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By W. C. Smith, P. J. Hickey

After a short historical background of the process evolution, this article descvibes present-day plant facilities and operating techniques utilized for high-purity bismuth production. The plant is one of the world's largest, with an annual output of some one million pounds of refined bismutlz. PREVIOUS papers1 written by staff members of Cerro de Pasco Corp. have referred briefly to the production of refined bismuth. Since the Corporation is one of the world's foremost producers of high-purity bismuth, a detailed description of the process for extracting the metal may be of general interest. Following a short historical background of the development of the actual process, this presentation will trace the progress of bismuth from its entry into the primary smelting circuits to its concentration in electrolytic lead cell slimes. Our facilities for the treatment of anode muds will be described and the extractive methods given in some detail, with particular emphasis on the techniques which result in the production of refined metal. HISTORICAL BACKGROUND Shortly after Cerro de Pasco began smelting operations at Oroya, Peru in 1922, it became apparent that the dust carried by copper converter gas contained appreciable amounts of bismuth. Although dust collection efficiency was poor prior to building of the 550-ft stack and installation of the central cottrells in 1938, a large stock of dust was accumulated during the intervening years, having the following approximate composition: Oz. per ton Ag - 11.0 Pct Sn — 0.5 Pct Pb - 49.0 Pct Zn - 6.5 Pct Bi - 2.0 Pct Insol. - 1.5 Pct Cu - 0.7 Pct Fe - 2.3 Pct Sb - 3.0 Pct S - 10.0 Pct As - 7.5 In the mid-1920's, experimental crucible melts of this dust with carbon indicated that most of the bismuth and silver, and some of the lead, could be reduced to a fairly clean bullion. Other products were a small amount of leady copper matte and a slag high in zinc, arsenic, antimony, and lead; this slag contained some tin but only small quantities of silver, bismuth, and copper. After the laboratory results had been confirmed by operation of a small reverberatory, a dust reduction furnace was constructed. The ±10 pct Bi-Pb bullion produced from this operation was stocked until 1930, when an Oroya-designed converter type furnace3 was installed for the elimination of arsenic, antimony, and some lead from the bullion. This process concentrated the bismuth from 10 to about 60 pct. By means of the bismuth process developed4 by W. C. Smith at East Chicago (1909-1914) and the discovery of a method5 for separation of lead from bismuth with chlorine gas in 1929, it became possible to begin production of refined bismuth. Unfortunately, bismuth deleaded with chlorine always contained residual chlorides, and the removal of the chlorides by caustic soda left a lead content of 0.02 to 0.04 pct. This final problem was solved6 by substitution of air-blowing for the caustic treatment, which effectively removed all excess chlorine and gave bismuth which was practically lead-free. In 1934, a pilot electrolytic lead refinery began operations at Oroya. Lead smelting was resumed in 1935 and two years later a 100-ton-per-day lead refinery was put into service. In conjunction with the latter, the present-day Anode Residue Plant was constructed. Until 1940, the plant treated both lead anode slimes and dust reduction bullion. The dust reduction furnace was shut down in that year, and all cottrell dusts (with the exception of the product from the arsenic cottrell) were mixed with pyrite and treated in a Wedge roaster to eliminate all possible arsenic. Calcine from this operation joined the sinter plant feed; hence the bismuth from the copper and lead circuits was collected in the lead bullion and subsequently in lead anode slimes from the electrolytic lead refinery. The latter source has been the only bismuth-bearing material of any consequence entering the Anode Residue Plant from late 1940 to the present. A copper refinery began operating in 1948, and the cell mud from this plant is mixed with lead slimes and processed through the same circuit, though only a small quantity of bismuth is present in electrolytic copper cell residues. BISMUTH INTAKE Present-day routes which are followed by the new bismuth feed from its entry into the primary smelting circuits to its arrival at the Anode Residue Plant are traced schematically in Fig. 1. As illus-

Jan 1, 1962

By R. H. Walpole, J. M. Kane

IN all probability the mining and metallurgical industry as a whole can demonstrate a larger ecorlomic return from installation of dust-control equipment than any other major industrial group. This fact has partially accounted for the marked increase of dust-control installations made during the past decade. While the primary objectives for installation of dust-collecting systems are improved working and operating conditions for men and equipment, the fact that an economic return can be anticipated on salvageable materials is an added advantage which shows in partial or complete equipment write-off. The conditions apply to most phases of the mining, milling, and smelting industry, both non-metallic and metallic. As with any mechanical devices, selection of suitable dust collector equipment involves evaluation of available products with characteristics most nearly meeting conditions of the application at hand. When there is valuable product to be collected, and/or when there are possibilities of air pollution or public nuisance, collector selection is often guided by the maxim of "highest available collection efficiency at reasonable cost and reasonable maintenance." A brief review of dust collector designs will permit outlining of major characteristics of each group. Final selection will involve detailed data against a background of the problem under consideration. The dry centrifugal collectors, see Fig. 1, represent a group of low cost units with minimum maintenance. They are subject to abrasion under heavy abrasive dust loads and to plugging with moist materials. Efficiency drops off rapidly on particle sizes below the 10 to 20 micron group. Because of the large amounts of —10 micron particles in most mining dust problems, they will normally be used as primary collectors and will be followed by high efficiency units. This combination is cspecially popular where the bulk of material is desired in a dry state with wet collection indicated for the final cleanup portion. In remote plant locations, dry centrifugal~ can be used alone if product in dust form has no value or if dust loading is light enough to eliminate a nuisance in the plant area. Where high efficiency dust colleotion equipment must be selected, choice will normally involve fabric arresters, wet collectors, or high voltage Electro-Static precip-itators. Fabric arresters, see Fig. 2, rely on the passing of dust-laden air at low velocity through filter fabric. Velocity ranges from 1 to 3 fpm for the usual installation and may be as high as 10 to 20 fpm in arrangements where automatic frequent vibration or continuous cleaning of the filter media is employed. Fabric is normally suspended in either stocking type or in an enlvelope shape. Collection efficiency is excellent even on sub-micron particle sizes. Equipment is bulky, must be vibrated to remove the collected dust load, and is restricted in applications from temperature and moisture standpoints. Condensation of moisture on the fabric filter mcdia causes plugging of the passages with great reduction in air flow. Temperatures for the usual medias of cotton or wool are 180" and 200°F maximum, although the introduction of synthetic materials such as nylon, orlon, and glass cloth have increased the possibilities of this type of collector for higher temperature applications. The wet-type collector may employ a number of different principles so that entering dust particles in the gas stream are wetted and removed. Principles usually include impingement on collector surface or water droplets, often in combination with centrifugal forces. Variety of wet collector designs is indicated by typical collectors illustrated in Figs. 3 and 4. Collection efficiency is a function of the particular design, although the better collectors will have high collection efficiency on particles in the 1-micron range. Wet collectors have the advantage of handling hot or moist gases, take up small space, and eliminate secondary dust problems during the disposal of the material. At times collection of the material wet is a disadvantage. Wet collectors may also be subject to corrosion and freezing factors. The high voltage Electro-Static precipitator, see Fig. 5, is probably the most expensive type of high efficiency collector. It finds its applications generally in problems in which collectors previously discussed cannot be employed. Its collection efficiency is based on its design features and can be excellent on the finest of fume particles. Material is normally collected dry. Gas temperatures are of no great concern as long as condensation does not occur within the dry type of precipitator and the temperatures do not exceed the limits for materials used in its construction. As with the fabric arrester, provisions

