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[NORTH AMERICA UNITED STATES Alabama BIRMINGHAM BURROWS, WILLIAM C. CORD, RICHARD H. COSTON, OTIS D. JR. FAIRHOPE RUFFLES, WILLIAM R. HUNTSVILLE WAGGONER, JERRY B. MOBILE PETROUTSON, PETER C. SELMA JONES, JAMES J. JR. UNIVERSITY CUDWORTH, JAMES R. JONES, WALTER B. RICHARDS, EDWARD F.]

Jan 1, 1961

By F. H. Wilson, R. M. Brick

WITH the papers of Palmer and Smith1 and of Burghoff and Bohlen,2 published in 1942, understanding of the problem of the development of ears on deep-drawn brass cups was brought to the point where, from a practical standpoint, producers of brass sheet could keep earing under control. However, these very practical results raised questions concerning the reasons for the observed behavior. Since plastic deformation is fundamentally a function of crystallographic slip, these reasons must be considered in the light of the textures to be found in the annealed sheet. Various attempts have been made to interpret the mechanism of ear formation by correlation with the preferred orientation and the anisotropy of the sheet. However, none of these has satisfactorily explained why ears are usually found in the rolling and transverse directions for copper but at 45° to these directions for brass. This paper offers additional data on these two related subjects and has been divided into two sections. The first section provides a survey of the recrystallization textures of brass as affected by annealing temperatures and prior reductions, and an account of the earing behavior which accompanies these textures. The second section reports new data on the anisotropy that accompanies a characteristic texture for brass and endeavors with partial success to establish the factors that account for the difference in earing behavior between copper and brass. EARING BEHAVIOR OF BRASS Review of Textures The recrystallization texture of severely rolled brass was first reported by Bass and Glocker.3 The preferred orientation to which this texture, obtained from metal annealed at 500°C., was most akin was (113)[112]. This texture has been confirmed by Bauer, von Göler and Sachs;4 Brick;* Brick, Martin and Angier;6 and Cook and Richards7 who, in general, used annealing temperatures under 500°C. Bass and Glocker3 also reported the recrystallization texture at 850°C. to be the same as at 500°C. They analyzed their textures by means of single photograms obtained with white radiation. The photograms for both temperatures are reproduced in their paper, and there is a strong similarity between the two. However, for the latter temperature, the number of spots registered on the film was remarkably large for the grain size to be expected, and the authors made no mention of using a technique that would integrate a large enough area of the specimen to produce so many spots. The only other attempt to determine textures resulting from high temperature

Jan 1, 1945

By Earle Schumacher

COPPER-CALCIUM alloys are of interest as materials for use in deoxidized conductors of high conductivity. That calcium is effective in deoxidizing and degasifying copper is well known. Brandenberg and Wiens1 have described the use of calcium in the casting of sound copper and state that the deoxidation can be carried out without difficulty. The castings that they prepared were sound and sufficiently ductile to permit wire drawing. Pratt,2 in British Patent No. 1699 (1907), has claimed the use of calcium for the deoxidation and degasification of copper. Masing3

Jan 1, 1929

By T. H. Oxnam

The predominating value of the ores now being treated by the Palmarejo and Mexican Gold Fields, Ltd., is silver, although some gold also is carried. The present method of treatment consists of wet-crushing and concentrating, followed by the cyanidation of the un-roasted sands and slimes. The sands are treated by leaching, and the so-called " accumulated slimes " by a system of agitation and decantation. It is only within very recent years that the cyanidation of unroasted silver-ores has been commercially successful. In fact, at the time operations were begun at the cyanide-plant at Chinipas, February, 1902, I knew of no other leaching-plant treating similar ores successfully. The cyanide treatment of the Palmarejo ores differs but little from the ordinary practice in cyaniding gold-ores; and perhaps but little, if any, new information concerning the metallurgy of silver is to be gleaned from it. Palmarejo Mines. The Palmarejo mines are located in the southwestern part of the State of Chihuahua, Mexico, on the foothills of the Sierra Madre mountains, at an elevation of 3,200 feet. The mills, 12 miles distant, are situated on the Chinipas river, near the town of Chinipas, which is about 150 miles northeast of Agiabampo, on the Gulf of California. Supplies are shipped via this port as this route is the best and most direct to the property. The ore-bodies in the Palmarejo mines have been deposited along a series of rock-fractures, caused by an intrusion of eruptive rock. The most important of these fractures or fissures, both in width and value, are the Prieta and Blanca veins, which

