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By G. D. Hobson, I. Mrosovsky

Material balance relationships for expansion-type reservoirs above the bubble point have been discussed in recent years by H. N. Hall and M. F. Hawkins, Jr. The former drew attention to the effects of rock compressibility, and the latter to the effects of the compressibility of any interstitial water. Hawkins derived a general relationship which took note of oil, water and rock compressibilities, and then by assuming first, the absence of interstitial water and secondly, no effects due to interstitial water or rock compressibility, obtained relationships symbolically of the same form as those previously derived directly by Hall. Hawkins defined his terms clearly, and noted an approximation, due to the omission of a term involving the product of two compressibilities, made in reaching his final equation. There is, however, possible ambiguity with regard to Hall's written definition of the oil production term. One interpretation would mean that the produced oil and initial oil-in-place, if both required as stock tank barrels, would be obtained by using different formation volume factors in the conversion in order to satisfy the conditions implicit in Hall's formulae. The other would involve an approximation which, if used, was not stated. In both Hall's and Hawkins' studies the effect of the approximation or inconsistency is very slight. Nevertheless, it may be justifiable to give a somewhat more consistent derivation, since the complexity of the final relationships is not thereby greatly increased. Let the initial pore volume be Vi and the volume after a pressure drop of Ap, V. Then V = V, (1 - ?p . cr), where c, is the rock compressibility expressed as change in pore volume/unit pore volume/unit pressure change, and is defined with the initial pressure as base. Suppose that the interstitial water saturation under the initial conditions is Sw. The total volume of interstitial water under those conditions will be ViSw. If the volume of the water after dropping the pressure by ?p is V., this will be given by Vw = ViSw (1 + ?p.c,w), the compressibility of the water being c, which is ex- pressed using the volume at the initial pressure as base. If Boi is the reservoir volume factor of the crude oil for the initial reservoir conditions, and B. the equivalent factor when the pressure has dropped by ?p, with N the initial amount of oil expressed as stock tank barrels. N.Boi = Vi - V,Sw If n is the amount of oil produced (in terms of stock tank barrels) as a result of the pressure drop ?p, the remaining subsurface volume of oil at the lower pressure will be Bw, and Bc can be related to the compressibi:ity of oil and the pressure drop, and if c, is the compressibility factor based on the initial conditions, The relationship derived by Hawkins was case to a standard at the lower pressure, while a term (Ap) had been dropped, because of its smallness arising from its dependence on the products of two compressibility factors. When there is no interstitial water and rock compressibility can be ignored, Eq. 1 reduces to:

Jan 1, 1957

By P. K. Koh

With identical annealing heal treatment the development of major annealed texture component seems to depend primarily upon the degree of cold reduction. Cube texture was evident on annealing- 1/2-, 1,/4- , and 1/8-mil tapes at 760°C, but it dissap-)eared on 927°C annealing of 1/8-mil tape cold reduced 96.9 pct. Some cube texturee remained as tile strongest 927 °C annealed texture component in 1/4- and 1/2-mil tapes cold reduced 93.8 and 87.5 pet, respectively. The switching coefficient increases and the squareness ratio of the hysteresis loop decreases proportionally with increasing cube pole concentration. PREVIOUS studies 1,2 on the 1/8-mil ultra-thin molybdenum permalloy tape established cold rolled and annealed textures and their magnetic performance for switch-core and coincident-current memory applications, The major cold-rolled texture was found to be of {110}<335> which is quite similar to the cold-rolled texture of silver and 70-30 cartridge brass. The major annealed texture components were found to be of {120)-- <001> and {113)<785>. Although the direction for easy magnetization for this type of alloy by the single-crystal technique is not avaliable, knowledge from related studies indicated [Ill] as the easy magnetization direction, similar to that of nickel.&apos; Therefore, a cube orientation, if present in the tape core, would be most detrimental to its magnetic performance.3 In its cold-rolled state the tape had < 111 > directions in the rolling plane 14.5 deg from the rolling direction.&apos; But the coercive force of the tape in such condition will be excessive due to large amounts of internal stresses, and therefore makes its use impossible for memory applications due to long switching time. In lower nickel alloys, suchas 50-50 nickel-iron and 65 pct Ni-Fe sheets, previous investigators4"7 found the presence of cube texture on annealing at 900° to 1000°C. Although no cube texture was found in annealed 1/8-mil tape,"&apos; its presence in some annealed 1,/4-mil tape cores was firmly established a year ago as verified by significant differences in magnetic properties. The present investigation is devoted to the orientation study and related magnetic measurements on three thicknesses of the ultra-thin tape, namely, 1/8 mil, 1/4 mil, and 1/2 mil, cold rolled directly from annealed 4-mil stock in the cold-rolled state as well as after they were annealed at 760°C (1400° F) and 927°C (1700°F). The results obtained might serve to elucidate the development of annealed texture as well as to establish clearly the importance of preferred orientation on the magnetic performance of such memory tape core despite its well-known low magnetic anisotropy exchange energy. EXPERIMENTAL PROCEDURE Samples were taken from one production heat (0.010 wt pct C, 0.004 P. 0.016 S, 0.80 Mn. 0.29 Si. 79.69 Ni. 4.42 Mo. 0.054 Co, 0.002 Ti, 0.12 Al, 0.04 Mg, 14.56 Fe). Annealed 4-mil sheets were cold re-

