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By D. J. Schmatz, H. I. Aaronson, H. A. Domian

Diffusion kinetics in disordered hcp Cd-Mg alloys have been investigated by means of the Kirkendall effect and concentration-penetration curves determined with an electron-microprobe analyzer. Self-diffusion coefficients of both species were determined at the three marker compositions obtained, averaging 27.6, 46. 7, and 78.1 at. pct Mg, by means of the Darken analysis. These coefficients were then corrected for the unequal and concentration-dependent partial molar volumes of the two elements with the Balluffi analysis, and for the vacancy flux effect by the Manning analysis. The latter correction reduced the Balluffi correction produced larger changes in the self-diffusiv-ities; neither, however, produced statistically significant changes in the Do's or the H'S. The most striking result of this investigation is that at all three compositions and at all temperatures studied both the uncorrected and corrected self-difjusivities of magnesium are higher than those of cadmium. The Cd-Mg system is the first one found in which the higher melting, lower vapor pressure element diffuses more rapidly. Both an empirical correlation due to Toth and Searcy and considerations of the atomic mechanism of diffusion indicate that this anomaly is probably due to a comparatively low value of the activation energy required for a magnesium atom and a vacancy to exchange sites, perhaps occasioned by the higher compressibility of magnesium atoms. KIRKENDALL effect studies have been previously reported for only two hcp solid solutions: the E phase of the Zn-Cu system1 and the a phase of the Cd-Hg system.' In neither investigation were the marker-movement studies supplemented with the concentration-penetration curve determinations necessary to evaluate self-diffusivities by means of the atano and the Darken analyses. The present program was undertaken to obtain both types of data on a hexagonal solid solution in order to provide more detailed information relevant to the mechanism of diffusion in this type of lattice. The Cd-Mg system was chosen for this study because the disordered solid solution extends across the entire phase diagram at temperatures above 253"c5 and the substantial difference in the melting points of the component pure metals promised that marker movements would occur at reasonably rapid rates should the diffusivities of the two species be as unequal as might be anticipated. The experimental convenience of the relatively low melting points of cad-miun and magnesium and the availability of extensive and accurate activity data6 (required for application of the Darken analysis) were additional reasons for selecting this alloy system. Since the anisotropy of diffusion is not large in either pure cadmium7 or pure magnesium,' the diffusion couples were prepared from polycrystalline components. The presence of a well-defined texture in the couples—the c axis of individual crystals tended to be normal to the diffusion direction— however, provides a fair degree of crystallographic definition to the data obtained. The principal (and entirely unexpected) finding of this investigation, that magnesium, the high-melting low-vapor pressure element, diffuses more rapidly than cadmium, in contradiction to a broad range of results in fcc and bcc alloys, as well as in the previously studied hcp alloys,172 makes the self-diffusivity determinations of immediate interest in understanding the origin of this anomalous result. EXPERIMENTAL PROCEDURE The cadmium (Belmont Smelting and Refining Co.) and magnesium (Dow Chemical Co.) used in this study were both of 99.99 pct purity. Alloys containing 51.0 and 65.6 at. pct Mg were prepared from these materials by melting under a MgC12-base flux in a high-purity graphite crucible. These alloys were subsequently hot-worked and then homogenized in a helium atmosphere at temperatures close to their solidus points. Sandwich-type diffusion couples of the type g/d/g were prepared from the pure metals by solid-state diffusion. Two-piece alloy couples of Mg/65.5 at. pct Mg (Mg/gCd) and Cd/51.0 at. pct Mg (Cd/CdMg) were welded by a liquation technique. The individual components of both types of couple were initially cylinders 1.27 cm in diam and in length; the ends of these cylinders were machined accurately flat and parallel. For both welding techniques, the pure cadmium cylinders and the alloys were chemically polished in a mixture of 40 pct ethyl alcohol, 40 pct hydrogen peroxide (30 pct conc), and 20 pct nitric acid,g while those of pure magnesium were polished in a solution of 10 pct nitric acid in ethyl alcohol.' Immediately afterwards, both metals were rinsed in freshly distilled acetone, and then in similarly purified methanol.' The Mg/Cd/g couples were assembled in a carefully cleaned stainless-steel welding fixture, in which a screw operating through a self-centering arrangement permitted a controlled pressure to be exerted upon a couple prior to welding.'' Tungsten marker wires 0.005 cm in diam were placed at the d:g interfaces of some of these couples, and imbedded in the couples during the application of pressure. As soon as a couple had been assembled, the welding fixture was inserted into a Pyrex capsule containing a packet of zirconium chips at each end. The capsule

