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By M. J. Mullikin, J. B. Conway

for use in describing combined first- and second-stage creep data. In the above ?o represents the instantaneous strain on loading, ?t the limit of transient creep, ?S the steady-state creep rate, t the time, and ? a constant leading to the exhaustion rate of transient creep. It was noted that this equation was similar in form to that proposed originally2 by McVetty. This type of equation was also suggested by Andrade and Aboav3 in studies of the shear strain of cadmium. Calculation of the constants ?o, ?t, ?, and ?s, in Eq. [ l] is somewhat involved due to the slight complexity of this relationship. In the paper by Garofalo a computer approach based on a least-squares analysis was recommended. Such an approach involves a trial and error solution but when a computer facility is available the difficulties in this calculation are of little consequence. It does mean however that the evaluation of this type of equation would become quite tedious if computer facilities were not available. Some recent studies have identified a fairly straightforward method for calculating the constants in the Garofalo equation. While not leading to a least-squares evaluation the approach is accurate and is recom-

Jan 1, 1967

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By K. R. Van Horn

RESIDUAL stresses in metals operate under a cloak of mystery, as they have neither been seen in the laboratory nor detected by means of the microscope. In spite of their phantom-like nature, they frequently exert metallurgical effects that cannot be ignored. In some cases the results have been detrimental, causing rejections or premature failures, but frequently the effects have been highly beneficial to the producer or consumer of metal products. First, however, what is a residual stress? When a metal is plastically deformed by bending, rolling, pressing, or by a phase transformation or precipitation from solid solution, or by a sharp temperature gradient resulting from nonuniform cooling, quenching, or welding, it remains in a state of strain. The strains or strain gradients produced by such operations and retained after all external forces are released are known as residual strains, and the accompanying stresses as internal or residual stresses. Many defects or failures in metal products have been ascribed to residual stresses, sometimes erroneously, because there was no other apparent explanation after the usual metallurgical tools of diagnosis had been applied. For example, during World War 11, the forged aluminum alloy aircraft cylinder head in the reciprocating engine began to replace the cast head with the familiar cooling fins. The fins were machined in the solid forged head by an ingenious milling operation. One plant reported an epidemic of excessive distortion during the delicate high-speed milling. A thorough examination revealed that the composition, heat treatment, mechanical properties, and metallurgical quality of these heads were comparable to those of forgings that machined satisfactorily. It was then claimed that the cause of the machining difficulties was connected with residual stresses resulting from the quenching during the solution heat treatment. An elaborate stress analysis actually demonstrated, however, that the magnitude of residual cooling stresses was lower in the cylinder heads which machined poorly than in those which were satisfactory in this respect. Subsequent tests proved that the machining problems in this case originated from variations in the tools and tool design. Sources of Residual Stresses in Metals Residual stresses are of two origins—mechanical and thermal. Thus, stresses may be produced in a metal by any cold-working process. The distribution and magnitude of these mechanically produced stresses can be calculated in a satisfactory, although approximate, manner for such simple cases as bending, torsion, and expanding of tubes. However, most manufacturing processes are too complex, and the original stress-strain relations in the products are not sufficiently known to permit calculation of the resulting residual stresses. Also, a specific process, such as wire drawing, may vary in complexity or uniformity of working, and large or small residual stresses may result, depending on the conformation of the dies and other features of the working process. Neither substantially unidirectional deformation, such as can be imparted by stretching a metal product having essentially the same mechanical properties throughout the cross section, nor deformation

Jan 1, 1954

By Frank R. Milliken, Robert Goodwin

In September 1937, the Ohio Copper Co. inaugurated the treatment of its copper-bearing mill tailings at Lark, Utah. These tailings had been accumulated during the regular operation of the Ohio Copper mine and mill over the period 1907 to 1919. Gravity concentration had been employed except for a comparatively short period in 1919, when flotation was used. The ore milled during that period assayed about I per cent Cu. The chief copper mineral, chalcocite, was disseminated in a shattered quartzite, mainly along fracture or cleavage planes. The quartzite gangue was extremely hard and grinding to liberation resulted in excessive sliming of the "sooty" chalcocite, with consequent high tailings losses. Recovery on the seven million tons treated was probably less than 60 per cent of the total copper content. As early as 1918, attempts had been made to sample the dump. In 1928, a complete sampling program was undertaken. The sampling consisted of seventy-four 5-in. post auger holes drilled to the full depth of the dump at regular intervals of 250 ft. Each 10-ft. portion thereof comprised a sample for analysis. Each sample was screened, rolled, divided into three parts, dried and assayed. The reject was retained for testing purposes. From the depth of the auger holes a contour map of the dump was plotted, Fig. I, which gives percentages of tonnage and copper content. The tonnage within the limit of the drill holes was estimated at about five million tons with an average content of 0.42 per cent Cu, 31 per cent of which (0.13 per cent) was acid-soluble. A screen analysis of the composite dump sample is shown in Table I. Flotation tests by several companies and individuals were then made, the results of which ranged from 62 to 74 per cent recovery. On the basis of these, a 200-ton pilot plant employing straight flotation was built and operated for a few months. Operation of this plant was unsuccessful, as no provision had been made to handle the copper-bearing solutions resulting from the water-soluble copper, a point that was overlooked in the laboratory test work. Attempts to decant the copper-bearing solution for precipitation in the usual manner ahead of flotation were not satisfactory because of low water recovery (owing to poor settling characteristics of the pulp) and contamination of the copper precipitate with unsettled slime. Low copper prices in 1931 necessitated the termination of testing. With the stimulus of higher copper prices in 1937, a review was made of metallurgical