Jan 1, 1962

By A. G. Guy

Zinc vapor from a reservoir of liquid zinc maintained at lower temperatures was diffused into sets of copper-zinc alloys at 759° and 870° C and into sets of silver-zinc alloys at 650° and 700° C. Each set of ,four copper-zinc alloys consisted of pure copper and 90/10, 80/20, and 70/30 brass. Similarly the set of silver-base alloys consisted of specimens containing 0, 7, 15, and 20 pct Zn. Natural markers at the initial surfaces of the specimens ware "trapped" under a thin electroplate and their depth of burying was measured after diffusion. The ratio of diffusivities of the two components determined from these data and the chemical diffusion coefficient calculated by the Matano method agreed with previously reported results. The line of markers was irregular and was often discontinuous when a grain boundary was crossed. TECHNIQUES involving the vapor phase have been widely employed in studying diffusion phenomena in metals. Many investigators have evaporated the more volatile component from an alloy, but it is generally believed that the porosity created under these conditions interferes with adequate interpretation of the experimental results. The extensive work of Gertsriken6 has been criticized on this score. Accary1 found that the diffusion coefficient for de-zincification of brass is larger by a factor of five than that for zincification, although he attributed the difference to a higher vacancy concentration under conditions of dezincification. Balluffi and siegle2 thoroughly investigated the technique of adding a more volatile component to a less volatile base metal as a means for studying diffusion. They verified that no porosity forms in a brass under these conditions and that the diffusivities of the two components can be determined from observations of the motion of markers originally placed on the surface of the specimen. The mathematical analysis that they developed for treating the experimental data was modified in a later note, but essentially it involved using the graphical Boltzmann-Matano method that is customarily applied to solid-solid diffusion couples. The experimental method used in the present research was similar to that employed by Balluffi and Siegle except for two modifications. Balluffi and Siegle used alloy chips as the source of metal vapor. This procedure has the disadvantage that the concentration of solute at the surface of the specimen changes during the diffusion experiment as the alloy content of the chips is gradually decreased. This disadvantage was overcome by employing liquid zinc as the source of zinc vapor in a manner similar to that described by Herasymenko.9 There was then no limitation on the amount of solute usefully available, and several relatively large specimens could be diffused in a given experiment. The second modification was the use of natural markers on the surface of the specimen rather than larger, artificial markers, such as the alumina powder employed by Balluffi and Siegle. It was expected that the fine, natural markers would permit more precise measurement of the buried interface as in the case of ordinary sandwich specimens.10 EXPERIMENTAL The experiments were designed so that zinc from the vapor phase would maintain a constant zinc content at the surface of pure copper (or silver) and

Jan 1, 1960

By W. M. Phillips

Processing kaolin clays from the sedimentary deposits of Georgia and South Carolina is described in this article. While the major processing steps are touched on briefly, emphasis is given to the dewater-ing of the clay-water slurries (slips) formed in the processing of kaolin clays. The dewatering steps discussed include gravity settling, centrifugal dewatering, vacuum filtration and thermal drying. Particular attention is given to vacuum filtration and the variables affecting filtration of these kaolin clays. Kaolin consists essentially of the mineral kaolinite, which is a hydrated aluminum silicate (Al2O3 . 2SiO,). Commercial deposits of kaolin occur in several areas of the U. S., but approximately 90% of the kaolin produced in this country comes from Georgia and South Carolina. These deposits are of sedimentary nature and occur in a geological fall line in the Tuscaloosa formation at elevations between 300 and 450 ft above sea level. Over two million tons of kaolin clays are used by industry in the U. S. each year. A big percentage of this tonnage is used in the paper industry for coatings in making glossy and high quality grades of printing papers. In addition, large tonnages are used as pigments; as fillers for rubber, plastic and fertilizers; and in ceramics. Properties of kaolin that make it widely used in the above applications are its particle size fineness, natural whiteness, chemical stability and non-abrasiveness. In addition to these desirable properties, it is relatively inexpensive. The finer coating grades of clays range in price from $15 to $28 per ton while the coarser filler grades sell within a range of $7 to $13.50 per ton. Pure kaolin particles are small hexagonal flat platelets. Above the 2-p size, the particles usually consist of stacks of plates, while below the 2-p particle size they occur as individual flat, hexagonal plates. Since these individual platelet particles provide the most desirable coating and flow characteristics, major importance is given to particle size fractions of 2 p and smaller. Generally, coating grade clays are those with all particles smaller than 15 p and at least 70% of the particles less than 2p. These coating grades also have 50% or more of the particles smaller than 1 µ in size. The extremely fine grades of coating clay currently being produced approach the range of 100% smaller than 2p. The filler grades of kaolin have 100% of the particles passing 325 mesh but have less than 70% of their particles below the 2-p range. Fig. 1 is a schematic representation of the major processing steps involved in preparing kaolin clays for marketing. MINING All kaolin mining is open pit. The ratio of overburden to clay will average 3:1, but this ratio can, of course, be much higher depending upon the grade of the clay and the size of the deposit. Most of the commercially mineable deposits occur from 20 to 120 ft below the ground surface. Both draglines and pans are used in removing the overburden and mining the clay deposit itself. After mining, the most common method of transporting the clay to the processing plant is by blunging or re pulp-

