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By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By Palmer DJ, Bain JH, Pullen JB

Over the last ten years at Risdon, zinc production capacity has almost doubled. This has resulted in modifications, many of which have affected zinc deposition operating conditions in the cells. Some of these changes appeared to have affected average current efficiency to such an extent that a special investigation was initiated, using multiple regression analysis to assess historic cell unit operating para- meters. The study highlighted the importance of certain parameters in maintaining maximum current efficiency for zinc deposition from !Risdon purified solutions under conditions of !changing current density, acidity and zinc con- centrations. Maximum current efficiency was obtained only within a zinc to acid ratio in cell electrolyte of 0.45 - 0.55 and a residual zinc concentration greater than 48 g.1-1, irrespective of actual zinc concentration or The investigation also established: ieters giving minimum power consumption at termined current density; the effect of ntration changes in common impurities on nt efficiency; the existence of high s of some impurities in solids precipit- in the cells and pure solution tanks.

Jan 1, 1975

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.

Jul 1, 1956

By Sam F. Carter

FOR some time melters and metallurgists have recognized the fact that steels may be made to identical compositions as ordinarily analyzed, but with considerable variations in physical properties. Good melting practice signifies a combination of furnace operations that will produce steel with consistently good physical properties after proper consideration of cost, production efficiency, and chemical control. In acid practice, these operations may be classified fundamentally as: (I) the oxidizing boil, (2) recarburization and deoxidation, (3) slag adjustment, and (4) final deoxidation. These operations affect the properties of the steel through variations in the minute quantities of several microscopic, submicroscopic, and dissolved constituents, which are out of reach of ordinary analyses but are very influential upon the crystallographic slippage and the molecular cohesion of the structure. One of these constituents is the FeO left in solution in the steel. Herty has shown that steels high in dissolved FeO have decreased ductility and impact and increased hardness and electrical resistance. There is also much evidence that FeO in solution affects carbon solubility and diffusion, and consequently abnormality and carburizing behavior.

Jan 1, 1947

By B. J. Shaw, R. Kossowsky, W. C. Johnston

High purity (99,95) Ni-51 wt pct cr eutectic alloy was unidirectionalty solidified at rates of 0.1 to 8 in. per hr. The resulting material was characterized by large grains, approximately 0.5 mm in cross section and extending through almost the entire length of the specimen, parallel to the growth axis. The eutectic structure of specimens the growth at -1/3 The per hr consisted of a continuous nickel-rich phase and chrome -rich lamellae approximately 2 thick, spaced about apart. Specimens were tested in compression at temperatures ranging from —196 to 850"C over which range the 0.2 pet yield strength dp -creased from 160,000 p si to 35,000psi, respectively. Swaging to 40 pet reduction in area, followed by a 30-min anneal at 1000c to remove residual cold work, increased the 0.2 pet yield to 260,000 psi at -196°C, dropping to 35,000 psi at 850°C. The increase in strength was attributed to a residual cell structure. The strength of the alloy could be rationalized by the simple rule of mixtures if one assumed that additional strength is derived front a size effect characterized by is petch equation IN recent years there has been increasing interest in dispersion and second phase strengthening in materials needed for high-temperature applications. inm role of structure on the mechanical The of such alloys has been well established of such some extent accounted for theoretically. and to of how the strengthening mechanisms due to fibers and lamellae operate has been reduced to its fibers form by the fabrication of composites of strong rods unidirectionally aligned in a From work on tungsten-fiber-reinforced copper, for example, it was established that the "Rule of Mixtures" could explain the strengthening.12 " some what more sophisticated technique for introducing strong fibers into copper matrix was used by Hertzberg strong Kraft3 who unidirectionally solidified the copper-chromium eutectic. The use of unidirectionally fied eutectics has advantages in that there are no matrix-fiber wetting problems and fine fibers are automatically aligned and uniformly fiber However, one Is restricted to a specific volume fraction of the second phase. Nevertheless, even though the volume fraction is fixed, the rod or lamella thickness, , can be varied by controlling the freezing interface velocity. Alternatively, the grown material may be worked down by swaging or rolling. Embury and Fisher, " using this approach, drew down pear lite in iron and studied the mechanical properties iron and that the yield strength, oy, was properties.proportional They that d was the wire diameter. It could be inferred that was also proportional to but the work hardening had to be taken into consideration at the same time. By varying the growth rate of the cadmium-zinc lamellar eutectic, Shaw'1 showed that was proportional to without the introduction of work hardening and suggested that the lamellar interface itself contributed to the strengthening of the composite. In this investigation we have evaluated the mechanical properties of the unidirectionally solidified fec-bec eutectic Ni-Cr. This eutectic was selected because it presented the possibility was selected beca temperature, and high corrosion resistant alloy, and also represented a hard-soft phase combination with two completely different slip systems. Specimens were tested in compression and tension up to 850°C and a detailed study of the micro structure as a function of plastic strain and temperature was carried out by light and electron microscopy. It was shown that the composite strength tested in compression can be accounted for by the simple rule of mixtures if one allows for an additional term representing the effect of Intereprese EXPERIMENTAL PROCEDURE 1) Unidirectional Solidification. Fig. 1 is a schematic drawing of the apparatus used to produce 0.2 in. diam by 12 in. long alloy ingots. The crucible tube is alumina, containing the charge which has been is swaged, or machined to 0.195 in. diam. The lower end of the tube is immersed to 0 .195in in.d iam. The upper end is supported by a 10 mil nichrome wire which lowers the crucible mil nic hr the] wire at a prescribed rate. Surrounding the furnace is a graphite susceptor into which a control thermocouple is inserted. The furnace is insulated with fiberfrax and enclosed in a quartz tube. There is a sliding seal at the bottom around the crucible and one on the top so that an atmosphere may be used for the sample and suscep tor. The power for the furnace is supplied from a 10-kw, 450 kc generator. The skin depth (the skin depth at which the field falls to l/e of its value at the outer surface) for graphite (p = 10 (j-ohm-cm) is 0.1 in. at this fre-