Jan 1, 1943

By Robert Goodwin, Frank R. Milliken

In September 1937, the Ohio Copper Co. inaugurated the treatment of its copper-bearing mill tailings at Lark, Utah. These tailings had been accumulated during the regular operation of the Ohio Copper mine and mill over the period 1907 to 1919. Gravity concentration had been employed except for a comparatively short period in 1919, when flotation was used. The ore milled during that period assayed about I per cent Cu. The chief copper mineral, chalcocite, was disseminated in a shattered quartzite, mainly along fracture or cleavage planes. The quartzite gangue was extremely hard and grinding to liberation resulted in excessive sliming of the "sooty" chalcocite, with consequent high tailings losses. Recovery on the seven million tons treated was probably less than 60 per cent of the total copper content. As early as 1918, attempts had been made to sample the dump. In 1928, a complete sampling program was undertaken. The sampling consisted of seventy-four 5-in. post auger holes drilled to the full depth of the dump at regular intervals of 250 ft. Each 10-ft. portion thereof comprised a sample for analysis. Each sample was screened, rolled, divided into three parts, dried and assayed. The reject was retained for testing purposes. From the depth of the auger holes a contour map of the dump was plotted, Fig. I, which gives percentages of tonnage and copper content. The tonnage within the limit of the drill holes was estimated at about five million tons with an average content of 0.42 per cent Cu, 31 per cent of which (0.13 per cent) was acid-soluble. A screen analysis of the composite dump sample is shown in Table I. Flotation tests by several companies and individuals were then made, the results of which ranged from 62 to 74 per cent recovery. On the basis of these, a 200-ton pilot plant employing straight flotation was built and operated for a few months. Operation of this plant was unsuccessful, as no provision had been made to handle the copper-bearing solutions resulting from the water-soluble copper, a point that was overlooked in the laboratory test work. Attempts to decant the copper-bearing solution for precipitation in the usual manner ahead of flotation were not satisfactory because of low water recovery (owing to poor settling characteristics of the pulp) and contamination of the copper precipitate with unsettled slime. Low copper prices in 1931 necessitated the termination of testing. With the stimulus of higher copper prices in 1937, a review was made of metallurgical

Jan 1, 1943

By L. R. Blair

Many hydrated silicates have been synthesized and sold for commercial use. However, this paper discusses only hydrated calcium silicates and, to a lesser extent, hydrated magnesium silicates. Synthetic calcium silicates were first formed by man when he found that mixtures of silica or silicates and lime in water set up to form cements. The material which was responsible for the cementing properties was calcium silicate hydrate, although this fact was not recognized until early in this century. In the early 19001s, synthetic calcium silicates, reinforced with fibers and formed simply by reacting calcium hydroxide and silica in water with fiber at atmospheric or under low pressure autoclave conditions, found increased use in thermal insulations and in building products. These insulations were found to have a low thermal conductivity and would withstand temperatures up to 650°C. This, combined with their very low densities (from 8 to 50 Ib per cu ft) and fairly high strength, also made them suitable for use as building products. Following the disastrous Morro Castle fire of the 1930Js, calcium silicate board products were used as partitioning material in all shipboard construction in the U.S. As autoclaving techniques were improved and developed, it was: learned that under hydrothermal conditions new and useful calcium silicates which could be used under more extreme temperatures (up to 980' C) could be prepared. These had high surface areas and other unique properties which suited them for use as fillers, pesticide carriers, low temperature insulating materials, and adsorbents for the removal of fatty acids from various solutions. Hydrated magnesium silicates have not been studied as extensively as the calcium compounds. Their first important use was in the filtration of dry cleaning solutions for the removal of fatty acids. With the introduction of detergents, it was found that these products lost their advantage because of their high affinity for the detergent chemicals. However, in recent years these chemicals are finding increasing use as decolorizing agents for fats and anti-caking agents for resins. Some materials with very high surface are finding new use as adsorbents. CALCIUM SILICATE HYDRATE COMPOUNDS AND THElR CONDITIONS OF FORMATION Within the past ten years much has been done in the field of calcium silicate hydrate chemistry. As a result of this work it has been found that at least 25 different forms of calcium silicate hydrate can either be formed synthetically or found as naturally occurring materials. The stability and composition relationships among these 25 compounds present a very complicated picture, and many of these very closely resemble other forms and are difficult to dis-