Jan 1, 1967

By A. U. Seybolt

The solubility limit of oxygen in columbium has been determined in the range between 775' and 1100°C by means of lattice parameter measurements and microscopic examination. The solubility is a function of temperature and varies, in the range given above, from 0.25 to 1.0 pct O, respectively. BECAUSE of the marked deleterious effect of oxygen upon the mechanical properties of some of the transition metals, it is desirable to know something about the solubility of oxygen in these metals. The brittleness caused by oxygen in solution is particularly marked in the case of the group VA elements, vanadium, columbium, and tantalum. The solubility of oxygen in vanadium has already been reported in an earlier paper,' and Wasilewski2 has given a value (0.9 wt pct) for the solid solubility of oxygen in tantalum at 1050°C. Brauer3 in 1941 investigated the Cb-0 system up to Cb2O5, but made no real effort to investigate the extent of oxygen solubility in the metal. He made the observation, however, that this solubility must be less than 4.76 atom pct (0.86 wt pct) oxygen. This estimate was made from X-ray diffraction results on the alloys CbO, CbO, and CbO; all alloys consisted of the terminal (Cb) solid solution plus CbO, but the last alloy containing 4.76 atom pct 0 showed only three very weak CbO lines. It is surprising that Brauer, by examining only three alloys, arrived at an estimate of the solubility which agrees very well with the results to be reported herein. Experimental Procedure A columbium strip obtained from Fansteel Metallurgical Products was cut into strips, 0.020x1/2x2 in. Two holes, about 3/16 in. in diameter, were made near the ends of the strips in order to hold them against a flat steel block for mounting in a General Electric X-ray spectrometer for lattice parameter measurements. The same holes were used to hang the specimens inside a fused silica vacuum furnace tube which was part of a Sieverts' gas absorption apparatus. The apparatus and method of adding oxygen gas has been previously described.1 According to the supplier, the columbium obtained had the analysis given in Table I. After degreasing the samples, approximately 0.001 in. was etched from each side of the samples in order to remove possible surface impurities from the last rolling operation. For this purpose the following cold acid pickle was found satisfactory: 8 parts HNO3, 2 parts H2O2 and 1 part HF. Various Cb-O compositions were obtained up to 0.75 wt pct O by the gas absorption and diffusion technique. After the sample had absorbed all the oxygen gas added at 1000°C, an additional 24 hr was allowed for homogenization. This treatment appeared to be adequate, as shown by the linearity of the lattice parameter-composition plot. More concentrated alloys were prepared by arc melting mixtures of Cb and Cb2O5 since it was very time-consuming to make Cb-0 alloys in the neighborhood of 1 pct O, or over, by the diffusion method. When the flat strip specimens were used, they were ready for the X-ray spectrometer after cooling from the Sieverts' apparatus. The cooling rate obtained by merely allowing the hot fused silica furnace tube to radiate to the atmosphere (when the furnace was lowered) was sufficiently fast to keep the dissolved oxygen in solution. Arc-melted alloys were reduced to —200 mesh powder in a diamond mortar, wrapped in tantalum foil, sealed off in evacuated fused silica tubes, and then heat treated as indicated in Table 11. The fused silica tubes were quickly immersed in cold water without breaking the tubes after the heat treatments. The tantalum foil prevented reaction between the fused silica and the sample; there was no reaction between the powdered samples and the foil at 1000°C, but some trouble was experienced at 1100°C. At this temperature level a reaction between the sample and the foil was sometimes observed, which resulted in erroneous parameter values. Experimental Results Hardness Tests: Since most of the X-ray samples were in the form of flat strip, it was convenient to obtain Vickers hardness numbers as a function of oxygen content. Compared to the V-O case,' oxygen hardens columbium much more slowly, presumably because of the larger octahedral volume in colum-bium (about 12.0 compared to 9.3Å3 in vanadium), hence, requiring less lattice strain for solution. The plot of VHN vs wt pct O is shown in Fig. 1.