Jan 1, 1954

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By Chas. A. R. Lambly

In the extreme northeast corner of the State of Washington, on the Canadian border, lies the Metaline mining district. This district is old in history, but young in production. Geology The Metaline district is a zinc-lead area of the replacement type in dolomite and limestone. The ore bodies of the Josephine horizon are in many ways similar to the ore bodies of the famous Tri-State zinc fields. The beds are faulted and folded and have varying low dips in varying directions, and underlie large areas of the district. History Production started in 1927 on a very limited basis. The property is now mining and milling 700 tons per day. The mine is opened by adit tunnels and a vertical shaft. As the ore horizons gained depth, it was necessary to sink inclines to follow the ore horizon (see Fig 1). From 1927 to date, approximately 600,000 ft of diamond drill was put down This work indicated that suficient tonnage existed to justify a redesigning of the whole operation, surface and underground. After four years of general study, the following program was planned: 1. A new mine entrance, which would be an incline, that could follow the ore body down at whatever pitch was necessary. The incline will be equipped with conveyors for the moving of ore and waste to the surface and with tractor-type locomotives for man and supply transportation. 2. The new incline also required a new type of mining which was developed and is now in use. It is called contour mining and will be described in a future paper. 3. The new incline exit would necessitate the moving of the mill and mine shops across the Pend Oreille River. This part of the program is now underway. The Incline The sinking of the incline was to start as soon as World War II ended and was as follows: The first leg of the incline was to be sunk from the surface 1600 ft on a 17" slope. The collar and first level at elevation 2180 ft, the second level at elevation 2000 ft, the third level at elevation 1875 ft, and the fourth level at elevation 1700 feet. From the 1700 ft elevation the incline was to flatten out to 12" for 400 ft to give the necessary depth for the ore pockets below the 1700 ft level and the necessary clearance for future sinking (see Fig 1 and 2). Due to lack of manpower in 1946, the program was changed and was as follows: A drift was driven from the old mine workings on the 1700 ft elevation in an easterly direction. At 1300 ft the drift was turned N 50" E and at this point a raise was driven 180 ft on a 50" slope. This raise intersected the Josephine horizon and commercial ore was encountered. At the 2000 ft mark, a main raise was driven, 245 ft on a 50" slope, and the 1875 ft elevation was cut. Exploration drifts were started on this level and production followed on a limited basis. The main drift at the 2500 ft point was turned N 35" E and ran parallel to and 10 ft east of and under the proposed incline line. At the proposed intersection of the drift and incline on the 1700 ft elevation, it was planned to raise the incline to intersect the 245 ft raise and to continue on to the surface, a distance of 1600 ft. When this proposed intersection point was reached, a heavy flow of water, approximately 800 gpm, was encountered and all work on the main drift face was stopped. This water flow flooded the main pump station in the old mine and the two lower levels with approximately 20,000,000 gal of water. The water was controlled and finally drained from the cave areas and lower levels after six months of pumping. After the heavy flow of water was encountered in the main heading, it was decided that the incline would have to be started from the surface, as originally planned, so that too much time would not be lost. The surface overburden had to be removed, a total of 6000 yards. A temporary dry house for 6 men was built. An 8 in. churn drill hole was intersected in the first raise driven from the 1700 foot elevation tunnel. Air and water lines were placed in this hole, and air and water were delivered to the collar of the incline from the mine working. The incline started down at 15 ft wide and 7 ft high through the Leadbetter slates. After sinking 4 sets, it was

Jan 1, 1950

By R. H. Gautschi, F. C. Langenberg

Rare-earth additions were made to laboratory heats of Type 310 stainless to observe their effect on as-cast ingot structure, nitrogen and sulfur contents, and nonmetallic inclusions. Lanthanum had a grain-refining effect in 30-lb ingots, but results with 200-lb ingots were inconsistent. Cerium, lanthanum, and misch metal lowered the sulfur content when the sulfur exceeded 0.015 pct and the rare-earth addition was greater than 0.1 pct. The rare-eardh content in the metal dropped very rapidly within the first few minutes after the addition. The size, shape, and distribution of nonmetallic inclusions was not changed in 30-lb ingots, but changes were noticed in larger ingots. RARE-earth* additions have been made to austenitic Cr-Ni and Cr-Mn steels to improve their hot workability. The high alloy content of these steels often results in a considerable resistance to deformation and inherent hot shortness at rolling temperatures, particularly in larger ingots. Rare earths in the metallic, oxide, or halide form are usually added to the steel in the ladle after deoxidation although they can be added in the furnace prior to tap or in the molds during teeming. The literature- indicates that the effects of rare-earth treatments on these stainless steels are not consistent, and sometimes even contradictory. Since no mechanism has been presented which satisfactorily accounts for the claimed improvements, the effects of rare earths are a qualitative matter. The work described in this paper was initiated to expand the knowledge of the effects of rare-earth additions on melting variables such as ingot structure, chemical analysis, and nonmetallic inclusions. REVIEW OF LITERATURE Ingot Structure—Rare-earth additions to stainless steels have been reported to cause a change in primary ingot structure in that there are fewer coarse columnar grains. However, the results are inconsistent. While one investigation1 has shown a large reduction in coarse columnar crystals, another2 has been unable to observe this effect, particularly when small ingots were poured. Post and coworkers3 observed ingot structures for a number of years and found that the columnar type of structure is not definitely a cause of any particular trouble in rolling or hammering, provided the alloy is ductile. Knapp and Bolkcom4 found rare-earth additions to be quite effective in preventing grain coarsening in Type 310 stainless steel. Chemical Analysis—Many effects of rare-earth treatment on chemical analysis have been claimed in the literature. Russell5 observed that some sulfur is removed by rare-earth metals, and that a high initial sulfur content improved the efficiency of sulfur removal. Lillieqvist and Mickelson6 report that rare-earth treatment causes sulfur removal in basic open-hearth furnaces, but not in basic lined induction furnaces. Knapp and Bolkcom found no sulfur removal in acid open-hearth and acid electric furnaces, probably because the acid slag can not retain sul-fides. snellmann7 showed that sulfur could be lowered apprecfably with rare-earth additions; however, a sulfur reversion occurred with time. Langenberg and chipman8 studied the reaction CeS(s) = Ce(in Fe) + S(in Fe), and found the solubilit product [%Ce] [%S] equal to (1.5 + 0.5) X 10-3'at 1600°C. Results in 17 Cr-9 Ni stainless were about the same as those in iron. Beaver2 treated chromium-nickel steels with 0.3 pct misch metal and observed some reduction in the oxygen content. He also noted an inconsistent but beneficial effect of rare earths when tramp elements were present in amounts sufficient to cause difficulty in hot working. It is not known whether rare earths reduce the content of the tramp elements or change the form in which these elements appear in the final structure. No quantitative data are available concerning a possible effect of rare-earth treatment on hydrogen and nitrogen contents. However, Schwartzbart and sheehan9 stated that additions of rare earths had no effect on impact properties when the nitrogen content was low (0.006 pct), but served to counteract the adverse effects of high nitrogen content (0.030 pct) on these properties. Knapp and Bolkcom4 analyzed open-hearth heats in the treated and untreated conditions and found the nitrogen content (0.006 pct) to be unaffected. These two results lead to the speculation that rare-earth additions can reduce the nitrogen content to a certain level. Decker and coworkers10 have observed that small amounts of boron or zirconium, picked up from magnesia or zirconia crucibles, increased high-tem-