Jan 1, 1970

By Dan Martz, Bill Moler, David Young, Wally Chen, Matthew Crow, Steve Norris, Tolga Togan

Two 610 m (2000 ft) long tunnels were driven through water bearing silts, sands and clays beneath the Sacramento River using a 4.59 m (15.1 ft) diameter Earth Pressure Balance Tunnel Boring Machine (EPBM). Four sheet pile shored shafts were sunk with and without dewatering. The pre-cast concrete segmentally lined and grouted tunnels were driven down at 6% grades beneath the river flood protection levees, buildings, roads, a railroad and adjacent to a Freeway Viaduct. Details of the schedule, cost, shaft construction, TBM, tunnel construction, and installation methodology for the twin1.676 m (66 in) steel force main pipes and environmental constraints are provided.

Jan 1, 2007

By Charles L. Morgan

In June 1996, the United Nations International Seabed Authority opened shop in Kingston, Jamaica as an autonomous international organization charged with the administration of seabed mineral developments in all areas beyond national jurisdictions. The Authority is a consequence of the 16 November, 1994 entry into force of the 1982 United Nations Convention on the Law of the Sea (UNCLOS) and the 1994 Agreement relating to the Implementation of Part XI of UNCLOS. The total seabed area included within the Authority?s purview has yet to be assessed accurately, but clearly constitutes the largest single jurisdiction on the planet. The Authority is governed by legislative bodies called the Assembly and the Council and an administration called the Secretariat. The Assembly includes representatives of the 132 member states which are currently parties both to UNCLOS and to the 1994 Agreement. These member states directly fund the operations of the Secretariat. They include most of the world?s developed nations, island nations, and others among the 188 independent countries which are members of the United Nations. Notably absent are the United States and Canada, which are the only developed coastal states not represented. The Council is a 36-member subset of the Assembly representatives selected through a somewhat involved process designed to achieve a balanced representation of the specific interests of the members. Ultimate responsibility for the Authority?s actions resides in the Assembly, but most initiatives originate in the Council. Also included in the Authority are two subsidiary advisory bodies, the Finance Committee, which reviews the Secretariat?s budget, and the Legal and Technical Commission, which evaluates claims and drafts technical regulations. The Secretariat itself includes a staff of about 30, including 15 highly qualified and competent attorneys, accountants, engineers, and scientists. Details describing the composition and activities of these bodies can be found at the Authority?s website (http://www.isa.org.jm).

Jan 1, 2000

By A. Boniface

The International Tunnel and Underground Space Association (ITA) has a number of working groups (WG) that meet at least once a year. One of these is WG12, ?Use of Shotcrete?, of which the author is a member. The purpose of this paper is to draw attention to a number of topics that were discussed at the WG12 meetings held in April and September 2008; and also to a number of other matters that arose from the presentation of thirty-four papers at the 5th International Symposium on Sprayed Concrete held in Lillehammer, Norway between 21 and 24 April 2008.

