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By Thomas S. Carnahan

The mining property of the Utah Copper Co. is situated in the West Mountain mining district, Salt Lake County;Utah, in the Oquirrh Range of mountains. Geology In a general way the rock formation of the district consists of a series of beds of quartzite and limestone intruded by a body of monzonite porphyry roughly elliptical in shape, with an east-west axis over a mile in length and a north-south axis of about 3,000 ft. This porphyry intrusion, accompanied by strong mineralizing action and fracturing, resulted in the formation of orebodies in the adjacent sedimentary rocks, and was itself sufficiently mineralized to make it one vast orebody. The Utah Copper Co.'s mining property comprises within its boundaries practically the entire outcrop of the monzonite mass, of a commercial grade. Genesis of Porphyry Ore Following an intricate system of fracturing, mineral solutions circulated freely through the porphyry, depositing small quantities of copper and iron, and resulting in a considerable silicification of the monzonite. The quantity of copper originally deposited was undoubtedly too small to have ever given the porphyry a commercial value, had not secondary enrichment, due to the leaching of the copper from the surface of the mass and re-deposition in the sulphide zone, been active over a long period of years. A large portion of the leached material has probably been removed by erosion, but there still remains a blanket of leached and oxidized porphyry of varying thickness covering the sulphide ore, known as capping. Over certain sections of the orebody, this capping contains commercial quantities of copper carbonates, but most of it contains little or no copper.

Jan 1, 1916

By G. B. Clark

Dynamic rock mechanic as it pertains to blasting has involved several areas of active research effort. Among the important problems which have been the subject of research are wave mechanics in rocks, mechanisms of rock breakage, cratering, applications of similitude, energy partitioning of explosives, coupling, and other related factors. In some of these areas many problems have received fairly complete answers, while in others, investigations have raised new questions while attempting to answer existing ones. The slabbing mechanism explains many of the phenomena observed in blasting, but is hot the complete answer to observed breakage and fragmentation phenomena. There is currently a gap between coupling experimental results and theory. Applications of similitude to open pit blasting have been made unnecessarily complicated. Basic scaling laws for large true and apparent craters have not been derived for either chemical or nuclear explosives. There are few useful data and little developed theory on the partitioning of energy of explosives in all types of blasting. No suitable mathematical model has been developed which will describe the stress waves in rock which are responsible for rock breakage: Significant progress has been and is being made in these areas of research, however. ELASTIC AND NONELASTIC WAVES Complete solutions for spherical wave equations in viscoelastic media are not available in the literature. Equations for certain viscoelastic models do show limited promise, however, of being applicable to rock masses, particularly for pulse type phenomena. Seismic investigations, blasting operations, the design of protective underground structures, and the evaluation of other explosive effects in solids would be greatly bene-

Jan 1, 1967

Dr. Healy's paper presents a concise state-of-the-art description of mechanistic, thermodynamic models available today for design, interpretation, and trouble-shooting flocculation processes and problems. Coagulation by manipulation of inorganic electrolyte concentrations is controlled largely by adjustment of electrostatic repulsive forces, guided by well understood theory. For simple solids in simple electrolytes, existing models are capable of predicting the influence of potential determining ion and one dominant, non-reacting, symmetrical electrolyte concentration on floc stability quantitatively. Concentration changes required to coagulate and disperse can be estimated. Convenient, easily understood means are available for summarizing the effects of key variables, (e.g., pH, ionic strength) on dispersion stability, and estimating tolerance to unintentional changes (Matijevic coagulation domain diagrams). These models have not been developed to the point that mixed unsymmetrical electrolytes can be easily handled. They are capable of describing two- solid heterocoagulation, but not “n-solid” heterocoagulation. In combination with recently developed computer codes for simultaneous computation of solution equilibria, ion exchange and electrical double layer properties (1,2), these models .should be capable of describing simple clay coagulation systems. This has not been done. Models developed for polymer flocculation are valuable interpretive tools, have some qualitative predictive value, but are less potent in quantitative needs. Most real systems probably involve more than one mechanism of floc stabilization. Little has been done toward developing combined models, even in the simplest systems.

Jan 1, 1979

To the members of the A. I. M. E., who have given much and risked all to fight "Over There" with pick, or gun, or brain, and to the members who have chosen the sometimes more self-denying duty of remaining at home to help produce metals for fighters: Your experience in foreign lands has bred in you that spirit of internationalism which will soon be infused into every corner of our country by virile lads thrilling from a great experience in an old, yet new, land over the seas. To them the East will not seem as far from the West as it was, nor the North from the South. Sectional jealousies will seen despicable to one who has fought for a great ideal shoulder to shoulder with real men of other nations. And they who have willingly sacrificed much on the altar of service will have little patience with an egotist, be he laborer, tradesman, capitalist or engineer. The problems which peace brings to us are more difficult than those of war and their solution requires not only cool heads, tolerance, and wise judgment, but the "getting together" of sections and classes and individuals. The triumph of justice over individualism, represented by the draft law, must be repeated, for there are "slackers" in peace Is well as in war, and the spirit of self-denial expressed in response to Liberty Loans, Red Cross, and Welfare drives and Food Administration appeals must live. We have only just begun to learn how to serve. It is often claimed by our members that the engineer is not given, in the community at large, the recognition which his training should merit; that his reward is not as great nor his service as welcome as it should be. Public service is generally assumed to be a logical activity for a lawyer,