Jan 1, 1961

By F. H. Buttner, H. Udin, J. Wulff

Using a modified Udin, Shaler, and Wulff technique, the surface tension of gold Udin, purified helium was found to be 1400 ± 65 dynes per cm for the temperature range 1017° to 1042°C. IN the original Udin, Shaler, and Wulff technique for measuring the surface tension of copper: variously weighted wires were allowed to extend or contract in a copper cell held at elevated temperatures in vacuum. By plotting stress vs. strain for a wire array in one test, the stress at zero strain is obtained. This is the point where the contractile forces resulting from surface tension are balanced by the applied load, according to the expression: y = e=o r [1] where y is the surface tension in dynes per cm; a,,,, the stress at zero strain in dynes per cm; and T, the radius of the wire in cm. The assumption that the wires deform viscously permits the drawing of a straight line through the points on the stress-strain plot. Justification of the assumption has received further experimental support recently.'-' The presence of grain boundaries in the wires requires a correction to the original expression used." Thus: y = d4=T [l- (dl) (ar)Y1 [2] where, n/l is the number of grain boundaries per unit length, and a, the ratio of grain boundary tension to free surface tension. Alexander, Kuczynski, and Dawson in studying the creep of gold wire in vacuum were unable to obtain reproducible values of the surface tension of gold. In plotting stress vs. strain for progressively longer times, they found that the stress at zero strain drifted with time from positive stress values to negative values. Similarly, for the surface tension of silver, reproducible values were obtained only when a purified helium atmosphere was substituted.' Evidently the evaporation rate of silver in vacuum is too high at the temperatures employed to obtain solid-gas equilibrium even in a similar metal enclosure. Thus reproducibility of results is lost. Experimental Procedure The experimental procedure was much the same as that originally developed by Udin, Shaler, and Wulff with a few modifications and improvements. For greater accuracy in strain measurements, knots gave way to cut gage marks as shown in Fig. 1. These were made with a hand-driven lathe in which razor blades serv'ed as cutting tools. Also a more precise cathetometer with a screw accurate to 0.00015 cm was used. The tests were conducted in an atmosphere of purified .helium rather than in vacuum in order to avoid possible evaporation difficulties. Five mil wire of high purity gold (99.98 pct) was used. After cutting in the gage marks, each wire of a series of about 12 was differently loaded by welding a gold ball to one end. This was done by dipping the end of the wire in a cooling gold droplet, previously melted on a charcoal block with a No. 2 acetylene torch. The other end of the wire was strung through a hole in a gold lid and twisted over the edge to hold the wires fixed and in suspension from the lid. The lid and mounted wires were then dipped in pure ethyl alcohol to dissolve any skin oils and dirt on the surface of the wires due to handling. Finally the lid was put in place on an alundum crucible lined with gold so that the wires hung freely within the gold-lined chamber. This whole assembly was next heated in a quartz nichrome wound tube furnace and heated for a few minutes at 600°C to soften the wires. After this anneal the wires were easily straightened with tweezers. The wire assembly was finally annealed 10" to 25°C above the subsequent test temperature for 2 hr. This treatment allowed the grains to grow to equilibrium size and shape. After the anneal, the lid was mounted in front of the cathetometer. The gage length was measured by sighting the 40 power microscope on the upper lip of the lower gage mark for the first reading, then traveling up to the lower lip of the upper gage mark for the final reading. This procedure was repeated four times to give an average gage length value. In this manner the annealed gage length and the final gage length could be measured to determine the strains. During all measurements, grain counts were made.

Jan 1, 1952

By ED. E. Furman, R. H. Atkinson

HITHERTO the practical creep testing of precious metals has received little or no attention. The only previous creep tests of precious metals have been made with wires under conditions such as to yield much more rapid rates of creep than in engineering tests.', ' Up to the present time the value of creep bars of adequate size, in the absence of real need for engineering data, has deterred investigators. However, the increasing use of platinum at high temperatures has demonstrated the need for reliable creep data for the guidance of engineers, especially those engaged in designing certain specialized chemical plant equipment. In order to supply this need, creep tests were conducted at 1382°F (750°C) on 0.290 in. diam specimens of platinum, 90 pct Pt, 10 pct Rh and palladium. The platinum was high purity, nominally 99.95 pct Pt. The 90 pct Pt, 10 pct Rh was of the same high quality as is used for making gauzes for the catalytic oxidation of ammonia. The palladium was also of high purity; two batches of palladium bars were tested, one deoxidized with calcium boride and the other with aluminum. Spectrographic examination of the palladium confirmed its good quality; the only significant impurities apart from the residual deoxidizers were traces of silicon and lead. Procedure The creep bars, which were furnished by Baker and Co. to our specification, were 6 ¾ in. in overall length with a 4½ in. (4 in. gage length) reduced section 0.290 in. in diam and had the ends threaded (?-NC16). It may be of interest that the bars were valued at up to $600 each. The specimens were supplied in a 50 pct cold-worked condition to facilitate attachment of the creep extensometer, which was of the push rod type. Because of the softness of the platinum and palladium, the extensometer rings were secured to the test section by means of circular knife edges instead of the usual pointed set screws. The extensometer rods extended through the bottom of the furnace and readings were taken with a 0.0001 in. "Last Word" dial gage fastened to the rods for the duration of the test. The bars were directly loaded by hanging weights from the lower specimen grip. All tests were conducted at 1382°F ± 2°F, and an effort was made to maintain the temperature gradient over the test section within 2°F. The ends of the furnace tube were packed with asbestos wool, which allowed a very slow circulation of air through the tube. Annealing was accomplished in the creep furnace before the load was applied. The platinum and palladium specimens were annealed at the test tem- perature for about 17 and 24 hr respectively; in the case of the rhodioplatinum it was found expedient to anneal for 1 hr at 1922°F (1050°C). Pilot samples cut from the same stock as the bars were used to check annealing procedures. Pertinent measurements of grain size and hardness were recorded. Results and Discussion The creep data obtained are given in Table I and the creep curves are plotted in Figs. 1, 2, and 3. Two platinum specimens, tested under a stress of 250 psi, had almost identical creep rates at 2000 hr, namely 0.000008 and 0.000009 pct per hr. A third platinum specimen, stressed at 400 psi, had a creep rate at 2000 hr of 0.000026 pct per hr; the reason for a rather sharp decrease in creep rate during the period from 1200 to 1600 hr is unknown. As it was thought that 90 pct Pt, 10 pct Rh would have a lower creep rate than platinum, the first sample was tested at 400 psi; however, the creep rate was approximately 50 pct greater. Microex-amination revealed that differences in grain size might be responsible for the unexpected result, as annealing at 1382°F developed an average grain diameter of 0.0021 in. in the rhodioplatinum specimen compared with 0.004 in. in the platinum bar. Annealing the alloy for 1 hr at 1922°F (1050°C) increased the average grain diameter to 0.0032 in. and materially improved the creep resistance, making it much better than platinum. A second specimen annealed at 1922°F (1050°C) and tested under a stress of 550 psi had a creep rate of 0.000022 pct per hr at 2000 hr, which was still substantially lower than that shown by the specimen annealed at 1382°F (750°C) and stressed at only 400 psi. In contrast to the creep behavior of the platinum and rhodioplatinum specimens, the palladium bars, whether deoxidized with calcium boride or aluminum, were characterized by high first stages of creep. However, after about 1200 hr of test, the creep

Jan 1, 1952

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman's results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman's demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman's experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman's experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman's experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman's Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author's reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By I. Fatt

A recently developed system for measuring electrical resistivity of liquids without use of electrodes offers some interesting possibilities in electric logging technology. The equipment as supplied by the manufacturer is satisfactory for continuous mud logging on a drilling rig or for measuring mud or filtrate resistivity in the laboratory. A simple modification of the commercially available instrument makes it suitable for measuring resistivity of core samples in the laboratory. The continuous measurement of mud resistivity on a drilling rig is a convenient means for detecting mixing of formation water with the drilling mud. Such information is useful to the geologist, the mud engineer and the logging engineer. However, continuous mud resistivity logging by conventional electrode-type resistivity cells is beset with difficulties. The mud, sand and rock chips abrade the electrodes, thereby changing the cell constant and eventually destroying the cell. Also, additives and crude oil in the mud may poison the electrodes by coating them with a nonconductive material. An electrode-type resistivity cell. therefore, may give erroneous readings under certain conditions. Electric logging companies circumvent the electrode poisoning problem by using a four-electrode resistivity cell for measurement of mud resistivity. In this cell, change in electrode area does not change the cell constant. However, the four-electrode cell is difficult to adapt for continuous reading and does not solve completely the problem of electrode abrasion by the sand and cuttings in the mud. The measurement of electric logging parameters on core samples in the laboratory encounters some of the same problems discussed in connection with mud logging. Ideally, the electrical resistivity of a core sample should be measured by placing platinum black electrodes in direct contact with the plane ends of a cylindrical or rectangular sample. Platinum black electrodes however, are much too fragile and easily abraded to be brought in contact with a rock sample. Also, oil or other constituents in the fluid contained in the sample will poison platinum black. In practice, gold-plated brass electrodes, in an AC bridge circuit operating at about 1,000 cps, are used for routine core analysis. For more precise work in research studies, a four-electrode scheme is used.',' Preparation of the samples for the four-electrode method is much too involved for routine core analysis. An apparatus for measuring resistivity of liquids without use of electrodes was described by Guthrie and Boys3 in 1879. They suspended a beaker, containing the electrolyte, by a torsion wire and rotated a set of permanent bar magnets around the vessel. The eddy currents induced in the electrolyte reacted against the rotating magnetic field to develop a torque, which was measured as a deflection of the torsion wire. In 1879 this method could not be made precise or convenient because of the lack of strong permanent magnets. The writer described a very greatly improved apparatus similar to that of Guthrie and Boys, but it was not suitable for continuous measurements or core samples.' Many electrodeless resistivity devices using radio frequency current are described in the literature.5, 6 These generally are suitable only for noting the end-point in a chemical titration. They do not measure resistivity, instead measuring a complex quantity which includes the dielectric constant and the magnetic permeability. The first description of the apparatus to be discussed in this paper was given by Relis.7 Improvements and modifications are described by Fielden,s Gupta and Hills,> and Eichholz and Bettens.10 DESCRIPTION OF APPARATUS The apparatus used in this study is based on the principle that the solution under measurement can form a loop coupling two transformer coils, as shown in Fig. 1. For a fixed AC voltage applied across Coil A, the voltage appearing across Coil B is a function of the resistance of the liquid-filled loop. The details of the voltage generating and measuring circuits are given in Refs. 7, 8, 9 and 10. A block diagram of the equipment is given in Fig. 7. Special features worth mentioning are the operating frequency of 18,000 cps and the automatic temperature compensation which results in the given resistivity readings being automatically correlated to 25°C. The liquid loop supplied by the manufacturer, shown in Figs. 1 and 2, was modified for use in core analysis (Fig. 3). The core sample under test is substituted for a section of the original loop. As shown in Fig. 3, the unit accepts only plastic-mounted cylindrical core specimens. A Hassler-type sleeve easily can be designed for the unit if unmounted cores are to be measured. EXPERIMENTAL PROCEDURE MUD LOGGING A simulated mud line was set up in the laboratory.