Jan 1, 2008

By W. D. Johnston, T. P. Thayer

THE minerals that collectively are known as chromite form an isomorphous series of the general formula (Mg,Fe) 0. (Cr,Al,Fe) 203. So wide is the range in chemical composition in this group that chrome ore consisting entirely of the mineral chromite may range from less than 30 pct to more than 60 pct Cr203. The most comprehensive published data on the chemical com- position of chromite are by Stevens,62 who made complete analyses of 52 samples of chromite concentrate from many localities in North, Cen- [ ] tral, and South America. These samples were mechanically purified to remove associated silicates and might be regarded as the cleanest chromite that could be obtained by any mechanical milling process. Fig 1 shows the predominant zone of isomorphism, within the triangular prism of composition defined by the mineralogical end members of the series, wherein his analyzed samples fell.

Jan 1, 1949

By John V. Beall

When the mineral seekers came, they brought romance, excitement and, too often, transitory riches. It has been so for uncounted centuries. While the rich ore lasted, living was high and money flowed-mostly out of town. The whole creation was like a circus. The headframe went up like the center pole of the big top. The reduction works was an ingenious affair; an opportunity for self-expression by the mining engineer on the job. When the high grade gave out or the bottom dropped out of the market, the whole show folded. Machinery was scavenged for the next location. About all that was left were the raw footings, like giantsteps on the hillside; and the headframe above the silent diggings. Mostly, the people went away too. Arizona Territory was like that at the turn of the century. It can still happen. But, in copper, the age-old pattern has been disrupted. From Mineral Park in the northwest to Chino in the east and Cananea in the South, a growing number of companies have emerged-large, stable, productive. Southwest copper is truly a mighty industry, accounting for one fifth of world new copper production. In this period of scientific development, changes are fast, often dramatic. But even mining engineers, or possibly more so because they have an intimate knowledge of the industry, fail to appreciate the evolutionary changes that have shaped Southwest copper into what it is today.

Jan 10, 1965

Surface Plasmon Resonance (SPR) spectroscopy, combined with cyclovoltammetry, has been successfully used to study the interactions between ethyl xanthate, heptyl xanthate, dithio-phosphate and propyl trithiocarbonate flotation collectors and a gold surface. Large, easily measurable responses have been obtained in the potential areas where the thiol collectors are known to interact with gold. The four collector types lead to differing SPR maximum values, with longer alkyl chains resulting in higher SPR responses, and the trithiocarbonate leading to the highest response values. The SPR responses differ considerably from the current density response at very anodic and cathodic potentials. There are indications that thiols might still be adsorbed at potentials as low as-300 mV (vs SHE). Keywords: flotation collectors; thiol collectors; cyclovoltammetry; surface plasmon resonance spectroscopy.