Jan 1, 1962

By C. S. Barrett, D. F. Clifton

THE transformation that occurs in lithium and its solid solutions containing magnesium1,2 is similar in many respects to other diffusionless transformations of the martensitic type. This general similarity makes it desirable to investigate the transformation curves in detail. The current interest in the phenomenon of stabilization in martensitic transformations has created a need for a careful appraisal of possible stabilization effects in both cooling and heating transformations in lithium alloys. The effect of prior heat treatment on the temperature at which transformation begins and the effect of various temperature cycles in partially transformed alloys also merit attention. Limited data on some of these features were presented previously,' but the present studies have been made with improved apparatus, in which erratic fluctuations were smaller than in the earlier work, and include many independent determinations of certain critical observations. Material and Methods Geiger counter X-ray spectrometers were used: a Norelco instrument, original model, and a General Electric XRD-3. The low-temperature specimen holder has been described elsewhere." Specimens 10 mm in diam and 1.5 mm thick were held in firm contact with a copper block which was attached to the lower end of a stainless steel tube that extended up to a reservoir of liquid nitrogen. A heating coil on the tube permitted a controlled temperature gradient along the tube, so that desired temperatures and rates of heating and cooling could be obtained by controlling the heating current. The specimen was surrounded by an atmosphere of evaporated nitrogen in an insulated chamber having double cellophane windows. The temperature of the specimen was read by a thermocouple imbedded in it close to the irradiated area; the specimen could be held at constant temperature within 1°C for long periods. The body-centered cubic 200 reflection near 8 = 26" was used as the index of the amount of b.c.c. material present; occasional checks were made using the most suitable line of the low-temperature phase, the close-packed hexagonal 110 line near 8 = 29". Copper radiation was used throughout. A continuous record was made of the reflected intensities on a strip chart recorder, both when the peak intensity of a line was being followed and when the lines were being scanned at constant temperature. On the continuous recordings of peak intensity, periodic checks were made on the background intensity between the lines, and on the setting of the spectrometer for maximum intensity. The lithium-base solid solution containing 12.4 atomic pct Mg (33.3 wt pct) that had been used previously' was chosen, as it had a transformation range at relatively high temperatures, so as to permit wide temperature cycling within the range. Just prior to use a pellet was cut from the ingot,

Jan 1, 1951

By Strathmore R. B. Cooke, Emert W. Lindroos, Norman F. Schulz

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by' flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (--CH2CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder[4] has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate-potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality.

Jan 1, 1952

By R. D. Nelson, F. E. Bowman

Assumptions are made of ideal mixing and that the density of silver can be obtained by extrapolating reported liquid density-temperature data through the freezing point back to the temperature range of interest. The results of this procedure using liquid silver density data of Kirshenbaum et al.5 are presented in Table I1 where it is observed that agreement is everywhere within <0.1 pct and generally is within 0.05 pct. Because the Sn-Ag alloys are dilute, the assumption of ideal behavior is, therefore, probably justified. In conclusion, the densities of dilute liquid solutions of silver in tin have been determined. Even for concentrations as low as 0.1 pct, the effect of silver on the density of liquid tin is clearly measurable. This work also suggests that for dilute alloys at temperatures far below the freezing point of the solute metal, densities may be accurately calculated by extrapolation of the pure metal data without having recourse to physical measurement on the alloy itself. plutonium having a grain size of about 100 µ. This paper presents data showing that large elongations of fine-grained a Pu can be obtained by using slow deformation rates. Large plasticity, however, of a Pu in compression has been observed.4 Reductions in thickness of 90 pct have been observed with no edge cracking. These large reductions are accompanied by concurrent re-crystallization. The deformation modes, which are quite complex, have been studied extensively by observing the deformation microstructures of polished surfaces that had been deformed in compression.5-7 Although slip apparently is a predominant mode of deformation at room temperature, grain boundary sliding and concurrent recrystallization become more predominant at high a temperatures.4&apos;7 Although recovery occurs,8,9 no grain growth has been reported in a Pu even at temperatures near the a =ß equilibrium temperature (-115oC), which is 0.7 of the calculated melting temperature of a Pu.10 From studies on other materials, it appears that high elongations can be obtained in alloys when the THE purpose of this technical note is to present briefly some data revealing high ductility of a Pu, which is normally considered brittle. The very low ductility of a Pu in tension has been reported by many investigators.&apos;-3 Gardner,1 for example, reported that the total elongation of a Pu at a testing speed of 0.015 ipm is less than 0.1 pct at room temperature and only about 1 pct at 100°C. The only tensile creep studies that have been reported&apos; indicate no large ductility, but they were performed on relatively low purity