By R. V. Mrazek, F. E. Block, S. B. Knapp

The mixed homogeneous and heterogeneous kinetics of the thermal decomposition of tungsten hexacarbonyl were studied by employing a batch reactor. The system was such that a sample of tungsten hexacarbonyl could be injected into the preheated reactor, and the progress of the reaction followed by a simple pressure measurement. Both the homogeneous and heterogeneous reactions were found to be first order, and approximate activation energies were determined for each reaction. It is shown that the dis-proportionation of carbon monoxide to give carbon and carbon dioxide cannot be the source of carbon in tungsten deposits prepared by this reaction. The kinetics of the thermal decomposition of tungsten hexacarbonyl have been investigated as part of a continuing study by the U.S. Bureau of Mines on the decomposition of organometallic compounds. Reactions involving the thermal decomposition of metal carbonyls have a potential application in the preparation of pure metals and fine metal powders. Indeed, it was these applications which provided the impetus for much of the early work involving the carbonyls of nickel1 and iron.' The relative lack of study of other metal carbonyls can be traced to the comparative difficulty in synthesizing these compounds. The most common use for tungsten hexacarbonyl has been as an intermediate in vapor-phase plating.7'8 However, attempts to obtain a carbon-free deposit of tungsten by this method have not been successful, and some investigators have taken advantage of the carbon contamination and used this process to form tungsten carbide deposits.lo Other investigators have studied the thermodynamic properties11"14 and molecular structure of tungsten hexacarbonyl. However, very little is known about the kinetics of this thermal decomposition, the mechanisms involved," or the source of carbon in the resulting plate. In contrast, studies have been made of the kinetics of the thermal decomposition of nickel tetracarbonyl, iron pentacarbonyl, and molybdenum hexacarbonyl.'l It has been found that these thermal decompositions occur by a mechanism which is partially heterogeneous in nature. Information available on the equilibrium constants for the decomposition of tungsten hexacarbonyl was used to determine a temperature range, 500" to 560°K, in which the reaction could be expected to be essentially complete. APPARATUS The apparatus used allowed the injection of a sample of tungsten hexacarbonyl into a preheated batch reactor and the use of a simple pressure measurement to follow the progress of the reaction in the sealed reactor. The pressure was sensed by means of a pressure transducer (Consolidated Electrodynamics Corp., 0.3 pct)* capable of operating at the *Reference to specific products is made to facilitate understanding and does not imply endorsement of such brands by the Bureau of Mines._______ reaction temperature. This type of sensing element was chosen to avoid the problem of condensation of the sublimed carbonyl in the capillary tubing leading to any type of remote pressure-sensing device. stirring was provided by rotating the entire apparatus. Glass beads placed in the reactor provided a pulsating agitation. To minimize thermal gradients in the reactor walls, the reactor was constructed of aluminum. The support tube which held the reactor in the furnace was thin-walled stainless steel to minimize heat conduction out of the reactor. As a result of these measures, a nearly uniform temperature (°C) was maintained throughout the reactor. Fig. 1 is a schematic diagram of the apparatus. The small gear motor rotated the entire apparatus at about 200 rpm. The bearings shown at the ends of the air cylinder were perforated to allow air to be fed to the charging piston and to allow inert gas to be fed to the reactor during the preheating period. The sample was simultaneously injected and sealed inside the reactor by operation of the air piston. Fig. 2 shows a cross section of the air cylinder and the adjoining portion of the support tube leading to the reactor. The sample carrier is shown in place at the right-hand end of the injection rod extending from the air piston. The piston is shown in the retracted position, as it would be prior to the start of an experiment. The small Teflon gasket which encircled the sample carrier at the end of the injection rod sealed the reactor when the sample was injected. This seal was maintained throughout the test by maintaining air pressure on the piston. The sample carrier was a 2-in. section of thin-walled, -in.-diam nickel tubing with an internal blank about 1 in. from the base and with the base end sealed.

Jan 1, 1969

By W. C. Hauber

Techniques previously published to predict the production performance of a water flood when the mobility ratio is not unity have been primarily restricted to a five-spot well pattern. When other types of well patterns are considered, the prediction of performance has required either a model study or a complex numerical solution of a multiple-fluid system with a high-speed digital computer. Simple methods are developed in this report for predicting the areal sweep efficiency and injectivity history of a water flood for arbitrary well patterns and mobility ratios. The effect of an initial gas saturation can be incorporated into this method of prediction. With the layer superposition concepts published by Prats, et al.,1 these methods can be used to predict the production performance of a water flood in a reservoir having a wide range in permeability. A reasonably good agreement is shown by comparisons of the results calculated by this method with those obtained either by model studies or by complex numerical solution of multiple-fluid systems. Therefore, it has been concluded that a reasonably accurate method has been developed for predicting the production performance of a water flood employing an arbitrary type of well pattern for any given mobility ratio. A medium-speed digital computer can be used in applying this method. INTRODUCTION Production performance of multi-fluid five-spot water floods can be predicted by the techniques published by Prats, et al.1 This technique takes into account the effects of initial gas saturation, mobility ratio and vertical variations in horizontal permeability. A basic assumption in applying this technique is that unit displacement efficiency does not vary with time after the passage of the flood front. Prats, et al. demonstrated that this assumption is valid for normal waterflood applications with small mobility ratios. To extend Prats' technique to other types of well patterns has required either an experimental model study or a numerical solution of a multiple-fluid system to describe the performance of an individual homogeneous layer. Sheldon and Dougherty2 presented an exact numerical solution employing any arbitrary well pattern. This technique is complex to apply, requiring (1) numerical solution of the single-fluid system, (2) conformal mapping of the streamlines and iso-potential lines to form a new grid network, and (3) a numerical solution of the multi-fluid system on the new grid network. A method was developed in this paper to approximate areal sweep efficiency and injectivity as functions of time for an individual homogeneous layer for arbitrary well patterns and mobility ratios. Analytic expressions were derived to directly apply this method to five-spot and direct line drive well patterns. For other types of well patterns, this method is similar to the approach of Higgids and Leighton,6 in that it utilizes the stream tubes and iso-potential lines obtained by the solution of differential equations when the mobility ratio is unity. However, this method is easier to apply than the Higgins-Leighton method since it does not require knowledge of the variation between oil and water relative permeabilities and saturation. Using the relationship between areal sweep efficiency, injectivity and the volume of water injected into an individual homogeneous layer as obtained by the method presented in this paper, and Prats' technique for the superposition of individual layers, one can predict the production performance of any water flood. ASSUMPTIONS GENERAL Basic assumptions made in this report are that fluids are incompressible and the layers are horizontal, homogeneous and uniformly thick. It is assumed that as water is injected into the layer, three distinct regions are formed —a water bank, an oil bank, and an unflooded region. Each region is assumed to displace other regions in a pis-tonlike manner, with only one fluid flowing in each region, so that there is no change in unit displacement efficiency with time after the flood front has passed in the reservoir. Therefore, the residual oil saturation in the water bank and the oil saturations in the unflooded region are constant throughout the layer. The ratio (F) of the bulk volume of a layer occupied by the oil and water banks at any time before oil breakthrough, to the corresponding bulk volume of a layer occupied by the water bank, is given' by the equation BREAKTHROUGH AREAL SWEEP EFFICIENCY To predict the behavior of any type of waterflood pattern, one must know the breakthrough areal sweep efficiency Eb(Mc,o, F) for the pattern for any water:oil mo-