Jan 1, 2005

By R. R. M. Cousens, W. S. Garrett

Discussion: L. T. Campbell Pitt: When Mr Garrett and I discussed the design and construction of plugs and bulk head doors to resist great water pressures in mines about ten years ago, we visualized an emeregeny when there would be no time for site preparation. We could not however, anticipate a problem of such magnitude and urgency as the one described in the paper under discussion. The paper very clearly describes the flooding and the measures taken to save the mine. The complete flooding would have been a national disaster. The account of the combat between man and water reads like the account of a military operation. It was an endeavour which achieved success because there was a master plan, tenacity and, in fact, heroism. The paper is of necessity a long one. In my contribution I will mention some historical facts and factors that I believe have relevance to the flooding and the saving of the mine. It is of great satisfaction to me to have been one of the two initiators of a new approach to underground plug design and construction. The investigation was taken over by a Chamber of Mines Committee which combined our early work with further research and the resulting data had a significant bearing on the West Drie emergency plug designs. The final plug length was correctly based on the requirements to obviate leakage. A plug to have structural strength only would have been very much shorter but so ineffective as to have become a waste of labour, material, and in consequence, wasted the limited time available to prevent flooding of the whole mine. The figure of 75 lb per sq in. sheer stress provided a very ample margin, in my opinion, but under the very difficult site conditions and the limitations of plug material suitable for the very unusual construction, justified such a figure. There must have been considerable temptation to reduce the safety margin due to the urgency to complete and commission the plugs, but it is much to the credit of the directors of this operation that nothing less than a safe design was permitted. In about 1945 Blyvooruitzicht Gold Mining Company, which was then mining in to the West Driefontein area to assist in early development, decided to protect themselves from a possible inrush of water from the latter mine. A bulk head door was accordingly designed and installed on 2 level between 1945 and 1948 at 4,218 ft below surface. Since West Driefontein paid for it, Gold Fields consulting mechanical engineers collaborated with their colleagues of Rand Mines who completed their design after a few modifications were agreed. This door was never used to prevent an inrush into Blyvooruitzicht but the exercise was very useful to Gold Fields when the high pressure doors initially installed on 10 and 12 levels between Nos. 2 and 3 shafts to enable isolation of one section of the mine from another were designed. At that time the capacity of West Driefontein to cope with an inrush of water was comparatively small because the storage in stoped areas and the installed pump capacity were much less than in later years. These doors together with others of the same design were later moved to the lower levels served by sub vertical shafts. In addition, doors to prevent flood water entering the pump chambers on 18 level were installed at each end of that level, and designed for a head of 360 feet so that water would have to reach 16 level before the pumps were flooded. All these doors were called upon to hold water and it is reported that only a small plug in one of the doors and a 4 in. dia flanged pipe joint failed. The lesson is that in these cases the smallest details warrant as much attention as the major ones. That these were the only equipment failures when so much depended on equipment, is very much to the credit of design engineers, both of the Gold Fields head office and companies who supplied both mechanical and electrical equipment. Until I had read the paper I wondered why the policy of isolation by bulk head doors was not continued as the development moved eastward towards the Bank Compartment and particularly when it pierced the Bank dyke. The reasons have been given in the paper. It was unreasonable to expect provisions to be made to counter the remote contingency that the large installed pumping capacity and mine capacity to store water would be exceeded during a peak inrush. When pumps were being considered for West Driefontein, it was decided that the Gold Fields standard underground main pumps at that time of 1 million gallons per 24 hours would be too small. Three alternatives were considered. 1. Very large units that would require underground sub assembly and dismantling of both pump and motor. 2. The largest pump and motor that could be conveyed as a complete pump or motor from surface to the pump chamber. 3. Pumps of higher speed to reduce dimensions and weight. It was decided to adopt alternate 2 because of avoidance of transporting pumps in parts and assembling underground. Alternative 3 was not favoured because high speeds would have introduced problems of more exact rotor balancing. I believe the decision was correct and in the crisis enabled comparative easy transport of pumps and motors to surface for overhaul and, if required, transfer to other pump stations. The standard pump thus became a 10 stage 1,500 rpm pump with a capacity of approximately 2 million gallons per 24 hours against a static head that varied

Jan 3, 1969

By Igor Gonzales G.

Southern Peru Copper Corporation (SPCC) has recently completed the construction of copper leaching, solvent extraction, and electrowinning facilities at their Toquepala and Cuajone plants in Southern Peru. Much of the ore for these new operations is the result of the existing mining operations that have been in existence as early as 1959. At Toquepala, pre-conditioning and bacterial dump leaching of the sulfide ore that was too low in copper content to be processed through the copper concentrator began in 1987. The Cuajone heap leach operation is treating copper oxide ore that has been stockpiled since the Cuajone concentrator began operation in 1976. The pregnant leach solutions from the dump leaching at Toquepala and the permanent pad heap at Cuajone are combined into one plant feed solution. Adjacent to the large dumps at Toquepala, a solvent extraction and electrowinning facility has been constructed. The electrowinning facility has a planned annual production rate of35,000 metric tons per year Grade A cathode copper. Initial production of the cathode copper began in November 1995.

Jan 1, 1996

By J. S. Kirkaldy, R. C. Dorward

The solubilities of copper and gold in silicon and germanium have been determined by equilibration of the solid semiconductors with coexisting liquidus phases. The experimental results were combined with estimated activity coefficients of the liquidus alloys to determine the following partial molar enthalpies and excess entropies of solution for the systems: Solubility measurements were also carried out below the eutectic temperature of the copper-silicon system. The partial molar enthalpy and excess entropy of copper in silicon with respect to Cu3Si were determined to be 40.2 ±0.5 kcal per mole and 9.7 i 0.5 cal per mole — OK, respectively. It has been dentonstrated that nu-cleation and growth of intermediate compounds are retarded in copper-silicon diffusion couples. This points out the dangers of determining equilibrium solubilities by dijjusion methods. THE thermodynamic requirement for equilibrium between contiguous phases at constant pressure and temperature is that the chemical potential of each component be constant throughout the system. Equating expressions for the chemical potential of solute, component 2 say, in two phases, alpha and beta, gives

Jan 1, 1969

By Toshiaki Akahoshi

Keywords: Wasted catalyst, Hydrodesulfurization, Ammonium vanadate, Ammonium molyb-date, Hydrometallurgical process. The fundamental reactions have been investigated in order to develop a hydrometallurgical process for recovery of molybdenum and vanadium from wasted catalysts generated in the hy-drotreating desulfurization of heavy oil. The principal steps of the process are a mild oxidation roasting of the waste catalysts at temperature around 500°C, leaching of the target metal components with dilute ammoniacal aqueous leachates, selective precipitation of vanadic acid, and ammonium molybdate precipitation. The selective recovery of vanadium as vanadic acid is successfully performed using ammonium sulfate as a salting-out agent. Recovery of ammonium molybdate is based on large dependence of solubility of ammonium molybdate in ammoniacal solutions upon temperature and ammonium salt concentration. In this process, the solution after recovery of vanadium and molybdenum is recycled to the leaching stage of the roasted materials, and the ammonium salts in the process liquor is in the repeated use. Employment of am-moniacal system makes it possible to operate the roasting at much lower temperature than that for the currently operating process.