Jan 1, 1906

By Oscar M. Wicken

Industrial minerals - being the basic materials for much of the industrial activity in the world -suffer or gain in the market place with changes in that activity. The period 1970 and early 1971 has been one of little growth in many of the mineral-consuming industries, particularly those associated with building and construction. Consequently, the production of many commodities revealed little or no increase above 1969 levels. The pick-up of construction activity in the last half of 1971, however, is expected to be at an intensity which will result in an over-all good year; for example, cement shipments may, establish a record. Some industrial minerals products that bucked downward trends were those allied with the agricultural industry. Phosphate rock shipments increased, particularly from Florida which contributes over 400/c of the phosphate rock in the western world. Potash had higher sales and production for the third straight year, which means that inventories are being eased. The catch-all term of ecology is an oft-mentioned theme among industrial minerals suppliers. Specifically, the need for control of dust emissions is adding a heavy capital investment burden to many of the producers; such a burden, in fact, that plants have had to cease operations because the cost of dust collection equipment could not be born. As an order-of-magnitude estimate, dust collection equipment for cement plants can run $2-3 million for a single plant; some estimates are that the total cost of dust collection equipment in a new plant can be approximately 20% of total investment. All minerals processers have dust control expense of greater or lesser proportion.

Jan 1, 1972

By G. P. Conard, E. H. Rennhack

The creep behavior of hot-rolled, hypoeutectic Zn-Ti alloys was investigated in the temperature range from 0.43 to 0.53 TM. Secondary flow was found to originate primarily from strain-induced gvain growth where grain boundary )nigvation served to relieve the strain energy of distortion introduced by slip, grain boundary sliding, and subgvain formation. The extent to which this recovery mechanism operated was determined by the ratio of grain width to the spacing between planar fibers of TiZn,, compound particles generated in these alloys during rolling. When this ratio was unity, creep resistance demonstrated a marked improvement. In this condition, which was fulfilled by annealing following rolling, structural stability was enhanced with decreasing grain size below the equicohesive temperature (-0.5Tm), while the reverse was true above this temperature. TITANIUM concentrations approaching the eutectic composition of 0.23 wt pctl have been shown to promote a significant increase in the creep resistance of rolled zinc,2 The alloying effect created with titanium is somewhat unique; a structure closely resembling that of a fiber-reinforced metal composite can be developed which selectively modifies creep strength in preference to other mechanical properties. In an earlier investigation,~ the present authors found that, while the fiber network, composed of individual TiZn,, compound particles, had a distinct influence on rolled texture, the crystallographic variations produced were of minor importance with respect to creep. Rather, creep resistance seemingly increased when the grain size appeared to coincide with the in-terfiber spacing. The work described here was undertaken to explore this effect in greater detail. EXPERIMENTAL PROCEDURE Three zinc-base alloys containing 0.05, 0.12, and 0.16 wt pct Ti were prepared from CP zinc and iodide titanium in the form of 4 by 2 by f in. chill-cast ingots. The melting and casting procedures for these alloys have been detailed el~ewhere.~ Individual ingots of each alloy were hot-rolled at 200°C (392°F) to total reductions of 10, 25, 50, 75, and 90 pct in from one to five passes, respectively, employing a 10-min reheat prior to each rolling pass. With grain, tensile-type creep specimens with a 1-in.-long, -in.