Jan 12, 1918

By J. F. Enrietto

Internal friction measurements were used to determine the effect of manganese on the solubility and precipitation kinetics of nitrogen. Manganese, in concentrations up to 0.75 pct, has little effect on the solubility at temperatures above 250°C. On the other hand, at Concentrations as low as 0.15 pct, manganese inhibits the formation of iron nitrides, especially Fe4N, even though it may not form a precipitnte itself. The precipitation and solubility of carbides and nitrides have been extensively investigated in the pure Fe-C and Fe-N systems.1-3 In recent years, some effort has been ispent in studying the influence of substitutional alloying elements on the behavior of carbon and nitrogen in ferrite.4 -7 In particular Fast, Dijkstra, and Sladek have investigated the effect of 0.5 pct Mn on the internal friction and hardness during the quench aging of Fe-Mn-N alloys.', ' They found that at low temperatures (below 200°C) the presence of 0.5 pct Mn greatly retarded quench aging. For example, after 66 hr at 200°C very little precipitation had taken place in the iron alloyed with manganese, whereas precipitation was complete after a few minutes in a pure Fe-N alloy. The effect of varying the manganese content and the details of the precipitation process were not mentioned in these papers. Fast' postulated that manganese causes a local lowering of the free energy of the lattice with a resulting segregation of nitrogen atoms to these low energy sites. The segregated nitrogen atoms are bound so tightly to the manganese atoms that they cannot form a precipitate. The internal friction measurements of Dijkstra and Sladek tended to confirm the concept of segregation of nitrogen around manganese atoms, and the increase in free energy on transferring a mole of nitrogen atoms from a segregated to a "normal" lattice site was computed to be - 2800 cal. Dijkstra and Sladek9 distinguished between two types of precipitates: ortho, a nitride of appreciably different manganese content than that of the matrix, and para, a nitride with a manganese content essentially that of the matrix. With each type of precipitate a solubility, again designated ortho or para, can be associated. Since the internal friction maximum in alloys which were aged several hours at 600" C dropped almost to zero, Dijkstra and Sladek9 concluded that the ortho solubility must be very low. The effect of temperature on the ortho and para solubilities has no1: been investigated. There are obviously several gaps in our knowledge concerning the influence of manganese on the behavior of nitrogen in a-iron. It was the purpose of the experiments described in this paper to determine the following: 1) The ortho and para solubilities of nitrogen as a function of temperature. 2) The details of the precipitation process at elevated temperatures. 3) The effect of varying the manganese concentration on the above phenomena. EXPERIMENTAL PROCEDURE Internal friction is conveniently employed in studying the precipitation of nitrides and/or carbides from a -iron because it is one of the few parameters, perhaps the only one, which is not affected by the presence of the precipitate itself. For this reason, internal friction techniques were heavily relied upon in the present experiment. A) Preparat of -. All specimens were prepared from electrolytic iron and electrolytic manganese. Alloys containing 0.15, 0.33, 0.65, and 0.75 wt pct Mn were vacuum melted and cast into 25 lb ingots. After being hot rolled to 3/4 in. bars, the ingots were swaged and drawn to 0.030 in. wires. The wires wen? decarburized and denitrided by annealing at 750° C for 17 hr in flowing hydrogen saturated with warer vapor. To obtain a medium grain size, - 0.1 mm, the wires were then heated to 945oC, allowed to soak for 1 hr, furnace cooled to 750°C, and water quenched. Subsequent internal friction measurements showed that this procedure reduced the nitrogen and carbon concentrations of the alloys to less than 0.001 wt pct. The wires were nitrided by sealing them in pyrex capsules containing anhydrous ammonia and annealing them for 24 hr at 580°C, the nitrogen being retained in solid solution by quenching the capsule into water. Immediately after quenching, the wires were stored in liquid nitrogen to prevent any precipitation of nitrides. By varying the pressure of ammonia in the capsule, it was possible to produce any desired nitrogen concentration. B) Internal Friction. The internal Friction measurements were made on a torsional pendulum of the Ke type,'' a frequency OF 1. or 2 cps being used. For

