4 galena,5 and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,8 who found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo+ + in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit&apos;s construction and operation have been discussed elsewhere,7 Only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

John S. Kennedy, Chamhersburg, Pa. (communication to the Secretary): The washing-plant described by Mr. Johnson is a good illustration of the advantages derived from a well-designed and care-

Jan 1, 1895

By Joseph E. Pogue

THE period of new oil discoveries in Illinois began in February 1937, when The Pure Oil Co. found the Clay City field the forerunner of a number of limestone pools. The importance of the area was emphasized greatly in December of the same year with the discovery of excellent sand production by The Carter Oil Co. at Louden and in June, 1938, with the discovery by The Texas Co. of the Salem field producing from two sands and one lime- stone horizon. By September, 1939, new discoveries in Illinois were estimated to have added, under prevailing production practices, some 500,000,000 barrels to the crude oil reserves of the United States and to have produced to that date some 63,000,000 barrels with daily production passing the 300,000-barrel mark by Sept. 1.

Jan 1, 1939

By C. S. Land

Relative permeability functions are developed for both two- and three-phase systems with the saturation changes in the imbibition direction. An empirical relation between residual nonwetting-phase saturation after water imbibition and initial nonwetting-phase saturations is found from published data. From this empirical relation, expressions are obtained for trapped and mobile nonwetting-phase saturations which are used in connection with established theory relating relative permeability to pore-size distribution. The resulting equations yield relative permeability as a function of saturation having characteristics believed to be representative of real systems. The relative permeability of water - wet rocks for both two- and three - phase systems, with the saturation change in the imbibition direction, may be obtained by this method after properly selecting two rock properties: the residual nonwetting-phase saturation after the complete imbibition cycle, and the capillary pressure curve. INTRODUCTION Relative permeability is a function of saturation history as well as of saturation. This fact was first pointed out for two-phase flow by Geffen et al. 1 and by Osaba et a1.2 Hysteresis in the relative permeability-saturation relation also has been reported for three-phase systems.3 Since saturations may change simultaneously in two directions in a three-phase system, four possible relationships arise between relative permeability and saturation for a water-wet system. The four saturation histories of this system were given by snel14 as 11, ID, DI and DD. I and D refer to the direction of saturation change (imbibition and drainage), with the first letter of the symbol indicating the direction of change of the water phase. As used in this paper, the second letter of the symbol refers to the direction of saturation change of the gas phase, i.e., D and I indicate an increase and decrease, respectively, in gas saturation. Only a few three-phase relative permeability curves have been published. Leverett and Lewis5 published three-phase curves for unconsolidated sand, and Snell4 reported results of several English authors for both drairrage and imbibition three-phase relative permeability of unconsolidated sands. Three-phase relative permeability curves for a consolidated sand were published by Caudle et a1.3 for increasing water and gas saturations (ID). Corey et a1.6 reported drainage (DD) three-phase relative permeability for consolidated sands. Recently, Donaldson and Dean7 and Sarem8 calculated three-phase relative permeability curves from displacement data on consolidated sands, also for saturation changes in the drainage direction. The only published three-phase relative permeability curves for consolidated sands with saturation changes in the imbibition direction (11) are those of Naar and Wygal.9 These curves are based on a theoretical study of the model of Wyllie and Gardner 10 as modified by Naar and Henderson.11 Interest in three-phase relative permeability has increased recently due to the introduction of new recovery methods and refinements in calculation procedures brought about by the use of large-scale digital computers. The scarcity of empirical relations for three-phase flow, and the experimental difficulty encountered in obtaining such data, have made the theoretical approach to this problem attractive. RELATIVE PERMEABILITY AS A FUNCTION OF PORE-SIZE DISTRIBUTION Purcell used pore sizes obtained from mercury-injection capillary pressure data to calculate the permeability of porous solids.12 Burdine extended the theory by developing a relative permeability-pore size distribution relation containing the correct tortuosity term.13 The works of Purcell and Burdine were combined by Corey14 into a form that has

Jan 1, 1969