Jan 1, 1965

By P. C. J. Gallagher

A number of recmt determinations for the ratio of extrinsic to intrinsic stacking fault energy in fcc solid solutions are examined. Some of these arise from incomplete analyses which can yield only approxi?nate values for the ratio. Reliable results, on the other hand, obtained using extrinsic-intrinsic fault pairs, show that the extrinsic and intrinsic fault energies are essentially equal in several materials. There is some reason to believe that this finding is of general applicability to fcc elements and alloys. A wide range of values has been obtained for the relative magnitudes of the extrinsic and intrinsic stacking fault energies (yext and yint, respectively) in recently published studies in a variety of materials. In contrast, Hirth and Lothe' using a central force model have shown that out to tenth nearest-neighbor interactions the perturbation in energy caused by both types of fault is the same. Although the model used is not completely valid in metals, there is nevertheless some indication that marked variations of yext/nnt should not be observed from one material to another. In early work in Cu-A1, Cu-Ge, Ni-Co, and stainless steel all the deformation faults observed in the electron microscope were found to be intrinsic in nature, which led to an attitude that the extrinsic fault energy must be considerably greater than the intrinsic. Extrinsic faulting arising from deformation has, however, more recently been directly observed in Au-4.8 at. pct n;~ Ag-6 at. pct Sn and Ag-8 at. pct sn; Ag-7.5 at. pct In and Ag-11.8 at. pct 1n;"' pure silwer and Ag-0.5 at. pct ~n;' and Cu-22 at. pct Zn, Cu-30 at. pct Zn, and Cu-7.5 at. pct ~1.l' Multilayer loops containing extrinsic faulting have also been observed in quenched aluminum." While peak asymmetries in X-ray faulting probability studies were generally attributed to the presence of twins,Lelel2 has recently reinterpreted earlier X-ray data in Ag-Sb alloysU in terms of the presence of extrinsic faulting. The determinations of yeXt/yint made from the above studies are shown in Table I, with a brief description of the techniques employed. A number of the methods utilized are deficient in one or more respects, and the reliability of the values listed will be discussed. ~ele'~ recognizes that his approximate determinations of yext/yint assumes equal numbers of extrin-sically and intrinsically faulted dislocations. It is well-known, however, that such an assumption is not at all justified since extrinsic faulting has but rarely been observed in samples studied in the electron microscope. The only conclusion that should be drawn from the X-ray results at present is that the total intrinsic scattering cross section (i.e., the product of the width of the intrinsically faulted dislocations with their density) is approximately ten times greater than for extrinsic faulting in these particular samples. An important point is that the relative magnitudes of the energies cannot be inferred from results of this type, unless the intrinsic and extrinsic faults form with equal ease. One must recognize that, although a formation barrier may restrict the amount of extrinsic faulting which occurs, this in no way implies that the extrinsic and intrinsic energies should be different. It is unlikely that a worthwhile estimate of the relative densities of extrinsically and intrinsically faulted dislocations can be made at the high deformations present in X-ray samples. ~oretto,'~ from a statistical argument applied to the nonobservation of extrinsically faulted tetrahedra out of a large sample, concluded that yeXt/yint could not be less than -4.5. However, the present author feels that a high-energy formation barrier as just supposed also explains this finding satisfactorily and that no conclusion can possibly be drawn concerning the actual extrinsic stacking fault energy. The same argument also serves to explain the fact that extrinsic faulting has been relatively little observed in the electron microscope. Extrinsic-intrinsic node pairs and isolated extrinsic nodes were first reported by Loretto~ and subsequently by Ives and Ruff,' Gallaher,' and Gallagher and Wash-burn.' Ives and Ruff' found a wide spread in the ratio of extrinsically to intrinsically faulted area in the node pairs they observed, and drew the very tentative conclusion that yeXt/yint 2 2. They recognized that a straightforward comparison of the size of the faulted areas could provide no more than a qualitative result without a theoretical analysis of the dislocation geometry associated with extrinsic faulting. A theoretical

Jan 1, 1969

By H. J. Tschirner, L. P. Davidson, R. K. Carpenter

HE electrolytic zinc plant of the American Zinc Co. of Illinois, at Monsanto, was expanded in 1943 to a capacity of 100 tons of slab zinc daily. This capacity was not attained because of inability of the leaching plant to deliver an adequate amount of solution for electrolysis. Changing the leaching method so that the acid was added to the roasted zinc material reversed the usual procedure and made it possible to attain the desired capacity. The conditions which prevented satisfactory work before this change and the difficulties which arose in reversing the usual leaching procedure are described. The "reverse" leach operation as now practiced is carried out as follows: All the calcine to be leached is fed continuously to a slurry mixing tank. About one third of the acid to be used is fed to the tank with the calcine. The slurry is discharged continuously to a Dorr duplex classifier in closed circuit with a Hardinge mill. The classifier overflow is pumped to any of six leaching tanks where the leach is completed. A finished leach is discharged through Allen-Sherman-Hoff pumps to Dorr thickeners, from which the overflow goes to the zinc dust purification and the underflow to vacuum filters. This change in leaching procedure from the usual one of adding calcine to a large amount of acid made it possible to provide an adequate amount of purified solution to the electrolyzing division and at the same time filter and dry all the residue produced. Operating savings in reagents and better metallurgical recoveries were also important benefits. The original flowsheet of the leaching plant provided leaching, sedimentation of the insoluble residue, and purification of the neutral zinc sulphate solution with zinc dust. The thickened residue was filtered and washed. The purification cake of excess zinc dust, precipitated copper and cadmium, and any insoluble residue was filtered off on plate-and-frame duplex classifier. Settlement in the thickeners was inadequate and the suspended solids in the thickener overflow gave rise to filtration difficulties after the zinc dust purification. Further, the filtration and washing of the leach residue was poor, and it became necessary to pump a large amount of unwashed or poorly washed residue to storage ponds outside the plant building. Two causes of the poor settling and filtration were determined: Soluble silica and ferrous iron in the calcine treated. The latter was a result of poor roasting and with more experience ceased to be a major problem. The silica was a normal constituent of the feed and the working out of the problem became a matter of controlling its solubility. The obvious method to render the silica insoluble was by intensive roasting. This, however, met with total failure as such roasting resulted in silicates, probably zinc, soluble in the 13 pct acid used for leaching. Attempts were made to coagulate the fine gelatinous slime with addition agents. Glue, lime, starch, beef-blood serum and others were tried without success. All the suggested tried-and-tested means of operating the thickeners gave no consistently good results. Variations in leaching time, in addition of calcine to the leaching tanks, "conditioning" of the pulp by prolonged agitation, immediate discharge of the leach upon completion to avoid breaking up flocs were all tried and given up as ineffective. Byron Marquis, of Singmaster and Breyer, worked with the plant staff on a beaker scale until a leaching procedure was developed which gave consistent results and a promise of overcoming the difficulties which had plagued the plant operation. It was suggested that the difference in solubility of silicates and zinc oxide in sulphuric acid could be made use of in a leaching method where the acidity was controlled carefully. Such control is possible when acid is added to a slurry of calcine. This process reverses the normal procedure of adding calcine to a vessel of acid, hence the term "reverse leach" was applied. In this way, the overall acid concentration can be kept very low. In the tests made, it did not exceed 0.05 g per liter free sulphuric acid. Numerous advantages were realized when no silicates were taken into solution and later precipitated as a bulky gel. The gel had made reasonable thickening and filtration of the leach pulp and practical drying of the residue impossible. When the gel was eliminated, thickening rates were increased as much as five times. The volume of residue after thickening represented about 10 pct of the total leach pulp and had been as high as 95 pct when the gel was present. The thickened pulp was filterable and the filtered cake was dried readily after washing. The zinc extraction from the calcine was slightly lower. This was more than compensated for by the increase in zinc recovered in solution from zinc which had been trapped in the gelatinous residue. The amount of copper recovered was lower. However, the amounts of other impurities, such as arsenic, antimony, and germanium, taken into solution were lower. This was particularly true of antimony. Since the inception of reverse leaching, no concentrates have failed to yield solutions free of antimony even when present in the calcine to the extent of 0.2 to 0.3 pct. Oxidation of ferrous iron is a problem of reverse leaching. Ferrous hydrate does not precipitate at pH 5.3 to 5.4 where a leach is finished. The usual oxida-

Jan 1, 1952

By Reaves. M. J.