Jan 1, 1970

The Alligator Ridge Project is owned jointly by Amselco Minerals Inc. and Occidental Minerals, with Amselco being the operator. It is the latest of Nevada&apos; s gold heap leaching operations , having gone into operation in October of 1980 after a design and construction period of only seven and one-half months. Alligator Ridge is located about 77 km (48 miles) northwest of Ely, Nevada. Three separate but adjacent ore bodies will be mined: Vantage I, II and III. The first lies virtually at the surface and is totally oxidized; the second is somewhat deeper and contains some carbonaceous material; and the third is at the lowest horizon and contains substantial carbonaceous ore. The ore is a Carlin- type siltstone which has been silicified, especially at depth, and contains finely disseminated free gold. Exploration drilling on Alligator Ridge resulted in the defining of an ore reserve of about 4.54 million mt (5 million st) averaging 4. 12 g Au per mt (0. 12 oz Au per st). A pilot heap leaching program was run during 1979. Because of the high content of fine material in portions of the ore body, one test heap of 5,000 tons was leached, after being crushed to 19 mm (314 in.), in the conventional manner using cyanide and caustic while a second heap of 2,500 tons of ore was agglomerated with cement before leaching. Results of this work were reported at the 1980 American Mining Congress meeting by Paul Chamberlin (see Bibliography). The test work clearly indicated the superior leaching qualities of the agglomerated ore, and the plant was designed on this basis. Run-of-mine ore is crushed in an open-air crushing plant using a jaw crusher followed by two cone crushers, one standard and one shorthead. Provision was made to bypass the shorthead when the ore is wet from rain or snow. Crushed ore at 19 mm (314 in.) size is mixed with cyanide solution and cement, with the ratio of the latter to the ore being 2 to 5 kg per mt (4 to 10 lb per st). The resulting moisture content is about 870, and the fines are effectively bound to the coarse particles so that migration of the fines in the heap does not take place during leaching. For agglomeration, Amselco uses a rotating drum 2. 75 m 0 by 6 m long (9 ft 6 by 20 ft). For the same agglomeration, Candelaria uses three "grasshopper" conveyors, with introduction of caustic- cyanide solution at the conveyor transfer points. Provision was made for future addition of cement slurry at these same points.

Jan 1, 1981

By T. G. Richardson, F. M. Perkins

In the recent paper of Richardson and Perkins entitled "A Laboratory Investigation of the Effect of Rate on Recovery of Oil by Water Flooding,"&apos; the authors found very little appzrent effect on oil recovery of having free gas saturation present prior to water flooding in unconsolidated sands. We agree that the effect in this particular system was small but do not feel that the data presented should be regarded as disproving work of others which has shown an appreciable effect. The authors do not make such a claim, but neither do they advance an explanation of the difference. In our experience the following factors must be carefully considered when studying the relation between residual oil saturation after water flooding and initial free gas saturation: (1) the magnitude of the inherent residual oil saturation, i.e., the residual oil saturation with no free gas; (2) the increase in oil-water viscosity ratio with pressure lowering if the gas saturation is obtained by solution gas drive; and (3) the oil shrinkage which occurs with pressure lowering and gas evolution. The system studied by Richardson and Perkins gave residual oil saturations as low as 20 per cent without free gas present, and one should perhaps not expect much further lowering. As an illustration of the magnitude of the effect when the residual oil saturation is inherently higher we submit the accompanying figure. These data were obtained on an unconsolidated sand under elevated pressure in a system similar to the one described by Richardson and Perkins. Gas saturation was established by gas drive before water flooding. The viscosity ratio was 600:1 under the conditions of the displacement. Here the gas was extremely effective in reducing residual oil saturation. This fact was also indicated by Kyte, et al.2 Their plots of residual oil saturation vs initial gas saturation show trends of greater free gas effect with higher oil viscosities. The pressure-dependent effects were not discussed by Richardson and Perkins. They should be separated from the free gas effect if the objective of the study is a correlation of residual oil saturation vs initial free gas saturation. The increase in oil viscosity when gas is released from solution tends to increase residual oil saturation. This effect is rather small in the viscosity range of kerosene. A Buckley-Leverett calculation, assuming an increase in viscosity ratio from 1.2 to 1.8, indicates an increase in residual oil saturation of about 1 per cent of pore volume. Thus, one would expect this system, if operated at constant viscosity ratio, to show a slightly greater free gas effect. As Dyes- as shown, oil shrinkage can offset the beneficial effect of free gas on waterflood oil recovery, if the gas saturation is established by depletion. Since