Jan 1, 1963

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen&apos; determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By C. W. Spencer, Che-Yu Li, R. J. Knight

The usual reaction product for the monotectic reaction in the Bi-Se system consists of rod -shaped particles of selenium-rich liquid embedded in a single crystal matrix of At certain crystallo-graphic orientations of the matrix with respect to the reaction interface, more complex shapes are as -sumed by the liquid particles. This reaction has been examined at different growth rates and relative crystallographic orientations of the matrix with respect to the reaction interface. The uhriation in auerage particle size of the liquid phase with reaction rate has been determined at one crystallograpIzic orientation of the matrix. On a plot of logarithm of average particle diameter vs logarithm of reaction rate, data points for crystals grown at rates of 10- to 1.0 cm per hr fall near a curve of slobe -0.4. MONOTECTIC reactions in binary alloy systems are reactions of the eutectic class in which, as the system is cooled through the three-phase reaction isotherm, one liquid phase (L) decomposes to a solid phase and another liquid phase (LII).&apos; A partial phase diagram, as taken from Hansen, showing the monotectic reaction in the Bi-Se system is given in Fig. 1. This diagram specifies the monotectic point at 618°C and 72 at. pct Se, and the monotectic reaction products as the intermetallic Bi Se3 and a liquid (LII) which contains approximately 98 at. pct Se. At a lower temperature, 217°C, this liquid may undergo a eutectic reaction in which the reaction products are BizSe3 and crystalline selenium. However, under conditions of rapid cooling, or quenching, from above 217°C, this selenium-rich liquid may be partially retained to room temperature in an amorphous or glassy state. The intermetallic BizSe3 is rhombohedral, of the space group jm;&apos; however, for convenience it is usually represented by a hexagonal struture. A pronounced plane of cleavage, which lies perpendicular to the main axis of the rhombohedral unit cell or parallel to the basal plane of the hexagonal cell, exists in the structure. The usual monotectic reaction product consists of rod-like particles of LII embedded in a single-crystal matrix of BizSe3, although at certain crystallographic orientations of the matrix BizSe3 other more complex shapes are assumed by LII. A similar rod-like, or cylindrical, morphology for the carbide phase has been reported by westbrook7 in the a Cr-Crz3Ce eutectic structure. In this paper the morphological characteristics of the LII particles, as retained to room temperature, have been examined under conditions of varying growth rate and crystallographic orientation of the matrix BizSe3 with respect to the growth direction. EXPERIMENTAL PROCEDURE Alloy specimens corresponding to the monotectic composition, 72 at. pct, or 50 w pct Se, were prepared from 99.999 pct pure bismuth and selenium obtained from the American Smelting and Refining Co. The two elements, corresponding to a total specimen weight of approximately 30 g, were encapsulated in 13 mm OD Vycor tubing under a vacuum of 5 x X mm of Hg. The capsules were suspended on a fine platinum wire in a Bridgman-type furnace which exhibited a temperature gradient of