The title of my talk, "What Happened to the Uranium Boom?" is old news. Certainly it is for this group. All of us that make our living in uranium know that the boom of the last half of the 1970's is over. U.S. production has been exceeding consumption by more than two to one. Mines and mills are closing and yellowcake prices have been dropping for over 20 months. The gloomy outlook for the industry in the near term has been well documented by soothsayers of various descriptions, your daily newspapers, and in the Nuexco Monthly Reports. I'd like to attempt to describe the next upturn in the market (speculate, really) based upon the clues we're seeing now. In order to do that, I'd first like to go over briefly, some of the market factors that contributed to the recent price drop and resultant production cutbacks, and then hypothesize on the way these factors are changing and will change. Market prices are greatly affected (maybe even entirely determined) by buyer perceptions. This is particularly true with uranium, because of the long lead times associated with nuclear plant construction and also with conventional mine/mill development. Before the price rise (say, 1975) utility uranium buyers believed that: 1) U.S. producers would have difficulty expanding to meet U.S. demand. 2) Australian and Canadian production was essential to avoid shortages in the early 1980's. 3) Uranlum prices would continue to rise as demand exceeded supply. 4) Enrichment capacity would become inadequate. It was thought necessary, therefore, to build enriched inventory in the early 1980's for use in the late 1980's. Artificially accelerated expansion of the uranium producer industry was necessary to accommodate anticipated enrichment demand. Current perceptions are largely the opposite. These are the beliefs that were held most of this year and late last year as prices dropped. 1) U.S. production is far in excess of domestic need. Contraction of the U.S. production lndustry is necessary. 2) Canadian and Australian supply is optional and not essential. Producers in those countries are expanding mainly by displacing higher cost production and not because they fill a void, 3) Prices may be essentially stable for some time. 4) Enriched uranium is in excess supply. That is 1981. 1982 is shaping up to look like this: 1) Prices will have bottomed out. (That is not Nuexco's opinion necessarily, by the way, but it is my opinion.) 2) There will still be substantial utility inventories, but fewer spot sales. 3) Canadian and perhaps Australian sellers will have made substantial sales in the U.S. and will be aggressively seeking more. 4) U.S. production will have been dramatically curtailed. U.S. utilities that wish to con- tract long term will have difficulty in finding domestic sellers. Concern will develop about the availability of U.S. production capability. Virtually all long term con- tracts signed will be with non-U.S. sellers. 5) An awareness will begin to develop among U.S. buyers that we are approaching a period of dependence upon foreign uranium (which will be true). The history of the uranium market has been one of dramatic changes and overreaction to those changes. The rapid price rise of a few years ago generated excess U.S. production capacity and the rapid price drop of the last two years will almost certainly result in too little capacity. It will soon be difficult for U.S. buyers to buy domestic material except on the spot market. The question is, "will they care?" The lack of demand, of course, is the underlying reason for the current poor health of the uranium industry. In 1972, 1973 and 1974 collectively, there were 105 nuclear reactors ordered in the U.S. That ordering rate was expected to continue and accelerate throughout this century. In 1975, 1976, 1977, 1978, 1979, and 1980 altogether, there were 56 more reactors cancelled than ordered. The net growth of our only customer since 1974 has been a negative 56. TO put this in perspective, if these 56 reactors were operating now it would more than double present U.S. uranium consumption. Underlying lack of demand is something that is simply not going to change in this decade. Time is going to be required. The NRC indicates that the maximum feasible number of new reactors that can be licensed each year is six. That would increase uranium consumption by only 10% per year. New reactors, if ordered tomorrow, would not generate new uranium demand until after 1990. Even so, United States' consumption of uranium will rise from the 1980 level of 18 million pounds per year, to

Jan 1, 1982

By P. Greenfield, C. C. Smith, A. M. Taylor

J. E. Harris (Berkeley Nucclear Laboratories, England)—Greenfield et al.11 attribute abrupt changes in slope of their log o/log i curves for heat-treated Mg/0.5 pet Zr alloy (zA) to &apos;atmosphere&apos; locking. It is proposed here that a more reasonable explanation of the apparent strengthening at low rates of strain can be based on precipitation either during the preanneal or during the creep tests. All the tests were carried out above 0.5 Tm where solute atmospheres are likely to be largely evaporated2 and can migrate sufficiently rapidly so as not to impose any &apos;drag&apos; on the moving dislocations. McLean3 has derived an expression for determining the temperature Tc above which, due to the high-migration rate of the atmospheres, Cottrell or Suzuki locking can play no part in determining creep strength. This expression, which holds for an applied shear stress of not greater than 5 X 107 dynes per sq cm is: Tc/Tm= 7/6.8 - log10? where i = secondary creep rate The values for T, corresponding to the maximum and minimum reported creep rates at each temperature have been calculated from the data of Greenfield et al. These are given in Table VII. All the test temperatures were above T,, the margin being greater for the higher temperatures and for the lower strain rates where the breaks in the log s/log ? curves occurred. Dorn and his collaborators14, 17 have studied systematically the effect of solute hardening on the creep properties of an A1/3.2 at. pet Mg alloy. In the temperature range where strain aging occurred in tensile tests, abnormally high-activation energies for secondary creep were obtained but at temperatures above 0.43 Tm, solute alloying did not have any effect on the creep parameters. Moreover, there have been no reports of any strain aging phenomenon during elevated temperature tensile tests with ZA material.18 Instead of the observed strengthening being due to atmosphere locking, it is now proposed that precipitates play an important role in enhancing the creep strength of the material. There are two possibilities—precipitation of zirconium hydride during the high-temperature preanneal and/or precipitation of the hydride or a-zirconium during creep. On the basis of the former the results can be interpreted in terms of a critical stress being necessary to force the dislocations through or over preexisting precipitates. From the latter, if the strengthening is due to pre- cipitation during the test then hardening should be associated with a critical strain rate. At low rates of strain, time is available during the tests for precipitation to occur either directly onto dislocations (thus pinning them) or generally throughout the matrix (which would impede dislocation movements). Examination of the data of Greenfield et al. suggests that both mechanisms may be operative since they observed precipitation during creep and also found that their alloys exhibited high-creep strength in the early stages of the low-stress tests, i.e., before creep-induced precipitation had time to occur. It is not easy to understand why they considered that precipitation of zirconium hydride is unlikely to occur at 600°C while it can take place in tests in air at as low a temperature as 200°C. Precipitation of the hydride during the preanneal cannot be ruled out merely on the basis of metallographic examination. Hydride precipitates in ZA type alloys are very small and can only be accurately resolved in the electron microscope.9 For example, in this laboratory20 hydride platelets with major dimensions <(1/10) µ have been observed by electron transmission through thin film specimens of hy-drogenated ZA material. Complex interactions between dislocations and such particles are illustrated in Fig. 12. Additional evidence for precipitation during pre-annealing is provided by the data presented in Greenfield&apos;s Fig. 1 and Table IT. These show that the creep strength at 200o and 400°C increases with the time of preanneal at 600°C. Such increases cannot be explained on the basis of increases in grain size alone for further improvements in strength were observed when the material was annealed for longer times than that required to stabilize the grains. Although the main discussion is confined to ZA material, similar arguments can be used against the strain aging hypothesis proposed to explain the binary Mg/Mn alloy data. In this case no precipitation is possible during the preanneal, but precipitation-hardening during creep can occur.