Jan 1, 1958

By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly 100 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson&apos;s X-ray data indicate that this decomposition is accompanied by a change in volume of as much as 5 per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson&apos; found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter5 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to 90 per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced 90 per cent when forged to ½ -in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By O. Katz, A. Spilners, M. Simnad

THE oxidation of titanium has been studied in recent years by a number of investigators.&apos;-W ne of the most important aspects of the reaction of titanium with oxygen, which has been observed by several of the investigators, is the extremely high solubility of oxygen in the metal. A detailed study of the Ti-0 systeml% as shown that the solubility limit of oxygen in a-titanium is approximately 14.5 wt pct 0 from 800" to 1700°C. The unusual oxidation behavior of titanium may be ascribed to this phenomenon, since part of the oxygen uptake enters into solid solution in the metal and only a part is available for scale formation. A more complete study of the kinetics of oxidation of titanium would require information on the influence of oxygen in solution in the metal upon the oxidation rate. Such information would also be of interest in regard to the theory of oxidation of metals. The authors have measured the oxidation rates of oxygen-saturated and oxygen-free titanium between 800" and 1200°C and have found appreciable differences in their rates of oxygen uptake and in the activation energies. The experimental set-up was similar to that described in a previous paper.u The course of oxida-dation was followed continously by attaching the specimen to a sensitive spring balance and observing the extension of the spring with time of oxidation. High purity electrolytic oxygen was used and precautions were taken to purify the gases employed. The specimens were prepared from iodide titanium and were ground on metallographic polishing papers to a fineness of 4/0. The furnace was first evacuated and filled with argon; the specimen was lowered into the furnace, which was then evacuated and filled with oxygen, after the specimen had reached the oxidation temperature in argon. The samples were presaturated with oxygen by means of the following procedure: Each specimen was first heated in oxygen at 1200°C until its increase in weight indicated 13.8 pct by weight uptake of oxygen. The furnace was then immediately evacuated and filled with purified argon five times. The specimen was heated in the argon atmosphere for a period of 72 hr at 1200°C in order to saturate the metal with oxygen by complete absorption of the scale. The temperature was lowered to the oxidation temperature, the furnace was evacuated and filled with oxygen, and the oxidation rate was followed by noting the extension of the spring balance. No oxide film was visible on these specimens at the start of the oxidation experiments. Titanium samples in the oxygen-free as-received condition were also oxidized and their oxidation rates measured. The results are shown in Figs. 1, 2, and 3, which indicate that the initial rates of uptake of oxygen by both the oxygen-saturated and oxygen-free specimens are parabolic at these temperatures. The rate of uptake of oxygen is, however, appreciably lower

Jan 1, 1956

By J. W. Borough

THE electrical conductivity of pure copper is markedly decreased by small amounts of impurity in solution. The magnitude of this effect has been very carefully determined by numerous investigators who studied a wide variety of impurity elements. Much of this work is summarized in an excellent review by Pawlek and Reichel.&apos; The case of zinc impurity in copper is an exception to the above in that there has been no well-documented study of the effect using high-purity starting materials. The values for the effect of zinc on conductivity, which are usually taken from unpublished work by Skowronki, indicate that zinc in low concentration has no effect whatever in lowering the conductivity of pure copper. This effect, if true, is unusual since it is generally known that even in lowest concentration, impurities exert an effect on conductivity which is proportional to the amount dissolved. It is more reasonable to suspect that in the original work on the effect of zinc some of the zinc was oxidized out of solution during specimen preparation. The following experi- and calculated d-spacings based on the unit cell dimensions of Baenziger et al. Since the single crystal studies of Baenziger et al. were limited to (hk0) and (hk 1) data, it was not possible to Compare all the intensities of the powder and single crystal patterns. However, the strongest reflections of both studies, the (321) reflection, agree very well when the appropriate multiplicity factor is used. Good agreement was also found in a number of other reflections of lesser intensity. Despite the precautions taken in annealing the U6Fe powder, an appreciable amount of UO, was detected in the powder pattern after heat treatment. The powder pattern reported by Groganoand Clews is given in Table I. Except for the 3.15A line, which is the strongest line of UO,, their pattern, as far as it goes, compares favoEably with the data from this study. Gordon and Kaufmann have reported a diffraction powder pattern purported to be U, Fe but it bears very little resemblance to the patterns of Table I. ments were carried out to redetermine the effect of zinc on conductivity using high-purity starting materials and processing conditions capable of producing oxygen-free alloys. Materials used in the experiment were ASR 99.999 pct Cu and Cumingo 99.999 pct Zn. Four 1 lb melts were prepared with identical procedure in argon atmosphere with crucibles made from Speer No. 580 graphite. The compositions were 0.0, 0.1, 0.3 and 1.0 pct Zn. Standard No. 14 wire (0.064 in. diam) was made from these melts as follows. The 1 pct Zn sample was first reduced 94 pct by cold swaging with five annealing treatments of 800o for 10 min in hydrogen between swagings, and then reduced 94 pct to the