Jan 1, 1955

By Paul M. Tyler

ROUGHLY one-half the value of mineral products at mines or quarries must be spent for wages. In view of the steady increase in hourly wages that continued for several decades prior to the onslaught of the recent depression, it is perhaps surprising to discover that labor's share of the gross proceeds of the mining and quarrying industries of the United States declined to 46.8 per cent in 1929, compared with 52.2 per cent in 1919 and 53.2 per cent in 1909. The actual percentages vary in different branches of the industry and in different localities but the downward trend is unmistakable. For the period 1909 to 1919 it was quite marked in every industry and from 1919 to 1929 it was apparent in all but six: namely, gold and silver lode mining, placer gold mining, crude gypsum production, marble quarrying, asbestos production, and fluorspar Tninino mining

Jan 1, 1933

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a' phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a' phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.' Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a', with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a' phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a'. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By W. R. Marks

Computer-aided torsional analysis of grinding mill drives is defined and related to the mill design process. Equations of torsional dynamics are developed for general mechanical drives. Consideration is given three solution types - specifically the determination of undamped natural frequencies, the calculation of steady vibration amplitudes, and the prediction of transient torques during starting. Following a summary of the methods of calculating drive motor performance, the problem in making practical application of this theory are discussed. Experiences in both calculating and measuring the torsional loads on a large ball mill with dual synchronous motors are reviewed. Conclusions are drawn on the effectiveness of computer-aided torsional analysis for improving mill drive reliability.

Jan 1, 1984

By J. Menashi, D. A. Douglas, A. S. Rappas

A process has been developed for recovering the refractory metals chromium (Cr), vanadium (V), molybdenum (Mo), and tungsten (W) in mixed secondary source materials, such as contaminated grinding wastes. The wastes are calcined with sodium carbonate in air to yield water-insoluble oxides of the base metals iron (Fe), nickel (Ni), cobalt (Co), and copper (Cu) and water-soluble salts of the refractory metals. An aqueous leach separates these two classes of metal values. Cobalt, nickel, and copper can be recovered from the oxidic residue by conventional processing methods. The leach solution is purified and then treated to recover the refractory metals. The process can accommodate a wide range of feed compositions and generates a minimum of aqueous effluents.

Jan 1, 1985

By M. J. Pearse

The processing of fine particles inevitably produces slimes. These present a dewatering problem, for which gravity thickening provides a partial or preliminary solution. The paper shows the effects of practical factors in carrying out laboratory sizing tests for thickeners. Several methods of determining thickener unit area have been compared for a lightly coagulated phosphate slurry and a highly flocculated kaolin slurry. Practical techniques of mixing and flocculant addition have significant effects on batch settling data. Pulp temperature and cylinder dimensions are very important. Errors in sizing thickeners for highly flocculated slurries by the standard methods are discussed. Such methods are suitable for less compressible slurries, however. Rules of thumb for flocculant selection are given.