Jan 1, 1962

By J. S. Rinehart, W. C. Maurer

The mechanics of impact crater formation in rock, particularly sandstone, has been sutdied, the velocity range being approximately that normally associated with oilwell gun perforators. The bullets were small steel spheres having diameters of 3/16, 9/32 and 7/16 in; impact velocities ranged from 300 to 7,000 ft/sec. The craters have two distinct parts — a cylindrical hole (or burrow) with a diameter the same as that of the impacting sphere, and a wide-angle cup comprising most of the volume of the crater. The burrow is fornred as material in front of the projectile is crushed and pushed aside, forming a cylindrical hole surrounded by a high-density zone. The clip forms as fractures are initiated in front of the projectile and propagate along logarithmic spirals, approximaling maximum shear trajectories, to the free surface of the rock. A most significant observation (made for the first time) was that, below the base of the cup in one type of sandstone, there are a group of similar fractures, not extending to the surface, which are spaced uniformly a few millimeters apart. Each fracture follows roughly the contour of the base of the cup and appears to require a certain threshold impulse to initiate it. These fractures comprise a relatively high fraction of the total, newly exposed surface area. The volume of the material removed by crushing varies as the first power of the impact velocity and the volume removed by fracturing, as the second power of the impact velocity. Penetration varies linearly with the impact velocity and is inversely proportional to the specific acoustic resistance of the target material, the proportionality constant being dependent upon the shape of the projectile. INTRODUCTION Yield of oil from a producing well is frequently enhanced by firing bullets and shaped charges through the well casing into the oil-bearing rock, forming craters and fractures from which oil can flow more readily. The purpose of this investigation has been to develop a better understanding of the mechanics of impact crater formation in rock, particularly sandstone, the velocity range being approximately that normally associated with oilwell gun perforators. FORCES OPERATIVE DURING IMPACT When a projectile moving at considerable velocity strikes a- massive target such as oil-bearing sandstone, intense and complex transient stress situations develop within both the projectile and the rock or sandstone against which it is striking. Usually the struck rock fails, the missile or projectile penetrating into the rock to some depth where it comes to rest or is forcibly ejected from its burrow by expansion of a plug of target material compressed in front of it. When the impact velocity is very high, the projectile itself may fail, breaking apart or becoming distorted; this situation is not considered here, the discussion being limited to nondeforming projectiles. Many experimental studies&apos;.&apos; have been carried out to determine the nature of the mechanics of crater formation and the salient features of the forces coming into play, some of the earliest studies being the French Army experiments performed at Metz between 1835 and 1845.&apos; The stratagem in most instances has been to make a post-mortem examination of the crater, measuring volume and depth of penetration and deducing force relationships from these observations rather than performing the more difficult (usually almost impossible) feat of measuring stresses during penetration. In many materials, the force acting during penetration of the projectile is found to be the sum of two components—(1) a constant force, independent of the velocity, representing some inherent strength of the target material; and (2) a component, proportional to the square of the velocity, representing inertial forces. For such materials, the average force per unit area acting on the projectile at any instant while it is in motion and being decelerated may be written F/A = a + bv2 . . . (1) where v is the velocity of the projectile at that instant, A is the cross-sectional area of the penetrating projectile taken normal to its trajectory, and a and b are constants which are dependent upon the target material and the shape of the projectile. It follows that the total penetration s is given by .........(2) where v, is the velocity of the projectile when it just strikes the target. Values of a and b for spherical projectiles impacting in a loose sand-gravel mixture and compacted earth were obtained in the Metz experiments. For sand-gravel, a and b are 620 psi and 0.0115 (psi) (ft/sec)&apos;, respectively; and for compacted earthworks, a and b are 432 psi and 0.0008 (psi) (ft/sec)&apos;. Figs 1 and 2

By S. J. McCarroll

Fig. 1—The belt shown at right carries filter cake to mixing station over calciner. Crude ore conveyors appear in right background. THE Three Kids mine, some six miles east of Henderson, Nev., is in a typical southwest desert area, with high dry summer heat and cool to cold winter seasons. The manganese deposit was located during World War I.&apos; During this period 15,000 to 20,000 tons of ore assaying up to 41 pct manganese were shipped. Interest in the deposit was not revived until the middle thirties, when experiments on the ore were initiated. Test work indicated possible recovery of only 70 pct by flotation, but in 1941 additional work was done at the Boulder City pilot plant of the U. S. Bureau of Mines and also by M. A. Hanna Co. As a result, the Manganese Ore Co. was formed and a plant utilizing the SO2 process was constructed. Numerous operation difficulties ensued, and the plant. was closed when the manganese situation in the country eased. In 1949 Hewitt S. West initiated negotiations to acquire the plant. In 1951 Manganese, Inc., was formed and contract entered into with the General Services Administration to supply 27 million units of metallurgical grade manganese in the form of nodules to the national stockpile. A second contract was made to upgrade 285,000 tons of stockpile ore. Test work was undertaken by the Southwestern Engineering Co. and likewise by the Boulder City pilot plant at the U. S. Bureau of Mines. Results obtained indicated the commercial feasibility of the flotation process. Construction of the plant, which is shown in Figs. 1 and 2, was started in June 1951, and operations on a break-in basis began in September 1952. Apart from the usual starting difficulties two major disasters caused serious setbacks, one a kiln failure in February 1953, and the other a fire that destroyed the flotation building in June of the same year. The nodulizing section of the plant resumed operation in November, and the flotation section in January 1954. The ore minerals are chiefly wad,* with minor amounts of psilomelane, and occur in sedimentary beds of volcanic tuff. The ore is overlain with beds of gypsum which outcrop or may be covered with surface gravel. Intermediate beds of red and white tuff occur frequently with lenses of red and green jasper and stringers of gypsum and calcite. Small amounts of iron are present; lead content averages about 1.0 pct and minute amounts of copper and zinc are found. Barite, celestite, and bentonite are present. Since these are made up of minute asicular crystals, moisture content is very high, averaging about 18 pct. Ore reserves have been estimated at 3 million tons averaging 18 pct Mn2 and up to 5 million tons after grade is dropped to 10 pct Mn. A good part of the orebody was stripped of overburden by the previous operating company . Approximately 50 pct of the ore, representing more than 60 pct of the manganese, can be mined by open-cut methods. A system for underground min- . ing has not yet been decided on. Open-cut mining with benches of 20 ft has proved satisfactory. Although the ore is soft and appears dry and dusty it has a certain resilience, probably due to the porosity and moisture which makes drilling and fragmentation difficult. Wagon drills have been abandoned in favor of the Joy 225-A rotary drill which will put down a 43/4 -in. hole at the rate of 2 ft per min. Holes are spaced in a pattern with 8 to 9-ft centers. Forty percent powder has been used, but better breaking to 2-ft size is obtained with low velocity bag powder of 30 pct strength. Loading is done with one 21/2-yd shovel, and cleanup follows with one D-7 bulldozer. The ore is hauled with Euclid trucks about 1000 ft from the pit to a blending pile, where the daily mine production is spread in layers by bulldozing until approximately one month&apos;s mill feed is accumulated. A new pile is then started and mill feed is drawn from the first pile by one 13/4-yd shovel and Euclid trucks, with a haul of approximately 500 ft. Mining is performed by an independent contractor with engineering and supervision by the company staff. Early test work indicated that the manganese could be floated with soap, a wetting agent, and fuel oil to give a recovery of better than 75 pct with a grade of 43 pct Mn. The concentrate when nodulized with coke would upgrade to 46 pct Mn or over, and the lead volatilized to 0.6 pct residual.