Jan 1, 1962

By H. A. Wheeler

That lead and zinc deposits are the result of prolonged,, slow deposition is the idea of most students of ore deposits, and in many cases, where the ore-bearing solutions have been very weak or the precipitating conditions have been very feeble, the ore accumulations have undoubtedly taken a long period of time. As these two vital conditions have been subject to great variations in the different mining camps, the following example is highly interesting in showing that deposition can be very rapid under favorable conditions, geologically speaking, and also extremely recent. In fact, the writer is inclined to regard most, if not all, of the Mississippi Valley deposits of lead and zinc as probably being very young, at least not older than Tertiary, if not Quarternary, in age. The extensive Joplin lead and zinc district, in southwestern Missouri, which is about 60 years old and has numerous mines that were abandoned from 1 to 50 years ago, shows that the lead and zinc today are in an active condition of solution and redeposition, although these two metals occur in the predominant form of sulfides. The mine waters from the older and more or less abandoned portions of the district are frequently so acid, mainly from the oxidation of associated pyrite, as to necessitate the use of wooden pipes and pumps. The first boom in the Oklahoma zinc fields, which is the southwestern extension of the Joplin district, occurred when ore was accidentally struck in drilling a water well. Among the mines then opened up was the Mission mine, at Lincolnville, Ottawa County, Okla. This mine was opened in 1903 in lean "sheet ground," or a flat blanket formation of chert carrying disseminated zinc blende, or "jack," and galena. Theore-body was very free from iron pyrites and the concentrates were very high grade, the "mineral," or lead concentrates, assayed 80 to 85 per cent. lead and the jack, or sphalerite, assayed 60 to 65 per cent. zinc. The orebody was very shallow, occurring at a depth of 76 to 95 ft. (22 to 28 m.) and very wet, requiring three or four pumps to handle the water. The mine was operated until 1914, when it was closed by litigation and immediately filled with water. The second Oklahoma boom, five years ago, opened up the large, active camps of Picher, Tar River, and Century, which are located 2 to 5 mi. west of Lincolnville. They are considerably deeper, being farther down on the westwardly dipping monocline that emanates from the Ozark

Jan 1, 1920

By S. Y. Ogawa

The effects of sulfur (up to 0.1 pet) on the deformation and fracture characteristics of iron, in cast form, were studied at strain rates up to 100 pct pcr sec and at temperatures of 1600o to -3300 oF. The effects of oxygen and manganese additions on the behavior of Fe-S alloys were studied under comparable test conditions. Brittle fracture characteristics, evident at all strain rates, resulted from the presence of the liquid iron sulfide phase at grain boundaries. Ductility could be restored in three ways: solution of the sulfide in solid y iron at higher temperatures, spheroid-zzation of the liquid sulfide, and increase. in the melting point ot the sulfide. THE literature shows that most previous studies of deformation and fracture at hot working temperatures have been based on measurements of energy absorption, reduction of height in forging upset tests, torsion tests of bar or wire samples, and so forth,&apos; but that relatively few tension tests have been used at high temperatures and strain rates. The present work was initiated to study the ef- fects of temperature, strain rate, composition, and structure on the deformation and fracture characteristics of iron, utilizing cast specimens tested in tension. As in a previous study,&apos; strain rates up to 100 pct per sec were chosen for the temperature range 1600° to 2400° to provide data which might be useful in the interpretation of the deformation and fracture behavior of steels under hot working conditions. The previous work was with Fe-P solid solution al10ys;2 this work is concerned with Fe-S alloys, and with the effects of oxygen and manganese additions. MATERIALS AND PROCEDURE Cast tes! specimens were employed throughout, since most of the difficulty during hot working occurs in the initial breakdown of the ingot. Alloy Systems. Ten 25 lb. heats containing sulphur were prepared. Of these, three had manganese additions, and two had oxygen additions. The sulfur content varied from 0.023 to 0.10 pct. Manganese contents were intended to be ten to twenty times the sulfur content of the particular alloy. Oxygen, being more difficult to control in small melts, was varied by the amount of solid deoxidizer added, but poor control of the oxygen content was experienced in most instances. Table I shows the chemical analyses of the heats. Melting and Casting. Electrolytic-iron chips were melted by high frequency induction in a prefired, clay-graphite crucible lined with rammed magnesite.