Jan 1, 1980

By John A. E. M. Church

THE prospector's pan was the first implement used for saving gold, and its action is so effective that it has never been equalled for thorough work. Copper plates, blankets, sluices, and amalgamators of several patented designs have thrust it aside, but in spite of all the advances made there is no dispute among experienced men as to the comparative thoroughness of the work done by it and its rivals. When its rivals are doing their best, the pan can take their discarded refuse and prove their inefficiency by producing from it not only gold, but even the mercury which has been lost from the machines themselves. The trouble with the pan has always been that it was only a tool. Man was the machine that moved it. His work was high-priced, the quantity treated small, and it was impossible to use the pan for any but the richest sands. As a consequence the best gold-saving appliance known has been discarded for years and replaced by machines of inferior excellence, but which could more than make up for their limited ability in saving gold by their capacity for treating great quantities of ore. Mr. Peck is one of the old-time amalgamators of the Comstock district, and the first idea of the new machine came to him as he used to pan below the tailrace of his mill. No matter how fine the work of the mill was, the pan invariably proved that better could be done. The tailings always contained gold, silver, and mercury. This state of things is just as true to-day, after all the improvements that have been made, as it was then, and the much-vaunted method of the " Washoe process" consists in extracting 72 per cent. of the gold and silver by one operation, and then repeating this operation half a dozen times to get out about one-third of the remainder. With all the advances of twenty years in milling, there is nothing more crude in metallurgy than the treatment of tailings in many of the large mills of the West.

Jan 1, 1880

By John R. Eckel

A Iaboratory drilling rig has been devised and placed in operation which permits the application of hydrostatic, terrastatic, and formation pore pressures to a rock sample for drilling under controlled conditions. Calibrated rests of this equipment in-dicate qualitative agreerment with field results on the effect of weight on bit, rotary speed, and rate of circ~~lation on drilling rate. Tests under pressure, using water and air as the drilling fluids, indicate that when drilling saturated limestone samples, a pressure differential between hydrostatic and formation pressure is the only pressure which affects drilling rate. A differential in either direction causes a reduction in rate, but the same diflerential from the wellbore into the formation causes the greater reduction. Also, in lime.stone, air favorably affected drilling rote only when compared to water at high hydrostatic pressurre, all other conditions remaining constant. Large increases in drilling rate with air could be obtained in the laboratory only while drilling a shale, which offered a limited permeability to nitrogen and which could be drilled with a differential from the formation into the wellbore. In general, the magnitude of the changes due to the pressure effect were small compared to changes in drilling rate obtainable by changing either bit weight or rotary speed. INTRODUCTION In the course of Humble's drilling research program, the desirability of investigating several factors which lend themselves to laboratory rather than field study became obvious. Principal reasons for this are the expense involved in field studies and the difficulty of exercising the required degree of control. Of primary importance are investigations of the effect of fluid pressure on rock rate, the effect of pressure on rock drillability, and a study of the fundamental mechanics of rock failure and chip generation. Several years ago some work in the laboratory on the effect of mud properties on drilling rate was re- ported to the API', but the completion of this work and the investigation of the other variables affecting drilling rate required equipment somewhat more elaborate than that used on these earlier tests. This equipment has been assembled to form Humble's Drilling Engineering laboratory. To date only the effect of pressure on rock drillability while using water and air has been investigated, and this work is not yet complete. Facilities are available to investigate the effect of fluid properties on rate of penetration, and information is being assembled on a current basis on the mechanics of drilling. The sequence of presentation in this progress report is somewhat different from that in which the data were obtained since the order of ex-

By A. M. Khan, I. Fatt

A new type of steady-state thermal conductivity apparatus is presented and described. Results of measurements on Berea sandstone, Solehofen limestone, Bandera sandstone and Bakelite are presented. The measurements were made in a two-hour period at temperatures up to 80C and axial stress to 125 bars. Results show that the thermoelectric heat pump and tbermistor-controlled electric heater can be used in a steady-state apparatus for measuring thermal conductivity of mck. Steady-state is reached within two hours. With Urethane foam insulation, not more than 3 per cent of heat is lost by radial flaw. The apparatus can be used as a comparator or for absolute thermal conductivity determinations. INTRODUCTION Calculations of heat flow through the earth, both for scientific purposes and engineering design, require thermal-conductivity data on rock. However, the high variability of rock often makes handbook thermal-conductivity data of little value. For engineering purposes in particular, it is desirable to have measured data on samples of the rock mass under study. Laboratory methods for measuring thermal conductivity of rock use either time-dependent1-3 or steady - state temperatures .4,5 The time -dependent (transient) techniques give thermal diffusivity from which thermal conductivity can be calculated if the specific heat and density of the sample is known. Most transient techniques require lengthy and involved sample preparation. Also, the accuracy tends to be low. Steady-state techniques are more exact and are the most commonly used. The steady-state methods, however, also have their difficulties. A long time is often required to reach steady state, troubles have been encountered in establishing good thermal contact between the heating and cooling elements and the rock sample, and unaccounted-for heat losses are difficult to prevent. In this paper we present a description of a new type of steady-state thermal conductivity apparatus. With it, measurements have been made in two hours at temperatures up to 80C and axial stress to 125 bars. Sample preparation is simple and no thermal conductivity standard is needed.6 APPARATUS Our steady-state apparatus is an improvement . over the conduction pile used by Zierfuss and van der vliet4 and Somerton.5 A linear heat flux is established through a conduction pile consisting of the rock sample and a standard material of known thermal conductivity in series. The thermal conductivity of the sample is calculated from the ratio of the temperature drop across the sample