Jan 1, 1962

By Irving B. Cadoff, Ernest Levine

The crack formation and propagation in the single -phase Cu-4 pct Ag alloys were studied. The alloys were loaded in mercury to various stress levels, the mercury was removed, and the specimen examined for cracks. Cracks were found to develop below the fracture stress; the frequency of such cracks increased with increasing stress level. Some cracks were nmpropagative. Fracture in mercury was found to occur by the link-up of cracks formed at various stress levels rather than by the growth and propagation of a single crack. If the mercury environment is removed prior to a critical amount of crack formation, then continued loading results in ductile fracture. The appearance of the cracks at selected grain boundaries is related to the relative orientation of the boundaries, as are the propaga-tive characteristics of the crack. The mercury interaction appears to be one of lowering the strength of the metal-metal bonds in the high-stress area of the grain boundary. GRIFFITH'S microcrack theory1 proposed a critical crack size above which a crack in an elastic material grows with decreasing energy at a stress of From his theory it was proposed that the presence of a liquid tends to lower the surface energy of the microcrack faces2 leading to a decrease in the critical crack size necessary for spontaneous fracture propagation. stroh3 proposed that the stress concentration at a grain boundary due to pile-up may initiate a microcrack at the grain boundary. petch4 and Stroh5 evaluated the stress distribution at the head of a pile-up in a polycrystal-line material and deduced that the critical crack size and hence of is dependent on the grain size. Experimental verification of this dependence was found by petch6 for hydrogen embrittlement of steel. Studies in stress-corrosion cracking7 have provided a picture of fracture which shows that initial separations occur in a scattered, independent fashion in regions of high tensile stress. A minimum or threshold stress is necessary to produce a sufficient stress concentration to initiate frac- ture. These separations join up to form a crack. The extension of fracture is largely discontinuous and consists of a joining up of cracks. In recent worka evidence of this scattered crack network was found in a Cu-Ag alloy embrittled by mercury. For the Cu alloy-Hg couple, the crack path has also been found to be dependent on the orientation of adjacent grains, and with the addition of zinc to mercury a reduction in embrittlement along with a change in fracture morphology was found.9 In this present study, a mercury-dewetting method was used to observe crack initiation and fracture morphology when a Cu-4 pct Ag alloy is deformed in mercury and Hg-Zn solutions. PROCEDURE Specimens of Cu-4 pct Ag were prepared as in previous crack-path studies.' The specimens were heated at 770°C for 24 hr and water-quenched Tension tests using a table-model Instron were carried out in mercury and in various concentrations of Hg-Zn. Loading was in steps up to the fracture stress, with the load being removed and the specimen examined for surface cracks at each step. The specimens were dewetted after each load to permit examination of the surface structure and rewetted prior to continued loading. The specimens were wetted by electro polish ing in phosphoric acid, rinsing in alcohol, and then immersing in a pool of mercury. Dewetting was accomplished by flame heating the specimen for 30 sec in a vacuum. Some surface contamination was found, but not enough to obscure crack configurations and grain boundaries. RESULTS Fracture Characteristics in Mercury. Fig. 1 is a stress-strain curve showing the progressive step-wise loading of the specimen. As may be seen from the graph, the first position stopped at a is at a stress 5000 psi below the expected fracture stress of 25,000 psi. Examination of the specimen after removal of mercury showed only one crack. The appearance of this crack at a stress far below the fracture stress of this alloy in mercury did not affect the stress-strain curve in any manner. The specimen was then recoated with mercury and deformation was continued (curve b, Fig. 1) raising the stress by 4000 psi, and the same procedure re~eated. The initial crack was located and appeared as in Fig. 2 (crack lb). In this figure the crack is

Jan 1, 1964

By Raymond C. Boettner

The present work had for its purpose: 1) the identification of crack nucleation sites in AISI 4340, quenched to martensite and tempered over a range of 'temperatures; and 2) the comparison of fatigue processes in AISI 4340 with processes observed previously in pure metals From constant def1ection-bending fatigue tests, martensite boundaries were identified as the favored crack nucleation sites in quenched and tempered AISI 4340. It, also, was concluded that the fatigue processes operating- in this lous-alloy steel were similar to Processes observed in pure tnetals. ALTHOUGH much engineering data has been accumulated on the fatigue properties of quenched and tempered martensitic steels,' fatigue as a process is not as well understood in martensite as it is in pure metals.' Important features of the fatigue process, such as the identity of the nucleation sites, have not been determined in the commercially important high-strength low-alloy structural steels. The present work had for its purpose: 1) the identification of crack nucleation sites in a low-alloy steel, i.e., AISI 4340, which had been quenched to martensite and tempered over a range of temperatures; and 2) the comparison of fatigue processes in the AISI 4340 with processes observed previously in pure metals. This comparison of the fatigue processes in the different tempers was restricted to the high-strain low-cycle part of the S-N curve. Under these test conditions, previous work on a number of metals has shown that a large number of cracks are nucleated in less than 30 pct of the fatigue life.3 Furthermore, crack nucleation sites are not restricted to inclusions but are also associated with intrinsic structural characteristics of the metal. MATERIAL A 20-lb ingot of vacuum-melted AISI 4340 (for composition see Table I) was hot-rolled to 1-in.-diam rod and then cold-rolled to a 1-in.-wide strip, 0.08 in. thick. Fatigue specimens, see insert of Fig. 1, were machined from the strip with the long dimension parallel to the rolling direction. m this orientation, the stringers of 1 to 2 p inclusions present in the sheet lay parallel to the stress axis in the specimens. The specimens were austenitited at 2050°F in order to obtain a large prior austenite grain size, i.e., 2 mm, which facilitated the subsequent identification of the prior austenite boundaries. A helium atmosphere was used to minimize decarburization. After austenitiza-tion at 2050°F, the specimens were transferred to a 1450°F furnace so that specimen distortion was held to a minimum in the subsequent oil quench. Previous work4 indicated that refrigeration in liquid nitrogen prior to tempering reduced the percentage of retained austenite in the quenched specimens to less than 5 pct. Tempering was carried out in air over the temperature interval of 200°to 800°F to produce a range of mechanical properties, Table I. The preparation of the fatigue specimen was completed by grinding about 0.005 in. from each surface and electropolishing in a chrome trioxide-acetic acid solution for 30 min. Examination of etched cross sections of specimens prepared in this fashion showed the foregoing specimen preparation to be adequate for the removal of the decarburized layer present after the heat treatment. Transmission electron microscopy showed that the as-quenched microstructure of this alloy consisted of a mixture of martensite plates containing either a high density of dislocations or microtwins. Previous work5'6 indicated that in the course of oil quenching autotem-pering resulted in the formation of E carbide on the martensite and microtwin boundaries. Tempering for 2 hr at temperatures up to about 400°F resulted in further precipitation of the E carbide. Finally, at about 400°F, cementite began to replace the E carbide on the martensite and microtwin boundaries in addition to forming a Widmanstatten structure within the plate matrix. EXPERIMENTAL S-N curves were obtained using electropolished specimens cycled at 1800 cpm as cantilever beams in fully reversed bending at selected constant deflections. The deflections were translated into surface strains by means of a calibration curve obtained through the use of strain gages. An argon atmosphere was used to minimize environmental effects. To investigate the development of fatigue slip bands, the specimens of the different tempers were unidirec-tionally bent to a surface strain of 0.005 to 0.007, photographed to record the location and appearance of slip bands so introduced, and then cycled to failure