-wide gage section were machined from the rolled strips for test purposes. Annealing studies to explore the influence of grain size on secondary creep flow were carried out at 400°C (752°F) in argon for times extending up to 60 min. The grain-size effect was evaluated in terms of average grain width and length values statistically derived from lineal intersection measurements.4 A similar method was applied in establishing the average interfiber spacing, i.e., average perpendicular distance between adjacent planar fibers. The creep characteristics of the alloys were investigated by means of constant-load and constant-stress creep tests. The former tests were conducted at 25°C (77°F) under an initial stress of 10,000 psi, while the latter were performed in the range from 25°C (77°F) to 90°C (194°F) at stress levels varying from 8000 to 22,000 psi. Total specimen strain, as determined with Budd HE-1161-B strain gages, was in excess of 0.10. Maintenance of constant stress was achieved through periodic load reductions made at 0.01 strain intervals to compensate for the attendant incremental reduction in specimen cross-sectional area. The maximum indicated error in the applied stress at these strain intervals was less than 3.0 pct. RESULTS AND DISCUSSION Constant-Load Creep. In an effort to clarify the in-terrelation between interfiber spacing and grain size with respect to the creep resistance of the Zn-Ti alloys, their separate effects on secondary creep rate were determined as a function of titanium content and rolling reduction. These results are set forth in Figs. 1 and 2, respectively. The average grain diameter plotted in Fig. 2 was resolved from average grain width and length values. No data are presented for reductions of less than 50 pct because of the inability to obtain consistent measurements on these strips. The curves of Fig. 1 indicated that, for a given titanium content, a decrease in interfiber spacing, as produced with increasing reduction, promoted a decrease in creep rate. Depending on titanium content, however, wide variations in creep rate occurred at the same interfiber spacing suggesting that interfiber spacing, by itself, has little or no influence on creep resistance. Grain size, on the other hand, decreased progressively with both increasing rolling reduction and titanium content, the effect of which led to a pronounced decrease in creep rate, particularly when the average grain diameter became smaller than 3.0 x 10"4 in., Fig. 2. The continuity of this relationship tended to support the view that grain size rather than interfiber spacing was predominant in controlling secondary creep. Annealing Effect. The observed dependence of creep flow on grain size suggested that a further contribution to creep resistance would result when the alloys were annealed to effect a coincidence between grain width and interfiber spacing, see Fig. 3(b). ~eiides creating an immediate barrier to grain boundary movement, annealing offered the possibility of providing increased structural stability by eliminating many high-energy, mobile grain boundaries.= To test this hypothesis, specimens from the Zn-0.16 Ti strips reduced 75 and

Jan 1, 1967

By Maurice Rey, Victor Formanek, Paul Chataignon

IT is found when floating oxidized lead ores by sulphidization, that the presence of calcium salts in the water is usually detrimental and lowers the recovery. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. The effect of calcium salts is readily visible. Whereas in their absence cerussite is quickly stained brown and then .black by sodium sulphide, in their presence the mineral remains very light in color. A similar- effect is produced when barium sulphide is used as a sulphidizing agent instead of sodium- sulphide. Magnesium salts have little or no effect and even tend to reduce the detrimental effect of calcium salts. A study of this phenomenon indicates that it is due to the precipitation of calcium or barium carbonate in contact ,with the mineral simultaneously with the formation of lead sulphide.