Jan 1, 1966

By J. E. Harris

The metallic elements, beryllium, calcium, cerium, lithium, manganese, titanium, vanadium and zirconium are used in metallurgical practice in relatively small percentages for the purpose of improving the physical properties of various alloys. No important uses for any of these elements have thus far been developed either in the pure form or in alloys of which they constitute the major constituent.

Jan 1, 1935

By B. S. Tani, R. V. Schablaske, M. G. Chasanov

MEASUREMENTS of the solubility of scandium in liquid cadmium from 349" to 606°C by Chasanov, Hunt, Johnson, and eder' led to the isolation and characterization of the intermetallic compound ScCQ. The solid phase found in equilibrium with a saturated solution of scandium in liquid cadmium above 422°C is ScCQ. The equilibrium solid phase below this temperature has not as yet been characterized. Hexagonal needles of ScCG were isolated from a 5 wt pct Sc alloy which had been ice-quenched from 500°C. Free cadmium was leached away from the intermetallic with saturated ammonium nitrate solution. The concentration of cadmium in successive leaches was followed polarographically and the leaching process was terminated when the rate of cadmium dissolution decreased markedly. Chemical analysis of the intermetallic thus isolated is as follows: 11.5 wt pct Sc and 88.3 wt pct Cd. The composition of ScCQ is 11.8 wt pct Sc and 88.2 wt pct Cd. X-ray diffraction powder photographs of ScCds taken in a 114.6-mm Debye-Scherrer camera with CuKa, radiation can be indexed on the basis of a hexagonal nit cell. Lattice coonstants are a. = 6.330 ± 0.001A to 6.324 i 0.001A and co = 4.853 i 0.001A. The a0 has a slight range with the lower value seemingly associated with the cadmium-rich terminus of the phase. With eight atoms in the unit cell the calculated intermetallic density is 7.54 g per cu cm; the density as determined by a liquid-displacement method is 7.7 g per cu cm. Powder-diffraction data for ScCQ are recorded in Table I. Stoichiometry, symmetry, unit-cell dimensions, and the number of atoms per unit cell indicate the MgsCd (D019) type structure for ScCQ; space group is D,&-P6,/mmc. Atomic coordinates are:

Jan 1, 1964

By Reuben B. Ellestad, Fremont F. Clarke

In the early days of the lithium industry most of the production was from lepidolite, zinnwaldite, and amblygonite. Nearly all the early extraction processes described in the literature involve heating the finely ground mineral with sulphuric or hydrochloric acid. On subsequent water leaching most of the bases present in the mineral (especially aluminum) are dissolved as sulphates. As a result, the leach solution required extensive chemical purification before the lithium could be precipitated as carbonate. Following the remarkable growth of the lithium industry to its present size, zinnwaldite and amblygonite ores must be considered of minor importance only. Attention is now focused on spodumene, abundant enough in North America to be a major source of supply, and there are important supplies of lepidolite and petalite in Africa. The extraction processes described below all apply to spodumene, although several will also operate on other lithium minerals, such as petalite. Base Exchange with Alkali Sulphates: A distinct advance was made with the disclosures of Wadman and von Girsewalt. In these methods the finely ground silicate ore (spodumene or lepidolite) is intimately mixed with an excess of alkali sulphate (usually K2S04) in at least a 1 to 1 proportion, and the mixture was heated to a relatively high temperature. Base exchange results, with the formation of lithium sulphate. A water leach dissolves the lithium sulphate, together with the excess potassium sulphate. Successful operation of this type of process requires very thorough grinding and mixing, as well as careful temperature control. The use of K,SO, is objectionable from cost considerations since purification of lithium carbonate re- quires the use of potassium carbonate, if the K2S04 is to be recovered and recycled. The lower solubility of K,SO, as compared with Na,SO, is also objectionable, since it limits the concentration of the Li,SO, solution to be precipitated by K,CO,. Early laboratory-scale investigation of this process by Lithium Corp. was not encouraging