Jan 1, 1968

By A. Kounosu, T. Fujita, J. Shimoiizaka, K. Nakatsuka

Stable aqueous dispersion of magnetite colloid of about 10 nm in diameter was obtained by allowing an anionic or nonionic surfactant to adsorb on the hydrophobic surface of magnetite particles prepared by monomolecular adsorption of oleate. Sodium dodecylbenzene sulfonate, sodium oleate and poly (oxyethylene) nonyl phenyl ethers whose hydrophilic-lipophilic balance (HLB) are higher than 12 were suitable for giving a second adsorption layer to obtain a stable dispersion. Stability of the colloidal suspensions depends upon pH of the solution and is controlled by the dissociation of the adsorbed surfactant in the second layer. The addition of ethyleneglycol, which was used for lowering the freezing point of the dispersion, did not affect the stability when used in amounts smaller than 60% of water. Preparation of diester-based ferrofluids was also attempted by the same procedure using a nonionic surfactant as second layer molecule. Hydrophobic magnetite colloid, which had been preliminarily coated with mono-molecular oleate, was suspended in di(2-ethylhexyl) agipate, azerate, and sebacate respectively, and dispersion stability was investigated by adding various poly (oxyethylene) nonyl phenyl ethers of different HLB values. It was found that those with HLB values between 10.9 and 13.3 were suitable for this purpose. Stabilities of the dispersions in a magnetic field were investigated up to 1 T by applying an electromagnetic field. No separation of dispersant was observed and each magnetite dispersion displayed the characteristics of a magnetic fluid.

Jan 1, 1980

By Joseph Singewald

I. THE GENESIS OF THE DEPOSITS THE ore deposits at Firmeza have been worked continuously since 1884; those at Daiquiri since 1895. It is surprising, therefore, that they have not been the object of careful geologic study until quite recently. It is true that considerable attention was paid to these deposits by A. C. Spencer, in 1901, in the report on the geology of Cuba, by Hayes, Vaughan, and Spencer,1 but this was only incidental to a hasty general reconnaissance of the Island. As far as the Daiquiri deposits are concerned, this gap has been filled by the appearance of the two papers by Prof. James F. Kemp2 and by Prof. Waldemar Lindgren and Clyde P. Ross respectively.3 Max Roesler, first holder of the Emmons fellowship, made a detailed study of the Firmeza deposits during the past summer, so that soon we can expect a full description of them. Consequently, there is no. demand at the present time for a description of the deposits from other sources, rind that is not the purpose of this paper. The papers on Daiquiri, however, leave unsolved problems in regard to the age of the rocks of the district and certain phases of the genesis of the deposits, and it is with the. hope of aiding in the solution of some of these problems that this contribution is offered. Kemp, and Lindgren and Ross agree in assigning these deposits to the type of contact metamorphic deposits. They disagree in part on the question of their localization. The deposits occur in an extensive area of diorite which includes numerous blocks of limestone, and some-

Jan 3, 1916

By Arthur S. Coffinberry, Ralph Hultgren

WE have studied the gold-aluminum system by X-ray diffraction and by the microscope over the entire range of composition for temperatures between 300° and 500° C. Results obtained are shown in Fig. 1, combined with the work of Heycock and Neville1 at higher temperatures. The diagram differs in important details from that given by Hansen2 in his critical compilation of the literature of binary alloy systems. This work was undertaken both because of the intrinsic value of a knowledge of the phase diagram of this system and because of the need of theoretical metallurgy for precise and accurate data, particularly X-ray diffraction data. Systematic studies of equilibrium diagrams, particularly by Hume-Rothery,3 have shown regularities that yield a certain insight into the nature of alloying forces. It has been shown, for example, that solid solubility depends on the concentration of free electrons in the alloy, on the relative radii of solvent and solute atoms, on the forces of attraction between atoms, and on the relative stability of intermediate phases. The well-known Hume-Rothery rule states that the crystal structures and compositions of many intermediate phases depend on the electronto-atom ratio. This has been confirmed and extended by wave mechanical calculations.4 A knowledge of the forces between atoms in alloys, even an imperfectly developed empirical one, should be a valuable guide in the preparation of technological alloys of desirable properties. Furthermore, such information is basic in such problems as rate of diffusion, age-hardening, phase transformations, and others. The most valuable data for this purpose are furnished by X-ray diffraction studies. Unfortunately, work has been