Jan 1, 1963

By V. A. Phillips, M. Safdar Ali

The tensile properties of Cu-0.20 pct Al, Cu-0.45 pct Mg, Cu-0.27 pct Cr, and Cu-0.22 pct Be solid-solution alloys were studied at -196°, 18°, 2509 and 500°C on wires internally oxidized at 900°and 1000°C. Internal oxidation produced marked increases in yield strength relative to pure copper, particularly at low temperature. The yield strength decreased with increase in temperature to a much greater extent than predicted by current theories of dispersion hardening. The strengthening effect of internal oxidation persisted throughout the entire stress-strain curve, but since a marked loss of ductility occurred at all test temperatures, only modest increases in tensile strength were realized. INTERNAL oxidation involves the preferential oxidation of a baser solute in a relatively noble solvent by diffusion of oxygen into the solid. Since the process is diffusion controlled, it is expedient to carry it out at a high temperature often approaching the melting point. The amount of solute is limited and the oxidation conditions adjusted so that oxygen diffuses inwards to meet the solute causing reaction to progress inwards and form subscale instead of only sur face scale. The reaction can be made to occur throughout the thickness of thin material producing a fine dispersion of oxide inside the metal. C. S. Smith1"3 appears to have been the first to recognize the true nature of the process of internal oxidation. Although extensive kinetic and metal-lographic studies followed by Rhines and coworkers,4-5 Chaston7 andMeijering and Druyvesteyn8 working independently were the first to report hardening effects due to internal oxidation. These results prompted detailed studies of the effects of internal oxidation on the hardness, tensile, creep, and fatigue properties of a number of alloys by G. C. Smith and coworkers9-12 in England, on hardness by Gottardi13 in Italy, and on hardness and tensile properties by wood14 in the U.S.A. Publications dealing with other aspects of internal oxidation will not be reviewed here. Internal oxidation of solutes having a high affinity for oxygen provides a means of obtaining very fine dispersions stable in a suitable atmosphere at temperatures well above those at which most age harden ing precipitates coalesce. The process therefore offers a method of producing thin sheet and wire of possibly outstanding creep resistance. The size limitation might be overcome by internally oxidizing porous powder compacts made from alloy powder before final sintering. PREPARATION OF ALLOYS The alloy ingots, which were approximately 5 1/2 in. long by 1 in. diam, were made up in a high-frequency furnace, using as raw materials OFHC copper, 99.99 + pct Al, high-purity magnesium, and master alloys of Cu-4.19 pct Be and Cu-10 pct Cr. The alloys containing aluminum and magnesium were melted ii closed high-purity graphite crucibles and solidified in the crucible which was lowered partly Out of the coil to give a hot-top effect. The alloys containing beryllium and chromium were made by melting in vacuo in alumina-lined sillimanite crucibles. The magnesium, chromium, and beryllium

Jan 1, 1960

By Nicholas J. Grant, David S. Bloom

An investigation of the Cr-Ni system has revealed that there exists a eutectoid transformation at about 1180°C. &apos;The transformation in chromium implied by the eutectoid reaction was detected at about 100°C below its melting point. Associated with the eutectoid transformation, a metastable transition structure has been found. THE Cr-Ni phase diagram is shown in current literature to be a simple eutectic system in which the high chromium end of the diagram is incompletely determined, Fig. 1. The last investigation of this system was undertaken in 1936.&apos; Because of limitations in metal purity, especially of chromium, and temperature measuring techniques, the diagram should be accepted with some reservations, as was indicated by Hansen.V or examwle.-, the wresence of the compound Cr²Ni, with a tetragonal structure," remains unverified and incompatible with the simple eutectic diagram. The work reported here began because of discrepancies that appeared in experimental studies in the binary alloys Cr-Ni and in the ternary system Cr-Mo-Ni. The existing binary Cr-Ni diagram failed to provide a complete explanation of observations made by microscope, X-ray, and thermal analyses. Experimental Methods The materials employed were of a higher degree of purity than were available to previous investigators. The Mond nickel used had a nominal purity of 99.87 pct, while the electrolytic chromium analyzed 99.03 pct with the major impurity being 0.5 to 0.7 pct oxygen with some iron. All alloys were melted in a vacuum furnace to remove dissolved gases, sufficient carbon was added to the charge to combine with all the oxygen as CO. Final analysis determined the carbon as about 0.02 pct and the oxygen around 0.06 pct or slightly more. Stabilized zirconia crucibles and thermocouple protection tips were used throughout and contributed no detectable impurity to the melts, as long as the oxygen in the chromium was kept low. Heats averaged about 250 g, which permitted about 2 in. of the thermocouple protection tips to be submerged. The temperature drop across the thermocouple protection tip was determined to be about 3°C, a minor source of error. The alloys, after removal from the vacuum furnace, were placed in a furnace operating in a purified argon atmosphere for the thermal analyses. An- nealed wolfram-molybdenum thermocouples provided the primary means of temperature determination, though a Pt-Pt-10 pct Rh couple was employed for a check when possible. A sensitive, high-speed Leeds and Northrup Speedomax recording potentiometer indicated the thermocouple output. X-ray diffraction patterns were obtained primarily on a Norelco unit, which permitted diffraction angles only up to 45" (28 = 90"). In general, either rotated or stationary solid samples were used, because it later evolved that many samples were susceptible to transformation resulting from the cold working involved in pulverizing. It was also noted that rotating a sample sometimes suppressed weak lines, so, usually, samples were not rotated. Later a high temperature camera was adapted for use at temperatures up to 1400 °C on the Norelco unit utilizing both solid and powdered samples. Unless otherwise noted, all X-ray patterns were made with a chromium tube and a vanadium filter. Further-

Jan 1, 1952

By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.&apos;-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton&apos; argued in favor of silicification of erosion