Jan 1, 1962

By A. H. Daane, B. J. Beaudry

The uranium-antimony system has been investigated by metal-lographic, therma1, and X-ray methods. There are four intermediate phases present: USbz and U,Sb, which undergo peritectic decomposition at 1355°and 1695OC, respectively, and USb and UPSbs which melt congruently at 1850"and 1800°C, respectively. There is a eutectic between U4Sbs and USb which melts at 1770°C. USb,, UsSb4, and USb are line compounds while U4Sbs has a solubility range of approximately 1.5 at. pct at 1770°C. Single crystal studies of the cmpo,und U.,SbS show it to have a hexagonal unit cell with a, = 9.268A and c, = 6.201b;. The solubility of uranium in liquid antimony increases from 0.1 at. pct at 650°C to 1.5 at. pct at 900°C. The solubility of antimony in a, P, and y uranium is approximately 0.02, 0.1, and 0.05 at. pct respectively. IN nuclear reactors, uranium has been used mainly in the form of solid-fuel elements of the pure-metal or uranium-rich alloys. However, in attempts to overcome some of the difficulties inherent in solid-fueled reactors, reactor concepts hive been proposed in which the fuel would be a liquid metal, such as a solution of uranium in another metal. The liquid-metal fueled reactor (LMFR) designed by the Brook-haven National Laboratory of the U.S. Atomic Energy Commission is an example. Fuel for this reactor is a solution of approximately 800 ppm enriched uranium in bismuth.&apos; To design such liquid-fueled reactors, a background of information on the solubility of uranium in various metals is obviously necessary. The present study was undertaken to pro- vide information for such purposes, and in addition, to study the uranium-antimony system as a whole. A preliminary literature search showed that some work had been done previously on uranium-antimony alloys, but no attempts had been made to make a complete study of this system. The solubility of uranium in antimony was studied by Cammack and Bridger&apos; up to 950°C and by Hayes and Gordon up to 900&apos;-C. Their data are plotted in Fig. 1. Ferro, in an X-ray structure study of some uranium-antimony compounds, found USg to be tetragonal with a, = 4.2724 and c, = 8.471A, U3S4 to be b.c.c. with aO = 9.095A and USb to be f.c.c. with a,= 6.191A. Colani reported the compound UsSba; however, work by Ferro and by this Laboratory showed that this compound does not exist. foote&apos; reported several intermediate phases in the uranium-antimony system, but did not identify them. Greninger&apos; re-ported finding an intermediate phase in a 5 at. pct Sb

Jan 1, 1960

By Holbrook G. Botset

It is possible by means of the electrolytic model to simulate water-flooding or gas recycling systems involving input and output wells, and also the encroachment of a natural water drive. The results are obtained pic-torially, and by simple measurements and calculations the percentage of recovery is obtained qualitatively as a function of the total input. Introduction The increased demand for petroleum products, together with the decline in discovery rate and the higher cost of recovery as deeper formations are brought into production, has stimulated interest in methods for studying and predicting efficiencies of various production programs. Among methods Of recovery that have become of increased significance recently are gas recycling in condensate fields and secondary recovery by water-flooding. The electrolytic model is a useful device for studying such methods in the laboratory, at least in a qualitative way. The original experiments with electrolytic models and the development of their application to the study of secondary reCoverY problems were published in 1933. 1,2,3 Subsequently other investigators continued the development and modification of the bait method, with resultant improvements and extension of its applications.4-7 The method and equipment to be described here are thought to represent still further improvement in the results obtainable, with increased validity in their application to field problems. Sand OF Principles of Operation The underlying theory of the operation of the model is given in references I, 2 and 3. However, a brief statement of principles involved is given herewith. The applicability of the model is based on the fact that Ohm&apos;s law and d&apos;Arcy&apos;s law are exactly analogous; whence, electrical flow through a conducting medium may be used to simulate homogeneous fluid flow through a permeable medium. If two electrodes are placed in a conducting (ionized) solution and connected to the positive and negative terminals of a source of direct current, the positive ions of the solution will move toward the negative terminal, Since the velocity of an ion in an electrolytic medium is proportional to the electrical gradient, just as the velocity of a fluid particle in a porous medium is proportional to the pressure gradient, the motion of the ions in the potential field will be the same as the motion of fluid particles in a porous medium if the positive and negative terminals (input and output wells) and boundary conditions are made equivalent in shape and distribution. In order for the analogy to hold exactly, the sand must be assumed to have uniform porosity and permeability and the input