Jan 1, 1938

By Victor A. Phillips

A series of specimens of a Cu- 3.23 pct Co alloy were prepared with particle diameters from zero to 590A. The samples were then cold-rolled 95 pct and the effects of the particle size on the behavior on annealing for hr at temperatures between 100" and 900°C were studied (by hardness, light, and electron metallography). Particles, particularly for d r 105 to 590A, greatly impeded softening and vecvystallizn-tion, and tended to give elongated grains. Particles deformed fairly homogeneously with the ,matrix, be- IN a previous study by the author,' the growth of cobalt-rich precipitates was followed electron microscopically in Cu-3.12 Co alloy as a function of aging, typically at 650°C. The coherent spherical precipitates grew to 520 + lOOA average diam before spontaneously losing coherency and developing (111) facets. Stretching a few percent after precipitation 2aused loss of coherency to occur sooner at about 220A average particle diam. The particles apparently retained their fcc structure after loss of coherency. coming lau2ellae. For d = 55 to 180A, these lamellae gave streak-contrast effects apparently due to coherency strains , and spheroidized on annealing at 600" to 650°C, forming coherent particles. Particles of d = 250 ov 320A lost coherency during t-olling, giving incoherent lamellae. Recrystallization apparently occured by growth of new grains into unrecrystallized (recovered) material at temperatures below that at which cobalt atoms had much mobility. The present study was undertaken to explore the effect of cobalt-rjch particles of various average sizes from 50 to 600A diam on the isochronal annealing behavior of copper after heavy cold rolling. The previous work' was used as a guide in preparing the two-phase series of prerolling structures. The solution-treated alloy was also rolled for comparison. A further question of interest in the present study was whether dislocation and particle hardening were additive, since the prerolling structures covered the full range unaged - peak aged — overaged, and further precipitation might occur on annealing after cold rolling. Although there have been exhaustive studies of the isothermal2"6 and is~chronal annealing behavior of

Jan 1, 1967

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By Roland Kammel, Takeo Oki

A suspension electrolysis method has been developed which enabled a direct anodic extraction of zinc from zinc sulfide concentrate and simultaneously oxidized sulfide sulfur to elemental sulfur. The investigation was performed in a laboratory-scale electrolytic cell, where the zinc sulfide concentrate particles (chemical composition in weight percent: 61.1% Zn, 2.3% Fe, 30.6% S, 3.4% SiO2 were suspended with or without graphite powder in a dilute sulfuric acid electrolyte. The main parts of the cylindrical electrolytic cell are shown in [Fig. 1]. The cathode (1), a rod of aluminum, is set at the center of the cell. The anode (2), which consists of four plates, is mounted on the inner face of the cell wall. Both PbO2(Pb) and graphite anodes were used. The cathode compartment (3) is separated from

Jan 1, 1976

By L. C. Brown, S. K. Behera

The diffusion rate in Ag-Sb couples is sensitive to con~pressive load with the width of Ag3Sb, the only phase present in the diffusion zone, increasing with stress up to 800 psi and remaining constant above this. Kirkendall marker experiments show silver to diffuse much faster than antimony in Ag3Sb and incipient porosity may therefore develop at the Ag/Ag3Sb interfnce restricting the transfer of atoms from the silver into the diflusion zone. Application of compressive stress reduces the tendency for porosity to develop and so increases the growth rate. In a recent paper Brown et al.1 observed a significant increase in the thickness of Cu2Te in Cu-Te diffusion couples on application of a compressive stress as low as 20 psi. Similar stress effects have also been observed in the Fe-A1,2 Al-u,3 arid cu-sb4,5 systems. It has been suggested that the increase in growth rates of intermetallic phases in these systems is due to a decrease in the amount of Kirkendall porosity with applied stress. In the present paper, results are presented of the effect of compressive stress on diffusion in Ag-Sb, together with a detailed examination of the Kirkendall effect. The Ag-Sb phase diagram6 shows that antimony has a moderate degree of solid solubility in silver, 5.7 at. pct at 350°C, but that there is essentially no solubility of silver in antimony. There are two intermediate phases— (hcp7) from 8.8 to 15.7 at. pct Sb and Ag3Sb (orthorhombic8) from 21.8 to 25.9 at. pct Sb. EXPERIMENTAL Diffusion couples were prepared from fine silver of 99.95 pct purity and from antimony of 99.7 pct purity. Both the silver and antimony were produced in the form of discs 1/2 in. in diam by approximately $ in. thick, with surfaces ground flat to 3/0 emery paper. Diffusion anneals were carried out in the apparatus previously described.1 A compressive load was applied to the diffusion couple through a lever arm system, with a reproducibility estimated to be ±10 psi. All runs were carried out in a protective hydrogen atmosphere. Following the diffusion anneal specimens were sectioned and polished and the width of the diffusion zone was measured metallographically. Composition profiles were measured using an electrostatically focused electron probe with a spot size of 10 , counting on Sb L radiation. Corrections for matrix absorptiori and fluorescent enhancement9 were not required. S. K. BEHERA, formerly Graducate Student, Department of Metallurgy, University of British Columbia, is now Postdoctoral Fellow, Whiteshell Nuclear Laboratories, Atomic Energy of Canada Ltd., Pinawa, Manitoba. L. C. BROWN, Junior Member AIME, is Associate Professor, Department of Metallurgy, University of British Columbia, Vancouver, B.C., Canada. Manuscript submitted June 14, 1968. IMD RESULTS Fig. 1 shows an electron probe traverse of a typical diffusion zone. In all couples examined only one intermediate phase was observed and the composition of this phase, 23 wt pct Sb, was in good agreement with the composition of Ag3Sb, 23 to 28 wt pct Sb. The presence of this phase was confirmed by X-ray diffraction of filings taken from the diffusion zone. The probe traverses showed no detectable solid solubility in either the silver or the antimony although the phase diagram indicates that some antimony, up to 6.5 wt pct pct Sb, should be in solid solution in the silver. However the width of this portion of the diffusion zone would be expected to be very small in view of the low diffusion coefficient in the silver, 4 x 10-l6 sq cm per sec at 350°C, 10 compared with that in the Ag,Sb, estimated as 3 x 10-8 sq cm per sec in the present work, and this region would therefore not be expected to be seen in the probe traverse. Application of stress resulted in a significant increase in the width of the diffusion zone, Fig. 2. At 350°C, the thickness of Ag3Sb increased from 250 at 0 psi to 400 p at the limiting stress of 800 psi, indicating an apparent 150 pct increase in the diffusion coefficient. Similar behavior was also observed at 400°C, indicating that the stress effect is not characteristic of just one temperature. The growth of Ag3Sb at 350°C and at various stresses is shown in Fig. 3. In every case the growth rate was parabolic indicating diffusion control. The kinetic curves all passed through the origin showing that delayed nucleation of Ag3Sb was not responsible for the stress effect and that it was a real growth effect. A series of tests were carried out in which diffusion was allowed to take place at a lower stress following an initial high stress diffusion anneal. Speci-