Jan 1, 2005

By W. F. Hosford, E. W. Kelley

By testing polycrystalline specimens from textured plates which had Previously been used to provide materials for growing single crystals, it has been possible to relate the plastic anisotropy of textured materials to the deformation behavior of single crystals. The deformation studies have been conducted at room temperature on textured polycrystalline magnesium and binary Mg-Th and Mg-Li alloys. Variously oriented specimens of the textured materials were deformed in plane-strain compression and in uniaxial tension and compression. The stress-strain curves are similar in their general jorm of anisotropy and stress levels to those obtained on single crystals of the same alloys. The degree of anisotropy is lower, however, in the polycrystalline materials and correlates with the intensity of the basal texture. Yield loci for the textured materials appear reasonable in terms of the deformation mechanisms, and deviate sharply from the form predicted by the Hill analysis for aniso-tropic material. A N earlier study1 of single crystals has shown that magnesium and magnesium alloys with thorium and with lithium deform at room temperature primarily by basal slip, {10i2) twinning, and (1011) banding. The (10i1) banding mode is a combination of {10ll) twinning followed by (1012) twinning and basal slip within the doubly twinned material.2, 3 Magnesium with lithium can also deform by {1010)(1210) prism slip.1'4'5 Still other deformation modes have been reported for magnesium6-11 but these are considered to play a minor role in room-temperature deformation. In a polycrystalline material, plastic deformation must occur in the individual grains through the operation of one or more of the various deformation modes. Because the critical shear stress for basal slip is very low compared to the activation stresses for the other deformation modes,' basal slip accounts for much of the deformation in the polycrystalline aggregate. However, since there are only two mutually independent basal slip systems, and because five independent systems must be active for an arbitrary shape change in any material,'' modes other than basal slip must account for some of the strain. The deformation of textured magnesium, like that of other hcp metals, must be controlled by the same mechanisms observed in single crystals. In strongly textured material, the form of the anisotropy should be similar to that of single crystals, and the degree of anisotropy should depend on the intensity of the texture. EXPERIMENTAL PROCEDURE The anisotropy of deformation was investigated through the use of plane-strain compression tests, as well as uniaxial tension and compression tests. Materials. Test specimens were cut from the three textured plates of magnesium which had previously been used to provide material for single crystals.' These plates, furnished by Dow Chemical Co., had been reduced about 80 pct during the process of being hot-rolled to their final 1/4-in. thicknesses. The plates had the three respective compositions, pure magnesium, Mg-0.5 wt pct Th (0.49 pct Th by spectro-graphic analysis), and Mg-4 wt pct Li (3.84 pct Li by chemical analysis). Impurities other than iron were less than 0.0005 pct Al, 0.01 pct Ca, 0.001 pct Cu, 0.0006 pct Mn, 0.001 pct Ni, 0.003 pct Pb, 0.001 pct Si, 0.001 pct Sn, and 0.01 pct Zn. Iron was 0.001 pct in the pure magnesium, 0.002 pct in the Mg-0.5 pct Th, and 0.014 pct in the Mg-4 pct Li. The textures of the three plates were determined by X-ray diffraction utilizing only the reflection technique out to an angle of 50 deg from the sheet normal. The resulting basal pole figures are presented in Figs. 1, 3, and 5. Grain sizes in the plates were ASTM number 4 in the pure magnesium and number 7 in each of the alloys. Plane-Strain Compression Tests. Plane-strain compression specimens approximately $ in. thick by 4 in. wide by $ in. long were prepared for each of the three compositions. These specimens were prepared in a manner similar to that used for the single-crystal specimens of the earlier study.' All polycrystalline specimens were stress-relieved at 500°F for hr as the final step in their preparation for testing. The testing procedure was identical to that used for the single crystals, involving compression in a channel and using 2-mil Teflon film as a lubricant. The specimens were tested in six orientations of interest, these being the six combinations of the rolling, transverse, and thickness directions of the material serving as loading, extension, and constraint directions in the plane-strain compression test. Each of the six orientations was assigned a two-letter identifying code. These are combinations of the letters (thickness direction), R (rolling direction), and T (transverse direction) with the first letter signifying the loading direction and the second letter the extension direction. For example, ZR specimens were compressed in the thickness direction while extension was permitted to operate in the rolling direction of the textured material. To facilitate comparison of the present work with that of the single-crystal study1 the orientations used for single crystals are given in Table I along with the polycrystalline orientations that most nearly correspond. To insure reproducibility, at least three duplicate