Jan 1, 1946

By Holbrook G. Botset

It is possible by means of the electrolytic model to simulate water-flooding or gas recycling systems involving input and output wells, and also the encroachment of a natural water drive. The results are obtained pic-torially, and by simple measurements and calculations the percentage of recovery is obtained qualitatively as a function of the total input. Introduction The increased demand for petroleum products, together with the decline in discovery rate and the higher cost of recovery as deeper formations are brought into production, has stimulated interest in methods for studying and predicting efficiencies of various production programs. Among methods Of recovery that have become of increased significance recently are gas recycling in condensate fields and secondary recovery by water-flooding. The electrolytic model is a useful device for studying such methods in the laboratory, at least in a qualitative way. The original experiments with electrolytic models and the development of their application to the study of secondary reCoverY problems were published in 1933. 1,2,3 Subsequently other investigators continued the development and modification of the bait method, with resultant improvements and extension of its applications.4-7 The method and equipment to be described here are thought to represent still further improvement in the results obtainable, with increased validity in their application to field problems. Sand OF Principles of Operation The underlying theory of the operation of the model is given in references I, 2 and 3. However, a brief statement of principles involved is given herewith. The applicability of the model is based on the fact that Ohm&apos;s law and d&apos;Arcy&apos;s law are exactly analogous; whence, electrical flow through a conducting medium may be used to simulate homogeneous fluid flow through a permeable medium. If two electrodes are placed in a conducting (ionized) solution and connected to the positive and negative terminals of a source of direct current, the positive ions of the solution will move toward the negative terminal, Since the velocity of an ion in an electrolytic medium is proportional to the electrical gradient, just as the velocity of a fluid particle in a porous medium is proportional to the pressure gradient, the motion of the ions in the potential field will be the same as the motion of fluid particles in a porous medium if the positive and negative terminals (input and output wells) and boundary conditions are made equivalent in shape and distribution. In order for the analogy to hold exactly, the sand must be assumed to have uniform porosity and permeability and the input

Jan 1, 1946

The Candelaria deposit was first discovered by Spanish prospectors in 1863; but its silver ore was not exploited on a large scale until 1873, when the Northern Belle mine was opened. The first Northern Belle mill was built at Belleville, 13 km (8 miles) to the northwest. From 1876 to 1886 the Northern Belle paid over $1 million in dividends each year. In 1882 a 43 km (27 miles) pipeline was built to Candelaria from the White Mountains to the west to furnish water for the mills and town at Candelaria; it was 100 mm (4 in.) in diameter, hand- riveted, and made in England. Sections of this pipe are used. as claim posts today. At its terminus at Metallic City, above Candelaria, a large concrete reservoir was built and called Metallic Lake. It is being used today by Candelaria Partners. Production at Candelaria declined after the mid-1980s, revived for a short period in the early 1890s, and during the 1920s a 300 ton mill operated for three years. Candelaria Partners is owned jointly by Occidental Minerals and Congdon and Carey, with Occidental being the operator. An engineering study done in mid-1979 resulted in engineering for the plant commencing in late that year and heap leaching being started in September 1980. Two million tons of ore per year containing 108 g Ag and 0.28 g Au per mt (3.15 oz Ag and 0.008 oz Au per st) will be mined from the Lucky Hill and Mount Diablo .areas about 1.6 km (1 mile) up Pickhandle gulch from the heap leaching operation. Waste -to -ore ratio is about 2:l. Ore is mined by front-end loaders and hauled by 85 ton trucks to the primary crusher, a 1,070 by 1,780 mm (42 by 70 in. ) gyratory. Primary crushed ore is conveyed to a stockpile of 10,000 tons live capacity from which it is reclaimed by hydraulic reciprocating feeders and conveyed to the crushing and agglomeration facility. This unit is composed of a 1.8 m by 2.6. m (6 ft by 12 ft) double deck screen, a 2.1 m (7 ft) standard cone crusher, and three conveyors. At the conveyor transfer points NaOH and NaCN solution is sprayed on the ore as it falls through a row of 75 mm (3 in.) hanging steel bars. During this process of turning and dividing the ore, the fines agglomerate with the coarse ore to give better percolation for the leach solution on the heaps. Provision was made for the later addition of 2 kg per mt (4 lb per st) of cement to aid in the agglomeration. Agglomerated ore at minus 50 mm (2 in.) size is then conveyed to a 390 mt (430 st) loadout bin where it is transferred to 85 ton rear dump trucks for haulage to the leach pads.

Jan 1, 1981