Jan 1, 1969

By A. F. Nylander, J. H. Jensen

Magnesium, in its combined forms, is the sixth most abundant element and the third most abundant metal in the earth's crust, but it is so reactive that it is never found in nature in the elemental state. As part of the rock-forming minerals like magnesite, dolomite, olivine, and serpentine, it is combined in virtually insoluble forms. As part of soluble minerals like kainite (KC1 MgS04 - 3H20), leonite (K2S0, MgSO, 4H20), langbeinite (K,SO, 2MgS04), and carnallite (KC1 . MgCl? 6H20), it is found in evaporite deposits, generally of marine origin, deep within the earth's crust. Since these minerals are soluble, they are found only in deposits protected from the percolation and leaching action of ground waters by an insoluble and impermeable mantle. Usually this mantle is from several hundred to many thousands of feet thick. Finally, as a solute in marine-like brines, magnesium is common in surface and subterranean waters throughout the world. The oceans, which contain 0.13% Mg, illustrate the inexhaustible nature of the reserve. The recovery of magnesium from the rock-forming minerals, usually by thermal decomposition, and from dilute brines such as sea water by precipitation with lime, are frequent industrial practices. But the recovery of magnesium as magnesium chloride from evaporites or natural brines of concentration greater than sea water has been of little industrial significance for economic and technological reasons. The present US capacity is preponderantly based on the sea-water magnesia process with thermal reduction capacity in second place. No present magnesium capacity is dependent on recovery from the stronger natural brines. But projected capacity, although still weighted in favor of the sea-water magnesia process, is partly based on the recovery of magnesium chloride as a byproduct of potash operations.

Jan 11, 1964

By Perry G. Harrison

The first autlientic description of an iron bath for the deposition of iron is probably that of Bottger in 1846, who used a bath containing ferrous sulfate and ammonium chloride. In 1861, Kramer deposited iron from ferrous chloride solution. Electrolytic iron was produced in 1869 by Bietz, who used it for making some magnetic tests. In the same year, Klein is. said to have worked out his process. Jacobil in 1869 described the results obtained in electroplating with iron on copper for making dies and plates for bank notes, by Klein's process. A letter from Klein to Jacobi describes the bath more fully. It consisted of FeS04 + (NH4)2SO4. Lenz2 described some properties of electrolytically precipitated iron. He used Klein's bath, FeS0, + MgSO4 + MgCO3, to neutralize and obtained fine-grained and hard iron. His conclusions were as follows: 1. Electrolytic iron and copper contain gases, notably hydrogen. 2. The volume of gas absorbed by iron varies within wide limits, but it is easy for iron to take up very considerable quantities of gas. 3. The absorption of gas is principally in the first formed layers of iron. 4. When iron is heated, gas begins to come off below 100°, principally hydrogen. 5. Heated to redness, reduced iron oxidizes in water, in part at least at the expense of the oxygen of the water, decomposing it and setting free hydrogen, which is partly or wholly absorbed. Siemens,3 in 1889, was the first to propose a general process embodying a step for leaching a sulfide mineral with ferric chloride or sulfate and a step for regenerating the leach and depositing iron on a cathode in a diaphragm cell. So far as is known, Siemens did not carry out his patent