Nov 1, 1955

By T. S. Hutchinson, C. E. Kemp

The bottom water drive analysis presented by Muskat has been extended to include fields with wider well spacings. Curves are presented from which volumetric sweepout, water-oil ratio, and rate relations may be calculated. The effects of non-unity ratios on sweepout eficiency and productivity decline have been studied by an approximate method. Also, the effect of gravity on volumetric sweepout has been approximated for a particurlar geometry. INTRODUCTION The purpose of this paper is to report work done in applying the analysis of bottom water drive reservoirs given by Muskat1 to a larger class of reservoirs, to extend this analysis to include the effects of gravity and non-unity mobility ratios in an approximate manner, and to investigate the rate of decline of productive capacity. The bottom water drive type reservoir is one where the oil is underlain by a water zone of sufficient thickness that water movement is essentially vertical. This system is defined in more detail in the appendix and a one well element is shown diagrammatically in Fig. 1. Muskat obtained solutions to the equations describing the volumetric displacement efficiency of idealized bottom water drive systems by assuming that gravity effects due to differences in density betwecn oil and water were negligible and that the mobilities of oil and water were the same. If either of these assumptions is not made, the complexity of the system makes an analytical solution well nigh impossible at the present stage of mathematical development. Coles and Stade' developed an approximation to consider these factors. The authors have refined approximations, starting with the same basic assumption, which should give a somewhat quantitative picture of bottom water drive performance when mobilities are not equal and the effects of gravity are not negligible. The results of these approximate calculations can then be used to obtain the decline in well productivity as the field is depleted.

Jan 1, 1957

By A. Hellawell

Binary alloys of compositions intermediate between solid-solubility limits and eutectic compositions have been completely separated into primary phases and eutectic by freezing unidirec-tionally at very slow rates (10-6 to 10-5 cm per sec). The alloys examined were Pb-1 wt pct Ag, Al-20 wt pct Cu, and Al-42 wt pct Cu. The compositions and proportions were close to those expected from the phase diagrams and provided information about the solid/liquid interface at certain free zing rates. DURING the directional freezing of an alloy the solute distribution is controlled by the efficiency of mixing in the liquid,'" whereas diffusion in the solid state is of negligible importance. It is known3 that mixing by convection is very efficient, but complete segregation is only achieved at very slow freezing rates4-6 or with forced stirring in the liquid. ' Yue9 and Yue and clark10 have previously illus- trated partial separation of primary phases in alloys close to eutectic compositions. In the present work, taking binary alloys of compositions intermediate between the limits of solid solubility and eutectic compositions, it has been possible to achieve complete separation of the primary phases by directional freezing at very slow rates. METHODS AND RESULTS The alloys concerned were Pb-1 wt pct Ag, A1-20 wt pct Cu, and A1-42 wt pct Cu. As may be seen from the relevant diagrams,11 these alloys should segregate into approximately equal proportions of primary solid solutions and alloy of eutectic compositions. Specimens, -12 cm long and 1 cm wide, were frozen in horizontal tubes by withdrawal from a furnace. The lead alloy, prepared from materials of 99.999 pct purity, was sealed into evacuated Pyrex tubes and the aluminum alloy of similar purity contained in graphite boats under vacuum. The molten alloys were seeded with some 3 cm of solid to prevent irregular initial freezing rates and the last portions to freeze were ignored. At the slow freezing