Jan 1, 1951

By J. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies. THE Picher Mining Field, fig. 1, which lies between Baxter Springs, Kansas, and Commerce, Okla., is the most intensely mineralized and the largest zinc-lead ore producing area in the Tri-State District of Missouri, Kansas, and Oklahoma. It has a vast lateral extent of underground workings that is unequaled for the observation of the geology of zinc-lead ore bodies in sedimentary horizons; and thousands of churn drill holes in the unmined areas supplement the underground observations with useful data for the interpretation of the geology. This paper is confined to the ore deposits of the Picher mining field. The reader is referred to the bibliography for the general geology of the Tri-State district which has been ably covered by many geologists. The writer was co-author of several publications on the Tri-State district.&apos;-" This paper is necessarily a repetition of parts of those publications but contains a few changes and additions on the deposition of the minerals. The parts of this paper concerning mineralization maps and pipe slump-structures are not covered in the above publications. Geology The geology of the Picher mining field is similar to that of the entire Tri-State district because the sedimentary horizons that are found here are found throughout the district, and the ore bodies in the respective horizons have similar characteristics. The beds that contain the ore bodies in the Picher field are illustrated and described in fig. 2. The five unconformities found in the mines of the Picher field are indicated on the geologic section, fig. 2. The unconformity shown at the base of Meramec (B bed) is relatively unimportant since B bed was mostly eroded from the area of the Picher field before the Chester beds were deposited. B bed has been observed in the cuttings from only a few churn drill holes. The Pennsylvanian (Cherokee shale) formation is the top horizon found in the Picher mining field. It has been eroded from the southeastern part of the field, but because of the regional dip of the sedimentary beds to the west, it attains thicknesses of 100 ft to 200 ft along the west edge of the field. It is 200 ft to 300 ft thick in the Miami trough. It was deposited on the Boone limestone surface, which contained relatively few shallow erosion channels and very few depressions. Subsequent to the deposition of the shale, solution of limestone from underlying limestone horizons by circulating solutions caused the overlying beds, including the Cherokee shale, to slump into the larger openings formed by the solution and removal of the limestone. Chert The origin of the chert in the Tri-State district has been a controversial subject among geologists. Tarr7 advocated a syngenetic origin for the chert, postulating that it formed from colloidal silica deposited in the Mississippian seas. Leith, Dake and Leighton&apos; argued in favor of silicification of erosion

Jan 1, 1951

By R. Maddin, A. Lawley

Single crystal Mo-Re alloys (99.99+ purity), grown by electron bombardment floating zone heating, were deformed in tension at temperatures from -196° to +200°C. At -196oC, Mo-6 pet Re and Mo-20 pct Re alloys deform by slip on systems of the type (101) [1ll]. Above-78oC, the operative slip system is of the type (112) [111], (101) [1ll], or (211) [1ll], depending upon orientation. Mo-39 pct Re alloys deform by twinning and slip at all test temperatures with a (112) [111] type twinning system. Critical resolved shear stress for slip and twinning is calculated as a function of composition and temperature, and the mechanical properties compared with those of less Pure polycrystalline alloys. HEXAGONAL close-packed rhenium, c/a = 1.615, is highly soluble in molybdenum. The bee molybdenum-rich solid solution extends to approximately 42 at. pet Re* at 2500°C,&apos; Fig. 1. Recent work on polycrystalline alloys has shown conclusively that the addition of rhenium to molybdenum improves both the fabricability and the low-temperature ductility.2"5 Similar behavior is observed for W-Re and Cr-Re alloys.5 Initially, Geach and Hughes2 found that the Mo-30 pct Re alloy could be cold rolled to approximately 90 pct reduction before the onset of cracking. The remarkable effect of the rhenium was later confirmed by Jaffee et al. 3-5 with an optimum condition of maximum strength combined with maximum ductility at the Mo-35 pet composition. At higher rhenium contents, the ductility was severely impaired due apparently to the presence of brittle tetragonal s phase, Fig. 1. In the Mo-35 pet Re alloy, at least 110 ppm (parts per million) oxygen could be tolerated before cold workability was reduced. By comparison, the corresponding tolerance figure in unalloyed molybdenum is ~ 10 ppm. The effect of rhenium was considered in terms of: 1) a reduction in oxygen solubility in the lattice; 2) a redistribution of intergranular oxide from grain boundary films to isolated spheres; and 3) the promotion of twinning as a further mode of plastic deformation. Paradoxically, twinning is often associated with brittle fracture in iron and the silicon irons.6&apos;7 Work to date has been restricted to are-melted and powder metallurgy polycrystalline material of ~ 99.9 pet purity. The present investigation was initiated for the purpose of determining the mode and crystallography of plastic deformation of a series of bee Mo-Re alloy single crystals over a wide temperature range from -196o to +200°C. Using high-purity zone-melted material (~ 99.99 + pet purity), the specific role of rhenium in the molybdenum lattice may be understood more fully since effects due to grain boundaries and oxide redistribution will be absent. At the same time, the study provides a comparison of single and polycrystalline deformation behavior. EXPERIMENTAL TECHNIQUES A) Preparation and Purity of Single Crystals. Alloys in the form of either are-cast and swaged or sintered and ground bar, 0.120 in. diam, were obtained from the Chase Brass and Copper Co. Alloy single crystals ~ 8-in. long were grown from the