Jan 1, 1969

By R. E. Smallman

R. E. Smallman (University of Birmingham, England)—Recently, Tedmon and Ferriss11 have determined the yield stress parameters oi and ky for tantalum by measuring the lower yield stress as a function of grain size 2d and fitting the results to a relationship of the form They report that although ky , which is taken to be a measure of the dislocation locking strength, is small (- 2 to 4 x 106 cgs units) a substantial yield drop is nevertheless observed in a normal tensile test. Niobium gives a similar result,12-14 as pointed out in the original work by Adams et a1.,12 and in order to check this apparent anomaly the yield-stress parameters of electron beam-melted niobium have recently been reanalyzed15 by the Luders strain technique. In this method the strain hardening part of the stress-strain curve is extrapolated to zero plastic strain; the intercept on the preyield portion of the curve is taken to give oi, whilst the difference between oi and the lower yield stress gives kyd-1/2. The results indicate that ky increases with increasing grain size and hence, a plot of vs d-112 yields an apparent ky, which is lower than the true value. A similar effect could account for the small ky found in the relatively pure tantalum used by Tedmon and Ferriss. The variation of ky with grain size shows that dislocations are more strongly locked in coarse-grained specimens than in fine-grained samples. In niobium, this may be attributed to the fact that the dislocation density in the fine-grained material is higher than that found in the coarse-grained samples which are given a sufficiently prolonged anneal to remove any residual substructure and, since the metal contains only a small amount of interstitual impurity, a variation in locking occurs. By contrast, application of both the grain size analysis and the Luders strain method to yield-stress data from commercially pure vanadium containing a large amount of interstitial impurity gives consistent values of oi and ky, with ky independent of grain size and temperature. Electron microscope observations show minor variations in dislocation density from grain size to grain size, but in any case in this material the dislocations are heavily locked with precipitate. On yielding new dislocations are generated and, as a consequence, the importance of any differences in dislocation density between the various specimens of different grain size is considerably reduced. It is perhaps significant that Adams and lannucci,16 working with a grade of tantalum containing a higher interstitial content than that used by Tedmon and Ferriss, prepared the specimens of different grain size by annealing in the temperature range 1500" to 2000° C to minimize any differences in dislocation structure, and found that ky had a value of 1.04 x 107 cgs units, independent of testing temperature. Such behavior is consistent with the dislocations being locked by carbide precipitates so that the generation of free dislocations is an athermal process. The recent work of Gilbert et al.17 also shows that in tantalum there is no significant variation of ky with grain size provided it contains 150 ppm of oxygen. In this case, however, the dislocations are not locked by precipitate and ky is temperature dependent. C. S. Tedmon and D. P. Ferriss (authors' reply)— We would like to thank Dr. Smallman for his interesting comments and discussion to our paper, "The Dependence of Yield Stress on Grain Size for Tantalum and a 10 pct W-90 pct Ta Alloy".18 It was suggested that perhaps the relatively small values obtained by us for ky of tantalum could be attributed to the same cause that accounts for the apparently small values of ky that result when it is determined by the Luders Strain technique. Since our values were obtained by plotting the lower yield stress vs the reciprocal of the square root of the grain size, it is not clear how this could be the case. The values of ky in this experiment have been calculated, using the Luders strain technique. With this method, values for ky on the order of 2 x 105 to 5 x lo6 cgs units were obtained. In spite of this rather large variation, the magnitudes are still small, and there appeared to be no good correlation between ky and the grain size or the yield stress, probably because of the difficulty in accurately extrapolating the work-hardening portion of the curve back to zero plastic strain. As was shown in the original data,18 there was little work hardening in any of the curves, at any temperature. In his discussion, Dr. Smallman also points out how ky has been observed to increase with increasing grain size, when determined by the Luders strain technique. There are at least two possible explanations for this. In the first case, if it is assumed that the bulk of the interstitial impurities are concentrated at the grain boundaries, then, of course, the available grain boundary area would decrease with increasing grain size, thus presenting less area for the interstitials, which would then presumably increase the concentration within the grains, thereby increasing the locking of the dislocations. In the second case, the increase in ky with increasing grain size would be attributed to the nature of the grain boundary itself. One of the several ways of deriving the Hall-Petch equation19 is based on the stress concentration arising from a pile-up of dislocations at the boundary. The ability of the stress concentration to unlock a source in a neighboring grain would depend on the strength of the grain boundary. As is well-known, the nature and struc-