Jan 1, 1965

US 4,132,758-Leaching of copper sulfide ore using nitrogen dioxide as the oxidant A slurry of ore in sulfuric acid is contacted with a nitrogen dioxide-containing gas at a temperature below 11 5" C and a pressure of from atmospheric to 35 PSI, the slurry agitated, and the resulting nitric oxide from the slurry regenerated to nitrogen dioxide for reuse About 90% of the copper In the ore IS dissolved, and the leach solution is separated for further processing. This procedure is also useful for sulfide ores of silver, molybdenum, nickel, cobalt, and zinc T C Franklewicz and R E Lueders, assigned to Kennecott Copper Corp Jan 2, 1979 7 pp (423-27) Filed 1 1-30-77 (855,983) (Drawings below ) US 4,138,231-Wet-cleanlng of gases from the roasting of copper sulfide ore, zinc sulfide ore, pyrite, or arsenopyrite The gases are washed in dilute sulfuric acid circulating in a closed system, the wash water treated to remove arsenic, the washed gas condensed by cooling; and the condensate separated, purified of residual arsenic, and neutralized B G V Hedenas, J E Wiklund, T R H Johansson, and KA Melkersson, assigned to Boliden AB Feb 6, 1979 7 pp (55-71). Filed 3-30-77 (782,908) Priority Sweden, 4-9-76 (76/04,219) (Flow diagram at right ) US 4,148,862-In the acid-leaching of silicate-bearing calcined zinc sulfide ore, finely divided calcine is leached at elevated temperature with sulfuric acid, and additional calcine is added at an optimum rate to precipitate SI~ICIC acid in the same stage In an easily settling, readily filterable form Reactions take place at a silica concentration so low that the solution is not greatly oversaturated An anionic flocculant- may be added to the slurry immediately before the filtration step S. P Fugleberg and J T. I Poijarvi, assigned to Outokumpu Oy Apr. 10, 1979 4 pp (423-106). Filed 10-6-77 (840,041) Priority Finland, 10-8-76 (76/2880)

Jan 1, 1980

By John A. Church

Jan 1, 1880

By Christie A. Callender, Harry M. Dahl

The Hobson uranium deposit is located in Karnes County, Texas, along the prominent south Texas uranium trend. The uranium mineralization occurs in the Deweesville Sandstone of the Whitsett Formation of the Eocene Jackson Group. The host rock is a friable, fine-grained, well-sorted, highly porous and permeable sandstone interpreted to be an ancient beach deposit. The sandstone contains significant volcanic constituents and ranges in composition from arkosic to tuffaceous. Locally, the host sandstone contains hard, dense opal cement. Bentonitic shales underlie and overlie the mineralized sandstone unit. Geometrically, the Hobson uranium-bearing zone resembles an elongated roll front type deposit. Chemical uranium values compared with gamma ray equivalent uranium values indicate that the uranium has been dissolved from the updip side and precipitated on the down- dip side of the roll front. Details of the uranium mineralization were studied using thin section microscopy, autoradiography, x-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The uranium mineralization occurs in the pores of the sandstone, as grain coatings and as replacement of sand-size and smaller grains. It is commonly associated with pyrite and other opaque minerals. Other favored hosts for uranium (other than pore openings) appear to be clay aggregates, altered rock and glass fragments, and carbonaceous plant debris. Aggregates of coffinite were identified by XRD and SEM/EDS analyses. Some uranium mineralization also appears to be dispersed and is postulated to be adsorbed on the clay and carbonaceous matter.