Jan 1, 1962

By D. C. Shelton

This paper discusses the metallurgical testing procedures and their applications at the laboratories and mills of Pima Mining Co. The author shows, using discussions and case histories, that routine sampling and evaluation of daily and monthly data can be as valuable as thorough laboratory investigations and mill test work. A great deal of valuable information can be made available this way. This paper discusses laboratory and mill metal-lurgical testing procedures and their applications at Pima Mining Co., located about 25 miles southwest of Tuscon, Ariz. The Company, incorporated in 1951 (the year the orebody was found) in California to operate the Pima mine, is jointly owned by Cyprus Mines Corp., Utah Contruction and Mining Co., and Union Oil Co. Milling started in December 1956. The main Pima orebody is a contact metamorphic vein of copper-bearing hornfels with an average dip of 45° to the south with an east-west strike. The hanging and footwalls are quartzitic pyroclastics (arkosite) containing some sulfides. Barren igneous intrusions are also present. Conglomerates and alluvial wash cover the deposit to a depth averaging about 200 ft. The principal copper mineral is chal-copyrite. Native copper, chalcocite, and minor amounts of chrysocolla and other copper minerals are also present, together with sphalerite and some molybdenite. Generally, it has been noted that the ratio of chalcocite to chalcopyrite is higher in the lower grade ores, while as the grade increases, there are only minor amounts of chalcocite. Open pit mining is employed at Pima, using both trucks and an inclined skiphoist system. A detailed description of Pima Mining Co. operations was presented by Spaulding et all. More recently another orebody to the north and east of the present pit has been discovered and will be placed in operation within a few years. This ore is of a porphyritic rather than a lode nature since values are disseminated in both igneous and metamor- phosed sedimentary rocks. The new orebody is expected to be harder and cleaner than the present deposit. The views expressed in this article are those of the author and do not necessarily reflect those of Pima Mining Co. nor of the profession in general. PlMA MILL The following outline of milling practice is presented to furnish a background for later chapters of this report wherein specific problems will be detailed and analyzed. Run of mine ore is crushed in three stages, using conventional equipment to 85% minus 1/2-in. for feed to two 10 x l6-ft rod mills operating in open circuit. Each rod mill discharge is split between two 10% x 13-ft ball mills in closed circuit with three 20-in. cyclones. In addition, a 7 x 12-ft ball mill with one 20-in. cyclone receives part of the discharge from one of the rod mills. This equipment was manufactured by Allis Chalmers and Equipment Engineers. The cyclone overflows are combined, sampled and, after joining the regrind cyclone overflow, are distributed into 12 10-cell Fagergren 66-in. flotation machines. The primary rougher concentrate produced

Jan 1, 1965

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer&apos;s patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly &apos;7&apos; according to one bibliography, Over go per &apos;ent were concerned with the metallurgical phase and less than &apos;0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer&apos;s patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly &apos;7&apos; according to one bibliography, Over go per &apos;ent were concerned with the metallurgical phase and less than &apos;0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By N. S. Stoloff, M. Gensamer

Pyramidal (1122) slip was observed in cadmium single crystals deformed in compression and bending at room temperature and —196°C. Crystals tested in tension twinned with no evidence of pyramidal slip. A critical resolved shear stress law for the propagation of twin nuclei appears probable. Twinning and low-stress kinking are believed to inhibit the appearance of pyramidal slip under ordinary experimental conditions. SEVERAL reports of nonbasal slip in cadmium have appeared in the literature recently, two of the reports having appeared after work on this project was in progress. Brown1 reported cross slip on electron micrographs, but did not identify the cross-slip plane. Wernick and Thomas2 observed nonbasal slip traces parallel to [1123] on a crystal bent with a pair of tweezers, but this too was an isolated observation, with no confirmation of the glide plane. The critical stress for pyramidal glide, and the temperature and strain rate dependence of glide on this system were not discussed. price3 has reported some observations of nonbasal slip in thin films of cadmium with the aid of transmission electron microscopy, but a full publication of these observations was not available at this writing. Pyramidal (1122) <1123> slip also has been observed on zinc single crystals4, 5 and (1122) <1010> slip on magnesium single crystals,6 all oriented with the basal plane nearly parallel to the specimen axis. Since the choice of slip system in the hexa- gonal metals is generally believed to depend on the axial ratio, with basal slip predominating for high-axial ratios, the occurrence of pyramidal slip in zinc and cadmium is unexpected. The objectives of the present investigation were to confirm the existence of nonbasal slip in cadmium, to identify the slip system, and to obtain an estimate of the critical resolved shear stress, assuming that the resolved shear stress law is applicable. EXPERIMENTAL PROCEDURE Two purities of cadmium, 99.95 pet and 99.99+ pet, were employed. As received bars were cold swaged to 3/16 in. rounds. Bicrystals and tricrystals were prepared by passing the polycrystalline rods through a gradient without seeds. It was desired to obtain a large yield of single crystals oriented xo* < 5 deg, in order to be able to suppress basal slip during deformation by keeping the resolved shear stress on the basal plane to a minimum. Cylindrical single crystals of cadmium were prepared by a seeding technique developed by Weiner,7 to obtain a predetermined orientation. The single-crystal rods were sectioned to specimen size by an acid-cutting technique originally developed for zinc crystals.&apos; An aqueous solution of nitric acid was the cutting agent. The acid was picked up by a plexiglass disc spinning at an optimum cutting speed through the acid, which was contained in a sump-like arrangement. The section to be cut, the acid bath, and the spinning disc were enclosed in a plexiglass case. The rod to be sectioned was coated with a thick layer of collodion. At the points at which sectioning was to be effected, the collodion was removed over a length of about 1/8 in. by dissolving it in acetone. To prepare a surface suitable for microscopic exam-