Jan 1, 1963

By Sandra L. Mesa-Espitia, Gretchen T. Lapidus

Gold present in arsenopyrite matrices is refractory and requires highly oxidative pretreatments in order to obtain acceptable degrees of extraction. However, these release many byproducts that are harmful to the environment. In the present work, a high-grade arsenopyritic ore was pretreated with different solutions, containing hydroxide ion, EDTA, oxalic, tartaric, or citric acids, to improve gold extractions in a posterior leaching step. The pretreatments were carried out at room temperature for 24 hours with a respective ligand concentration of 0.25 M. Once completed, the residue was leached in a thiosulfate solution to quantify the effect of the pretreatment on gold extraction. Only 29% of the gold content was leached, with very slow kinetics, in the untreated mineral. However, after pretreatment with tartaric or citric acid, the kinetics improved, although the percentage of gold extraction only reached 42-45%. The highest gold recovery, with very rapid kinetics, was found with the oxalic acid or the hydroxyl ion pretreatment (70 and 62%), respectively, but also corresponded to the most arsenic co-dissolution.

Jan 1, 2014

By N. H. van Lingen

A laboratory stud], has been made to determine what factors affect the penetration rate of roller bits, diamond bits and drag bits in rock drilling with clay /water muds. The rather simple relations that exist when pressures in and around the borehole are equal become more conzplicated when under down-hole conditions the penetration rate is hampered by the existence of a pressure differential between the mud at the hole bottom and the pore liquid at cutting depth. Expressions that have been derived for both the penetration rate and the magnitude of the pressure differential in permeable rock together fully account for operating, rock, mud and bit variables. In impermeable rock a similar pressure differential is caused by the bit action itself. In all cases, the pressure difierential and the reduction in penetration rate increase with the effectiveness of the plastering at the bottom of the hole by mud particles. Where bits are employed whose action is largely that of crushing, however, the plastering may become even more effective owing to the addition of rock particles rubbed into the pores of the rock. With roller bits, a plastically hehaving layer may be formed, which causes a further reduction in penetration. In the case of bits whose action is chiefly scraping, moreover, penetration may be arrested by the bit's becoming balled-up. The various adverse effects are reduced by thorough scavenging of the hole bottom. This paper shows how with jet bits the efficiency of such scavenging may he improved by suitable choice of the position of the nozzles. INTRODUCTION The reduction in a bit's penetration rate with increasing depth of hole has been the subject of many investigations. Various investigators ',' have independently reached the conclusion that this reduction occurs not so much because the rock-breaking process becomes more difficult as it does because the lifting of the rock fragments is impaired by a fluid pressure differential holding the fragments down. When such a pressure differential can be avoided, as in air drilling and to a smaller extent in water drilling, penetration rates remain high. Although the range of applicability of these techniques is being extended, most oil wells still have to be drilled with mud. In this paper we present the results of laboratory experiments carried out to determine what factors govern the hold down effect encountered in mud drilling. In the course of this investigation, the well known importance of bottom scavenging came more and more into prominence. Not only may it reduce the magnitude of the hold-down forces, but also it appeared to be a means of preventing the accumulation of a plastic mass of cuttings and mud on the hole bottom and bit which may cause penetration to cease almost completely. So that the effects of fluid pressures may be more readily understood, the factors that govern penetration rate in the absence of these pressures will first be discussed. The effect of down-hole pressures will then be assessed for the case of permeable rock where fluid pressures are well defined, and it will be demonstrated how rock strengthening due to confining can be accounted for. Subsequently, fluid pressures in less-permeable rock will be examined; we will show that in impermeable rock it is the bit action that governs fluid-pressure distribution and hold-down. In the case of poor scavenging and/or high bit load. cutting cake manifests itself. The effect, like various others. appears to depend on the type of bit used. From the very beginning, therefore, we shall base our discussion on the three main types of bits used in rotary oil-well drilling— roller bits, diamond bits and drag bits. Since space is limited, it will be impossible to make more than a passing reference to many aspects of the problem. Moreover. certain relations that are not of primary irnportance to our argument will unavoidably have to be stated in a somewhat dogmatic fashion, and the experimental data on which these are based necessarily must be omitted. EQUIPMENT The drilling experiments were performed on three machines, of which one has been designed for the realistic simulation of down-hole pressure conditions. HIGH-PRESSURES MACHINE In this machine (diagramed in Fig. 1) the mud, pore and confining pressures can all be adjusted independently. The foil-covered rock sample contained in the inner pressure vessel is confined by oil that is pressurized by means of a hand pump. The pore space of the watersaturated sample is connected to an arrangement which keeps the pressure in the pore space constant regardless of the rate of filtrate flow through the sample.