Jan 1, 1985

By T. F. Kassner

The dissolution kinetics of type 304 stainless steel in the Bi-Sn eutectic alloy have been investigated under the well-defined hydrodynamic conditions produced by the rotating-disc sample geometry. In addition, the mutual solubilities of iron, chromium, nickel, and manganese from 304 stainless steel in the eutectic alloy were determined over the temperature range 450" to 985°C. The convective -diffusion model for mass transport from a rotating disc was used to interpret the experinlental dissolution data. The dissolution process was found to be liquid-diffusion-controlled under specific conditions of temperature and Reynolds number. Liquid penetration into the 304 stainless steel resulted in a reduction of the di,ffusion-controlled mass flux and thus precluded the calculation of the diffusion coeficients of the four components from 304 stainless steel in the Bi-Sn eutectic alloy. The convective-diffusion model for diffusional limitations of electrode reactions and mass transport at the tationssurface of a rotating disc set forth by Levich 1,2 has found wide applicability in the investigation of electrochemical and dissolution phenomena in aqueous systems. Riddiford 3 and Rosner have reviewed the model and also include numerous references on work of this nature. More recently the rotating-disc system has been applied to the investigation of hetereogeneous reactions in liquid-metal systems. Shurygin and Kryuk 5 have measured the dissolution rates of carbon discs in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Shurygin and shantarin6 also studied the dissolution kinetics of iron, molybdenum, chromium, and tungsten, and the carbides of chromium and tungsten in Fe-C solutions with a rotating-disc sample geometry. In these systems it was possible to distinguish between diffusion and reaction control mainly through experimental confirmation of the velocity dependence of the dissolution rate predicted by the model. However in the absence of dependable solubility data and the virtual lack of diffusion data in these systems, a quantitative check of the magnitude and the temperature dependence of the rate was not possible. In many instances, estimates of the activation energy for solute diffusion and the diffusion coefficient based upon the experimental dissolution data are not credible. A recent study by this author7 has resulted in a critical test of the model in a liquid-metal system. The solution rates of tantalum discs in liquid tin were measured over a wide range of temperature and velocity conditions. In addition, the solubility and diffusion coefficient of tantalum in liquid tin were determined as a function of temperature. The latter data were used with the model to predict both the magnitude and the temperature dependence of the dissolution flux. In that work it was also deemed necessary to reevaluate the solution to the convective diffusion equation to incorporate the effect of the lower range of Schmidt numbers encountered in liquid-metal systems. Good agreement between the model and the experimental dissolution data in the region of diffusion control was obtained in the Ta-Sn system. The Bi-Sn eutectic alloy is used as a seal between the reactor head and the reactor vessel in the Experimental Breeder Reactor-11. The alloy is fused periodically prior to fuel-handling operations. In that connection, it was necessary to investigate the compatibility of the liquid alloy with the type 304 stainless-steel containment material. The results of a rotating-disc study in this multicomponent system are presented. EXPERIMENTAL METHOD The 5.08-cm-diam discs were machined from 0.317-cm-thick plate. Chemical analysis information for the type 304 SS material is given in Table I. The discs were ground flat on metallographic paper and given a final polish on Linde B abrasive. A thin support rod was threaded into the disc and the region around the threads was fused under an inert gas. The support rod was fitted with a quartz protection tube and then was attached to a supporting shaft which passed through a rotary push-pull vacuum seal. The disc and supporting shafts were dynamically balanced prior to insertion into the furnace tube. The apparatus is shown schematically in Fig. 1. The 58 pct Bi-42 pct Sn eutectic alloy melts were prepared from 99.995 pct pure Bi and Sn by fusing the components in a 7-cm-ID Pyrex crucible. The system in which the melts were made was evacuated to a pressure of 1 x 10-6 Torr and back-filled with purified argon several times before melting the charge. The ingot was reweighed and placed in a slightly larger-diameter Vycor crucible used in the dissolution runs. A run was started by lowering the disc into the liquid

Jan 1, 1968

By T. W. Turk, S. A. Sass

The engineering design features of the Mercur Gold Project crushing, grinding, carbon-in-leach, bullion, reagent, and tailings disposal areas will be discussed in this paper. It presents a project overview and flowsheet along with selected design alternatives. During the engineering phase, major equipment and other features were selected to optimize design within site location and environmental constraints. The project team organization and procedures were adopted to accommodate multiple optimization studies while maintaining a tight engineering schedule.

Jan 1, 1985