Jan 1, 1950

By Frederic L. Kadey

Diatomite is a siliceous, sedimentary rock consisting principally of the fossilized skeletal remains of the diatom, a unicellular aquatic plant related to the algae. Thus, it has been formed by the induration of diatomaceous ooze, and consists mainly of diatomaceous silica, a form or variety of opal which is first formed in the cell walls of the living diatom. Diatomaceous silica is not generally regarded as a synonym or the equivalent for diatomite, although it has been so used at various times. Accurately, diatomaceous silica is the preferred name for the principal mineral component of which the rock, diatomite, is composed. The terms diatomaceous earth and kieselguhr are used as synonymous with diatomite. The designations tripoli, tripolite, infusorial earth, etc., were used at one time but are now obsolete. With the changing nomenclature, these terms that were at one time correct when proposed and used for generations would be considered incorrect if used today in the light of current knowledge. The designation diatomite is reserved for those accumulations of diatomaceous silica that are of sufficient quality, size, and minability to be considered of potential commercial value. Processed diatomite possesses an unusual particulate structure and chemical stability that lends itself to applications not filled by any other form of silica. Foremost among these applications is its use as a filter aid, which accounts for over half of its current consumption. Its unique diatom structure, low bulk density, high absorptive capacity, high surface area, and relatively low abrasion are attributes responsible for its utility as a functional filler and as an extender in paint, paper, rubber, and in plastics; and as an anti-caking agent; thermal insulating material; catalyst carrier; and chromatographic support; polish, abrasive, and pesticide extender to name a few representative applications. The United States is the principal producing country, although diatomite is found in numerous other locations. Geology Composition and Morphology Diatomaceous silica qualifies as a. mineral of organic origin in much the same way that aragonite and collophane do. The silica of the fossilized diatom skeleton closely resembles opal or hydrous silica in composition (SiO2 • nH2O) .4, 12, 203 The silica is of acute biological significance, not only for the cell wall component, but also for the basic life process.45, 51 Without silica, cell development ceases .31 In addition to bound water, varying between 3.5 and 8%, the siliceous skeleton may also contain, in solid solution, or as part of the Si02 complex, small amounts of associated inorganic components-alumina, principally-and lesser amounts of iron, 46, 49, 55 alkaline earths, alkali metals, and other minor constituents.59, 63, 67 Boron is reported to be an essential element for diatom growth .52, 58 Since diatomaceous silica is not pure hydrous silica but contains other intimately associated elements, there is good reason to consider it a distinct type or variety.4 Associated with the diatomaceous silica, and integrated as part of the diatomite, may be variable amounts of organic matter, soluble salts, and particles of rock-forming minerals that were syngenetically deposited or precipitated with the diatom frustules. Sand, clay, carbonate, and volcanic ash are typical common contaminants. Other contaminating minerals may be present, such as feldspar, mica, amphiboles, pyroxenes, rutile, zircon-the result of weathering, then transporting, and subsequent redeposition of surrounding land masses. Commercial diatomite may also contain fragments and particles of

Jan 1, 1983

By C. R. Ince

THE term "differential flotation" is used to denote a flotation operation in which separation is effected between two or more minerals of the same class; e. g., lead sulfide from zinc sulfide, pyrite from blende, chalcopyrite from pyrite, chalcopyrite from blende. At present, so far as published work shows, there seem to be two theories as to the mechanics of differential flotation. The earlier and more generally accepted theory is that the so-called depressing agents alter the surface of one or more of the sulfides in the ore, either by chemical action or adsorption, so that it is no longer amenable to flotation, but that these depressed sulfides can be revived, after the unaffected sulfide has been floated, by reagents which react chemically with the altered surface and make it amenable to flotation. More recently, Professor Taggart1 has advanced the theory that slime adsorption is an important factor in differential flotation. He believes that, with the proper use of a class of agents, which he calls .dispersion agents and which include practically all the depressing agents, one can cause the slime to adsorb differentially on sulfide surfaces. A gangue-slime coated sulfide surface will act as a gangue particle and will not float. If, subsequently, an agent that will remove the gangue-slime coating is added, the sulfide again assumes its original surface and can be floated as an ordinary sulfide. This-is the basis of the slime theory of differential flotation. Timber Butte mill at Butte, Mont., is a typical lead-zinc flotation concentrator. Neihart ore, chosen for investigation in this work, is one of the custom ores treated at that mill. Practice at Timber Butte mill in February, 1928, was as follows: A combined lead-zinc concentrate was first made using 0.2 lb. per ton on the ore of potassium xanthate and 0.03 lb. per ton of Cleveland Cliffs oil after 1.5 lb. per ton of lime and 1 lb. per ton of calcium chloride has been added just before the ball mill. The concentrate was then thickened to 70 per cent. solids. Potassium cyanide to the amount of 0.3 lb. per ton and zinc sulfate in the quantity of 0.5 lb. per ton were added to the thickened pulp and the whole