Jan 1, 1955

By M. D. Arnold, H. J. Gonzalez, P. B. Crawford

A method is presented for estimating the effective directional permeability ratio and the direction of maximum and minimum permeabilities in anisotropic oil reservoirs. The method is based on the principle that production from a well in an anisotropic reservoir results in elliptical isopo-tentials about the well, rather than circular. Bottom-hole pressure data from three observation wells surrounding a producing well are required to apply the method. The method involves fitting field pressure data to a set of general charts of isopotentials and making a few simple calculations until a solution is found. The method is based on a steady-state equation for homogeneorrs fluid pow. In addition to the method, a brief discussion of the theory underlying it is presented. INTRODUCTION The existence of a different permeability in one direction than another in oil reservoirs has been mentioned in several papers. Hutchinson&apos; reported laboratory tests on 10 limestone cores and pointed out that one-half of them showed significant, preferential, directional permeability ratios, the average being about 16:1. Johnson and Hughesz reported a permeability trend in the Bradford field in the northeast-southwest direction with flow being 25 to 30 per cent greater in that direction. Barfield, Jordan and Moore -eported an effective permeability ratio of 144:1 in the Spraberry. Crawford and Landrum4 showed that sweep efficiencies could often vary by a factor of two to four, and sometimes considerably more, due to variations in flooding direction and patterns in anisotropic media. These findings indicate that the poss&apos;bility of anisotropy may be worthy of consideration in the development of an oil field. In considering this, it should first be determined if anisotropy exists. If it does, the direction of the maximum and minimum permeabilities and the ratio of their magnitudes are quantities which can be of value in planning the most efficient well-spacing patterns. Past methods of determining these quantities have included analysis of oriented cores and analysis of flooding performance of pilot injection patterns. In recent work, Elkins and Skov5 resented an analysis of the pressure behavior in the Spraberry which accounted for anisotropic permeability. This work was based on the transient pres- sure distribution in a porous and permeable medium, with the solution expressed as an exponential integral function involving rock and fluid properties. The purpose of this study is to provide a method, based on steady-state equations, of estimating the direction and relative magnitude of permeabilities in an oil reservoir from field pressure data and well locations only. The method presented is based on work by Muskat6 which shows that Laplace&apos;s equation represents the steady-state pressure distribution for homogeneous fluid flow in homogeneous, anisotropic media if the co-ordinates of the system are shrunk or expanded by replacing x with it is desirable that data be obtained early in the history of a field because knowledge of an anisotropic condition would allow new wells to be spaced in such a manner that reservoir development and subsequent secondary recovery programs could be planned more efficiently. THEORETICAL CONSIDERATIONS A brief discussion of the theoretical basis on which the graphical solution was developed is presented in this section. Muskat&apos;s two-dimensional6 olution for the pressure distribution in an homogeneous, anisotropic medium with an homogeneous fluid flowing can be algebraically manipulated to show that the isobaric lines are perfect ellipses. The ratio of the major axis to the minor axis, a/b, is related to the permeability ratio, k,/k,, as follows. alb = dk,/k,--...........(1) It can also be shown that the pressure varies linearly with the logarithm of the radial distance from the producing well. However, the gradient along any ray is a function of the orientation of that ray, and a ..xiable is present when anisotropy exists which cancels out for a radial (isotropic) system. For a system such as that described, a dimensionless pressure-drop ratio was developed which is completely independent of the actual magnitude of the pressures. This was done by arranging Muskat&apos;s solution in such a way that aIl variables cancelled out except k,/k, and well positions. However, this solution depends on having a co-ordinate system with axes coinciding with the major and minor axes of the elliptical isobars. Thus, it was necessary to introduce a co-ordinate system rotation factor. The two unknown variables are then k,/k. and 0, and the two measured dimensionless pressure-drop ratios are related to the unknown variables as follows.

By L. R. Woodyatt, H. J. Beattie, C. T. Sims

Theories correlating the formation of u and related intermetallic compounds to the electron-per-atom density of binary and ternary alloys have appeared regularly in recent technical literature. These same principles can be modified and applied to complex precipitation-strengthened alloys such as the iron-, cobalt-, and nickel-base superalloys and the stainless steels. Since these complex alloys contain carbides and other phases that normally precipitate before the U-type phases, the nature and amount of the precipitated phases must be calculated first. The following general formula is then applied to the residual matrix composition of the alloy: element. The magnitude of the resulting number is indicative of whether the alloy will form a a -type phase. When these calculations (which are computerized) are systematically applied to alloys of knoun phase analysis, a breakoff in average electron-vacancy number is noted between U-free and U-prone alloys. Alloys with an average electron-vacancy number higher than the breakoff form a-type phases, while those with lower ones do not form these phases. This method could then be used to eliminate from consideration all experimental compositions that would precipitate undesirable phases. It also is useful in evaluating analyzed heats of alloys where minor heat-to-heat variations determine whether the alloy is o-free or o-prone. THE highly significant development of strong, ductile superalloys to provide reliable construction materials in the 1000" to 2500° F temperature range has been due principally to unremitting application of Edisonian techniques and logic by the dedicated physical metallurgists who have shouldered this responsibility. Tools such as the electron microscope, phase analysis, and computers to accomplish regression analyses have been used heavily, but the effort has been essentially practice of an art, rather than a science. The objective of this paper is to describe and illustrate application of some relatively fundamental principles to certain of these alloy systems in an attempt to remove some of the empiricism from the technology. Specifically, the work presented here deals with the use of periodic-group relationships to predict the formation of intermetallic phases which can occur in primarily austenitic (fcc) structures. Calculations that have been developed might be applied in the design of new alloys and the evaluation of known alloys, and thus have the potential of eliminating vast areas of unnecessary alloy preparation and evaluation. ALLOYING CONCEPTS AND STRUCTURAL FEATURES OF SUPERALLOYS Strength is produced in austenitic superalloys by three principle mechanisms: 1) precipitation of y&apos;; 2) formation of carbides; 3) solid-solution hardening by soluble refractory metals. The first mechanism requires the addition of aluminum and titanium, the second requires carbon and carbide-forming elements, while the third calls for the addition of molybdenum and/or tungsten. A considerable concentration of chromium is usually maintained to resist oxidation/corrosion, but it is also an important carbide-forming element. Fig. 1 shows a sketch and electron micrograph of the structure of a typical wrought nickel-base super-

Jan 1, 1967

By P. R. Sperry, M. L. Holzworth, P. A. Beck

The basic work of Z. Jeffries 1,2,3 has long ago established the main features of grain growth in the presence of a dispersed second phase. Working with sintered specimens of initially fine grained tungsten, to which various amounts of thoria had been added, Jeffries found that grain growth was inhibited, that is, practically prevented, up to a certain annealing temperature. When this temperature, which increased with the thoria content, was exceeded, extremely large grains developed abruptly from the fine grained matrix. such a a temperature" was later found by Gross-mann~3,14 in certain types of steel, while ~~i~ showed15 that in other steels grain growth was gradual, without inhibition and abrupt coarsening. Later work demonstrated the connection between coarsening and aluminum additions. The viewpoint that the direct cause of inhibition and coarsening in aluminum killed steels is a fine dispersion of aluminum oxide21 appears to be held quite generally, although some doubts have been voiced even very recently, 20 In steels with Ti additions the titanium carbide phase is considered responsible for the inhibition effects found.20 The coarsening temperature increases with the titanium content. That coarsening may occur, as a result of, certain heat treatments, even in low carboil rimmed sheet steel, was shown by Samuels. He also detected coarsening in a steel ingot of similar composition, after giving it the same heat treatment as that used by him for the sheet material. In this instance the identity of the inhibiting phase has not been determined. However, Tangerding found23 that even the few small carbide particles, which occur in carbonyl iron, have a very marked inhibitive effect. As a result of an oxidizing anneal at 850°C, large grains begin to form at the surface of the carbonyl iron specimen, and gradually grow inward as the subsurface oxidation of the carbide particles progresses and eliminates the obstruction. The carbide particles Can be removed also by annealing in hydrogen, with similar results. But if the oxidizing anneal of 10 hr at 850°C in air is followed between in hydrogen for 75 hr at the Same temperature, grain growth is more hibition usually the whole specimen is transformed into a single crystal (approx. 1.5 cm X 5 cm). The reversed procedure, that is, hydrogen annealing followed by oxidizing annealing leads to smaller grains. Tangerding arrived at the logical conclusion that there must have been in his specimens some additional obstruction to grain growth hibition from a minor impurity, other than carbon. It seems likely that this obstruction was caused by an oxide formed during the oxidizing anneal and gradually reduced rtain the subsequent hydrogen-annealing. Other instances of grain growth inhibition of varying severity, associated with a dispersed second phase, have been described by several authors. Notable examples: lead with 0.06 pet Cu or Ni,24 cartridge brass with 0.12 pct Cr,25 or with up to 0.15

Jan 1, 1949