By J. B. Clemmer, P. E. Churchward, C. Rampacek

A cyclic method for processing manganese ores using sodium sulphate as the basic reagent is described. Sodium sulphate is electrolyzed in a diaphragm cell to give an anolyte-containing agentisdescribed.Sodiumsulphuric acid and a catholyte-containing iselectrolyzedincaustic soda, a part of which is carbonated in a cyclic manner to form soda ash. The reduced ore is leached with the anolyte to dissolve the manganese and the impurities are precipitated by addition of catholyte. Manganese in the pregnant todissolvethemanganeseandtheimpuritiessolution is precipitated as synthetic rhodochrosite with a carbonated catholyte, and sodium sulphate is regenerated. Calcining the manganese carbonate gives a high grade product and the carbon dioxide is returned to the carbonation step. The results of laboratory tests using cells equipped with synthetic-fiber diaphragms and permselective membranes, which permit transfer of anions or cations during electrolysis, are described. A METHOD which has been considered for pro-cessing manganese ores under emergency conditions to recover a product suitable for smelting to ferromanganese involves reductive roasting of the ore for leaching with dilute sulphuric acid followed by precipitation of the manganese from the purified pregnant solution with sodium carbonate. Although the process is operable and involves no novel or untried steps, it is noncyclic in regard to reagents. Research seemed warranted to determine if a cyclic process could be developed by electrolyzing the sodium sulphate formed during precipitation of the manganese with soda ash to regenerate sulphuric acid and sodium hydroxide. Reduced ore would be leached with acid anolyte to dissolve the manganese. The iron, alumina, and other dissolved impurities would be precipitated with the caustic catholyte, and the manganese in the purified pregnant solution would be precipitated as artificial rhodochrosite with carbonated catholyte to regenerate simultaneously sodium sulphate for electrolysis. Waste boiler gas and CO, from calcining the manganese precipitate would be recycled for carbonation of the caustic catholyte. There is a surprising lack of data in the technical literature on diaphragm electrolysis of sodium sulphate. One of the more comprehensive papers, by Atwell and Fuwa, describes the problem involved in electrolyzing byproduct sodium sulphate from the viscose process with particular regard to the design and operation of asbestos diaphragm cells. Frisk' also investigated electrolysis of sodium sulphate from viscose-spinning baths to recover caustic soda and sulphuric acid. The objective in these investigations was to produce, by electrolysis and evaporation, a concentrated caustic-soda solution and a sulphuric-acid solution low in sodium sulphate. Because of these requirements, the process was not too attractive despite a favorable yield of caustic and acid with a reasonable power consumption. Because strong acid and base are not required for processing manganese ores and nonelectrolyzed sodium sulphate is not objectionable in either reagent, the present problem was somewhat simpler than that of these investigators. The purpose of this report is to summarize briefly the results of laboratory electrolysis of commercial sodium sulphate in diaphragm cells of different types and the application of the acid and caustic for processing manganese ores in a cyclic manner. Electrolysis in Permeable Diaphragm Cells The principal problem in electrolyzing sodium sulphate in a permeable diaphragm cell is to prevent mixing of the acid and base formed in the anode and cathode compartments. It is not enough to separate the anolyte and catholyte by a single diaphragm. A three-compartment cell in which the sodium-sulphate solution is fed to the center compartment and flows through the permeable diaphragms to the anode and cathode compartments is more efficient electrically. Diaphragms should be porous enough to allow flow of solution to outer compartments but tight enough to prevent gross mixing of the anolyte and catholyte. In addition to being resistant to acid and alkali, the diaphragms should offer minimum resistance to the flow of current. It is also important that the electrolyte contain a high concentration of sodium sulphate to furnish an abundance of sodium and sulphate ions and thereby decrease the current carried by hydrogen and hydroxyl ions. A practical limitation of sodium-sulphate concentration is imposed by the decreased solubility of sodium sulphate with decreasing temperature. At 20°C, a concentration of 200 g per liter sodium sulphate can be maintained. Little is gained in conductivity by using a concentration greater than 200 g per liter. The small-scale continuous electrolysis tests were made in a 12x12 in. open-top bakelite cell equipped

Jan 1, 1956