Jan 1, 1962

By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By John T. Galey

The outstanding developments of the year in southwestern Pennsylvania were the establishment of the Summit Fayette County gas pool and the gas pool in Nicholson township, Fayette County, and Monongahela township, Greene County, as major producing areas, and the indication of four new shallow gas pools. Curtailment of drilling for shallow gas is expected to follow order M68 of the Office of Production Management. Gas completions were approximately 70 per cent higher, oil completions nearly 25 per cent lower, dry holes were unchanged and drilling wells as of Dec. 31, 1941, nearly loo per cent higher than last year. Shallow Development Oil.—Outside Butler County, only 11 producers were drilled, with a total initial of 221 bbl. The best of these was in a portion of Gilmore township, Greene County, which ordinarily produces gas. This well flowed 77 bbl. in 11 hr., along with about one million cubic feet of gas from the Fourth (U.Dev.) sand. Washington County had a 10.20 and a 25-bbl. well in Morris township and a 20-bbl. well in South Franklin township. These were all in the Fifth Sand. The price of oil to Jan. 27 was $1.80 per barrel, when a 15¢ increase was made. This was followed by a raise of 20¢ on Apr. 23, 15¢ on May 21, 20¢ on June 18 and 25¢ on Aug. 14. The last increase was canceled on Aug. 23 by the Office of Price Administration, which pegged southwestern Pennsylvania crude at $2.40 per barrel. Gas.—An almost doubled initial production of natural gas is the result of the large increase in number of wells drilled. The outstanding discovery of the year was in the vicinity of Armbrust, Hempfield township, Westmoreland County, where a well drilled to what at first was considered the Bayard sand, but what is now known to be the Fifth (U.Dev.) sand, at 2100 ft. found nearly 5 million cu. ft. of gas. Since this completion 14 wells have been finished, only one of which was dry, giving a combined total open flow of approximately 15 million cu. ft. The sand is 35 to 40 ft. thick and the saturation extends through most of that thickness. Rock pressure, which is 1040 lb. per sq. in., is abnormally high. An area of only about one square mile has been proven but some of the 24 new wells drilling as of Dec. 31 will no doubt extend it considerably. This development has taken place in an area heretofore considered to have had little prospect. There were three good wells in other parts of Westmoreland County. One well in Franklin township, which had 12 million cu. ft, of gas in the Fifth sand, was entirely surrounded by dry holes but is still pro- . ducing at a high rate. In Bell township a 1.6 million cu. ft. well was found in the Speechley (U.Dev.) sand and in Washington township the same sand produced 2.7 million cu. ft. with shut-in pressure of 970 Ib. at 2820 ft. This well is offset by two dry holes and one well with a capacity of only 10 M cubic feet.