Jan 1, 1930

Book Review MANAGEMENT AND MEN. By Meyer Bloomfield, Boston. The Century Co., New York, 1919, pp. 584, H.X. 5 1/2. $3.50. This hook is an exposition of English efforts to solve the problem of labor unrest in England. The first six chapters are reprinted from articles published in the Satur-day Evening Post, for whom the author went to England to study the problem at first hand. These articles deal with housing, increased production, eliminating the internal friction in the industrial machine and a chapter each devoted to the view-point of employer and employee. These chapters are written in the easily readable magazine style and give a complete general survey of the particular solution being tried. Perhaps their greatest., certainly not their least, worth lies in the fact that they form a vehicle for unusually voluminous appendices containing in full the famous Whitley Reports which are the basis of the new movement, together with various reports, which, except for this publication, would be largely inaccessible to those inter-ested in this country. The Whitley scheme considers each industry a unit and proposes to establish therein a Joint Standing Industrial Council composed of representatives of employers and employees to consider appropriate matters affecting the industry at large. There is to be a District Council for each industry which will, as its name implies, deal with the clatters pertaining to that interest in. the particular district. The third and last body in this scheme of Industrial Parliament is the Works Committee, which is com-posed of representatives of the management and of the workers employed in particu-lar plants or mines to act in close cooperation With the district quid national machinery. The Whitley or similar schemes have been tried in many communities in England and the book contains interesting comments on the result obtained, it being notable that most of the objections conic from plants which have not tried the scheme. Meyer Bloomfield, the author; is the specialist in industrial personnel problems who organized the industrial service activities of the United States Shipping Board, Emergency Fleet Corporation. P. E. B.

Jan 10, 1919

By Theodore Holt

Outline of the Process THE Mines Operating Co.'s plant at Park City, Utah, was designed to treat the low-grade fillings in the old stopes of the Ontario mine. These fillings carry 6 to 14 oz. of silver, 1 to 2 lb. copper, 0.01 to 0.015 oz. of gold, and a small percentage of lead and zinc. The treatment consists in mixing the crushed ore with coal dust and salt and then roasting in a new type of furnace y combustion of the contained fuel. The roasted ore is leached with an acid salt solution to dissolve the silver, gold, copper, and lead. At present these metals are precipitated together on scrap iron and the product sold to a refinery. The only new feature of importance in this scheme of treatment is the roasting process, which makes possible the chloridizing of ores without any loss of the valuable metals, and at a very low cost. History of the Development of the Process The roasting process had its beginning in connection with research work at the Utah State School of Mines. N. C. Christensen, Jr., who held one of the School of Mines' fellowships, was engaged in some experimental work on blast roasting. At the same time I was doing some work on the insoluble gold in Mercur base ores. Mr. Christensen roasted some of this base gold ore in his pot furnace, and found that when he mixed a sufficiently low percentage of fuel with the ore, it did not sinter but roasted to a leachable product. We considered this a new application of blast roasting, and proceeded to test out a large number of ores in several different types of small roasters which we constructed. This experimental work continued well into the summer of 1911.

Jan 7, 1914

By C. A. Winkler, V. Hospadaruk

PREVIOUS papers from this laboratory have discussed the effect of chloride ion on the cathode polarization during electrodeposition of copper from copper sulphate-sulphuric acid electrolytes, in the presence and absence of gelatin. The steady state polarization'" was found to decrease sharply and pass through a minimum with increasing chloride ion concentration in the presence of gelatin. The minimum shifted to higher chloride ion concentrations and to higher polarization values with increase in current density or gelatin concentration, while an increase of temperature shifted the minimum toward lower halide concentrations and lower polarizations. Since these observations were made in acid-copper sulphate electrolytes that contained no other addend than gelatin, there was obviously the possibility that they were not applicable to deposition of copper from commercial electrolytes that contain a variety of other substances in relatively small amounts. In particular, it was of interest to determine whether the presence of arsenic, antimony, or bismuth in the electrolyte would materially alter the behavior. Experiments have now been made under a variety of conditions with systems containing these cations, and the results are summarized in the present paper. Experimental Polarization measurements were made at 24.5oC in a Haring cell in the manner described previously.' Electrolytes were made with doubly-distilled water, and contained 125 g per liter of copper sulphate and 100 g per liter sulphuric acid, both of reagent grade Eimer and Amend gelatin from a single stock was used throughout. Chloride ion was introduced as reagent grade sodium chloride, and arsenic, antimony, and bismuth by dissolving the chemically pure metal in hot concentrated sulphuric acid and adding appropriate amounts of the solutions to the electrolyte. Each cathode, of 1/16-in. thick rolled copper, was first etched in 40 pct nitric acid and washed thoroughly with distilled water. The surface was then brought to a standard condition4~9 by electrodeposition from an acid-copper sulphate electrolyte containing no gelatin, at a current density of 3 amp per sq dm for 30 min, followed by deposition at a current density of 2 amp per sq dm for l hr. As in previous studies, the cathode polarization eventually attained a steady-state value (15 to 75 min) such that further change in polarization did not exceed 0.2 mv per min. The polarization values recorded are those for the steady states. "Excess weights" were determined with arsenic and antimony present in the electrolyte, as the difference between the weights of the deposits obtained in the presence of these cations and those obtained in their absence, with the two cells connected in series. When gelatin was present along with the arsenic or antimony, it was also added to the electrolyte in the cell in series. Results and Discussion The results of the study are summarized in Figs. 1 to 6. From Fig. 1, top, it is evident that the presence of arsenic or antimony alone results in an increase of polarization, while bismuth alone causes a decrease. The presence of gelatin (25 mg per liter) rather drastically modifies all three cation effects, as indicated in the lower panels of the same figure. The addition of chloride ion, when no gelatin is present, causes comparable decreases in polarization in the presence of antimony and bismuth, but a relatively larger decrease when the electrolyte contains arsenic. It is interesting to note that the decrease in polarization brought about by addition of chloride when both arsenic and antimony are present parallels the behavior with arsenic alone, while the polarization in the electrolyte containing the cation mixture, without chloride added, corresponds to that for an electrolyte containing only the antimony cation. Similarly, the polarization at zero concentration of chloride in electrolyte containing arsenic and bismuth is that corresponding to an electrolyte containing arsenic alone. From Figs. 3a, 4a and 4b, it is clear that, in the presence of gelatin at a level of 25 mg per liter, the effect of chloride in the presence of arsenic and antimony, or a mixture of the two, becomes quite analogous to that observed in the absence of added cations. When both bismuth and gelatin are present (Fig. 5), the decrease in polarization with increased chloride concentration is virtually absent. This is perhaps a reflection of the large decrease in polarization brought about by the bismuth itself in the presence of gelatin. The shifts of the minimum in the polarization-chloride concentration curves brought about by changes of temperature (Fig. 3b), gelatin concentration (Figs. 3c and 4c) and current density (Fig. 3d) when the metal cations were present are all similar to the corresponding shifts observed in their absence." The approximately linear "excess weightv-anti-mony concentration relation recorded in Fig. 6 would seem to indicate that antimony is codeposited with copper to a considerable extent. On the other hand, only very limited amounts of arsenic appear to be adsorbed or codeposited.

Jan 1, 1954

By W. F. Kieschnick, Eugene Harrison, W. J. McGuire

W. J. McGuire, et al, are to be commended for their undertaking of a mathematical solution of a very difficult problem. Unfortunately, however, a mathematical approach requires the application of several assumptions. These assumptions appear to be unrealistic and lead to answers which do not describe what actually happens when hydraulically fracturing oil and gas wells. Considering laboratory confirmation of breakdown phenomena, the authors appear to have tested their theories only on cement specimens and on samples of Austin limestone, much too small to provide any fracture system. This work resulted in the formation of vertical fractures. If the authors had tried similar experiments on thick walled cylinders made from almost any sandstone cores, they would have found that, using crude oil as the breakdown fluid, horizontal fractures would almost always occur, and at pressures much lower than any calculated. They would also find that by confining the fluid to within the bore (using oil base mud for example) on similar samples, the pressures required to burst the cylinders would be considerably higher and most of the fractures would be vertical. This breakdown pressure behavior has been duplicated in wells in Texas, Oklahoma, Kansas and in Wyoming. Considering field data the phenomena of different breakdown pressures for different breakdown techniques can be further illustrated. Most production and service personnel will agree that a breakdown can be more easily obtained if injection into a formation can be established prior to the occurrence of the breakdown. This is true whether the formation being treated is completed as open hole or as a perforated interval. This is clearly illustrated by a Lakota well in Wyoming, completed open hole at a total depth of 7,358 ft. An attempt to vertically fracture this well failed when a bottom hole pressure of 10,326 psi was insufficient to break down the formation. A non-penetrating type fluid (oil base mud) was in the well at the time the breakdown was tried." The oil base mud was then cleaned out of the well and replaced by a 30" API gravity crude oil. With this oil in the hole the formation breakdown was easily accomplished at a bottom hole pressure of 3,607 psi. This large difference in fracture pressures would be impossible according to the theories presented by McGuire, et al. The authors have used as an example the breakdown pressures experienced when acidizing Permian Basin wells. During acid treatments of limestone and dolomite the "breakdown" (drop-off in pressure) seldom occurs until some injection of acid has been accomplished. In these cases the breakdown is most likely to result from the chemical reaction of acid and rock in already existing vugs and fractures rather than from making a new fracture by hydraulic pressure. If this is true, then results in the Permian basin should not be used to validate the authors' calculations. *** AUTHORS' REPLY to ROSCOE C. CLARK and HENRY F. COFFER The purpose of our laboratory experiments in which thick-walled rock cylinders were hydraulically fractured was to determine the validity of the "thick pipe" formula for brittle materials, and not to predict nor demonstrate directly the orientation of field fractures. Our conclusions concerning field results resulted from calculations involving the "thick pipe" relationship as well as considerations of overburden stresses, rock strengths, and the geometry and dimensions of the field system. Clark suggests that had the models been more porous or contained weak bedding planes, horizontal fracturing would have occurred. This is undoubtedly true provided external stresses similar to those in the earth's crust are nor imposed. However, if we were going to design experiments to represent directly the field case we would impose the proper stresses on the models. It is generally recognized that the vertical compressive stress in the earth's crust arising from the weight of the overburden is approximately 1 psi/ft of depth. Then, as an example, even though a horizontal bedding plane has zero strength, the formation cannot be separated to form a horizontal fracture unless the hydraulic pressure exceeds the stress due to overburden. And in those cases in which the stress resisting vertical fracturing is significantly less than that resisting horizontal fracturing, vertical fractures should result, notwithstanding horizontal plane weaknesses. We agree that breakdown pressure will be less if the fracturing fluid penetrates the formation. In Appendix HI of our paper it is shown that leak-off reduces the pressure necessary to initiate either a horizontal or vertical fracture. It would be difficult to attempt to

Jan 1, 1955