Jan 1, 1942

By John T. Galey

The outstanding developments of the year in southwestern Pennsylvania were the establishment of the Summit Fayette County gas pool and the gas pool in Nicholson township, Fayette County, and Monongahela township, Greene County, as major producing areas, and the indication of four new shallow gas pools. Curtailment of drilling for shallow gas is expected to follow order M68 of the Office of Production Management. Gas completions were approximately 70 per cent higher, oil completions nearly 25 per cent lower, dry holes were unchanged and drilling wells as of Dec. 31, 1941, nearly loo per cent higher than last year. Shallow Development Oil.—Outside Butler County, only 11 producers were drilled, with a total initial of 221 bbl. The best of these was in a portion of Gilmore township, Greene County, which ordinarily produces gas. This well flowed 77 bbl. in 11 hr., along with about one million cubic feet of gas from the Fourth (U.Dev.) sand. Washington County had a 10.20 and a 25-bbl. well in Morris township and a 20-bbl. well in South Franklin township. These were all in the Fifth Sand. The price of oil to Jan. 27 was $1.80 per barrel, when a 15¢ increase was made. This was followed by a raise of 20¢ on Apr. 23, 15¢ on May 21, 20¢ on June 18 and 25¢ on Aug. 14. The last increase was canceled on Aug. 23 by the Office of Price Administration, which pegged southwestern Pennsylvania crude at $2.40 per barrel. Gas.—An almost doubled initial production of natural gas is the result of the large increase in number of wells drilled. The outstanding discovery of the year was in the vicinity of Armbrust, Hempfield township, Westmoreland County, where a well drilled to what at first was considered the Bayard sand, but what is now known to be the Fifth (U.Dev.) sand, at 2100 ft. found nearly 5 million cu. ft. of gas. Since this completion 14 wells have been finished, only one of which was dry, giving a combined total open flow of approximately 15 million cu. ft. The sand is 35 to 40 ft. thick and the saturation extends through most of that thickness. Rock pressure, which is 1040 lb. per sq. in., is abnormally high. An area of only about one square mile has been proven but some of the 24 new wells drilling as of Dec. 31 will no doubt extend it considerably. This development has taken place in an area heretofore considered to have had little prospect. There were three good wells in other parts of Westmoreland County. One well in Franklin township, which had 12 million cu. ft, of gas in the Fifth sand, was entirely surrounded by dry holes but is still pro- . ducing at a high rate. In Bell township a 1.6 million cu. ft. well was found in the Speechley (U.Dev.) sand and in Washington township the same sand produced 2.7 million cu. ft. with shut-in pressure of 970 Ib. at 2820 ft. This well is offset by two dry holes and one well with a capacity of only 10 M cubic feet.

Jan 1, 1942

By E. F. Bradley, R. I. Jaffee, H. R. Ogden, E. S. Bartlett, D. N. Williams

The mechanical properties of solid-solution-strengthened columbium alloys have been assessed as a function of alloying additions. Studies included the effects of tungsten, tantalum, molybdenum, and vanadium. Elevated temperature fabrication was required at alloying levels above about 15 pct W or 10 pct Mo. Tungsten, molybdenum, and vanadium additions increase tensile strength at room temperature and 2200°F, but tantalum additions exert little strengthening. Similarly, tungsten, molybdenum, and probably vanadium additions increase the ductile-to-brittle transition temperature, and tantalum additions decrease this parameter. The 2200°F stress-rupture strength is increased by tungsten and molybdenum additions; with 20 to 25 at. pct additions, 100-hr rupture strengths of 30,000 psi are obtainable. Small vanadium additions exhibit mild stress-rupture strengthening, and tantalum additions are innocuous. At 2500°F, tungsten additions retain stress-rutpure strengthening capability, but molybdenum additions are much less effective. Tantalum additions augment the stress-rupture strengthening of tungsten plus molybdenum additions at 2500°F. Of the refractory metals, columbium possesses specific potential for structural use in the temperature range from 2000" to about 2500°F. Desirable features of columbium are its good low-temperature ductility, ease of fabrication, oxidation mechanics (lack of a volatile oxide at moderate temperatures), good availability and reserves, and relatively low density. However, alloying is required to provide attractive strength at elevated temperatures. Published information concerning alloying be- havior of columbium relative to mechanical properties is sketchy, particularly in consideration for long-time applications at temperatures in excess of 2000°F. Only a few stress-rupture data at temperatures from 2000" to 2500°F have been reported;&apos;-&apos; these are too meager to allow rationalization of the effects of various alloying additions on creep or stress-rupture properties. Additional published data do, however, give some insight toward understanding of systematic alloying behavior for columbium relative to low-temperature strength4-&apos; and ductility,&apos; and elevated temperature tensile behavior.4,6 This paper is intended to augment previous knowledge, and to promote understanding of the alloying behavior of columbium for long-time structural service at elevated temperature. BASIC CONSIDERATIONS Solid-solution strengthening is recognized to be of prime importance in improving strength in columbium-base alloys. Other strengthening mechanisms may be (and are, in current alloys) used to augment solid-solution strengthening. As strengthening results primarily from lattice distortion, the strengthening effectiveness per atom depends upon atomic size mismatch between solvent and solute. Another factor in this regard is conformance to ideal solution behavior in the solid solution. Thus, for example, despite appreciable differences in the degree of mismatch between tungsten (5 pct), molybdenum (5 1/2 pct), and vanadium (7 1/2 pct) in solution in columbium, all are about equally effective in straining the columbium lattice at room temperature.&apos;-&apos; Similarly, tantalum additions do not strain the columbium lattice, and little strengthening is expected. Size effects being equal, maximum solution strengthening at high temperatures is anticipated to result from the addition of elements that increase the melting temperature of columbium. This expectation is based on an increase in the electronic bonding forces exhibited in the transition metal series as electronic structures approach those of the Group Vl metals. Of the metals that exhibit ex-

Jan 1, 1963