Jan 1, 1929

By C. W. Nicolson

The Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less. Practically all of the leases granted in the past required the erection of a concentrating plant on each lease, a condition that has had a pronounced effect upon the mining and milling methods of the district, since the apparent ore reserves on each tract were too small to justify large and elaborate mining and milling plants. Most of the leases were

Jan 1, 1940

By W. van der Knapp

A theoretical and experimental ana1ysis is given of the change in volume of a porous medium due to changes in external and internal pressures. The result enable one to deduce directly the effect of large increlents in stresses. It is shown that the three-dimensional representation of the volume of a nonlinear porous system is a cylindrical rules surface, the generating lines of Which have a slope according to the solid rock compressibility. Analytical expression for such a ,surface is very simple. It follows that the bulk and pore compressihilities depend only on the difference between pore fluid and external hydrostatic pressure, i.e., the effective rock frame pressure. From measurements on a number of sandstones as well as limestones it can be conduded that for practical values of this effective frame pressure the pore compressibility falls in the range between the compressibility of water and that of undersaturated crude oil. In general, pore compressibility is found to be higher the lower the porosity. For a particular limestone reservoir pore compressibility and porosity could he related by means of a simple empirical formula. Results from the described study find a direct applicxtion in material balance calculations and in prob1ems of liquid flow through porous media. Since the elastic constants of the rock bulk material enter into equatiorls for velocity of acoustic waves, the results are also of importance for calculating rates of wave propagation in these media. It is shown for sandstones with 1.5 to -10 prr cent porosity that laboratory measured porosities may differ from those lender reservoir conditions by about I per cent of their value. The difference for low porosity limestotnes can be of the order of 10 per cent. The subsidence caused by elastic deformation of reservoir rock is shown to he very small. General formulas relating pore and bulk volume to external and internal pressure can be derived, as has been shown by Biot1, Gassmann2 and Geertsma.2 Their theories describe the differential change in volume caused by a variation in pore fluid tension and external hydrostatic tension. It has been known for a long timei that the stress-strain relations of a packing of spheres are essentially noninear. Our experiments show that for almost all reservoir rocks which arc elastically deformable the relation between volume and loading is also a nonlinear one, resembling that of a packing of spheres very closely. The behavior of these media is often described by using the linear stress-strain relations for small incremental stresses and strains in the vicinity of a pre-stressed condition." The present study differs from these considerations in that it enables one to deduce the effect of large increments in the stresses directly. In analogy to the stress tensor for a homogeneous body the stress tensor for a porous body can be written in the conventional way: where the tensor components, o, and t, represent the total forces acting on the faces of a unit cube of porous material. This tensor can be split into two parts. a hydrostatic and a deviatoric part, as follows2,3,1 where the component of the hydrostatic stress system, a. equals The hydrostatic stress causes a change in volume whereas the deviatoric stress system gives rise to a change in shape only. One of the difficulties in describing changes of volume occurring in reservoir rocks is that the relations connecting these volume changes with external and internal stresses are essentially non-linear. A complete description requires the bulk volume, V,,, as well as the pore volume,V,,. to be known as a function of both the changes in pore fluid tension (v) and the hydrostatic tension on the outer boundary.

By L. C. Brown, C. St. John, C. C. Sanderson

The diffusion rate in Cu-Te couples is very sensitive to compressive stress, with a load of 20 psi making a significant difference to the width of the diffusion zone. At zero stress, two phases appear in the diffusion zone (Cu4Te3 and CuTe). Under compressive loading the third stable phase (Cuz Te) also appears, and its thickness increases progressively with increasing stress. The results are explained on the basis of an incipient Kirkendall porosity which restricts the transfer of atoms from the copper into the diffusion zone. DURING a study of the Kirkendall effect in Cu-Te couples prepared by clamping together the two components, it was found that the diffusion-zone width and shape in the plane of contact were not reproducible. Although the stresses involved in clamping are not normally sufficiently high to affect diffusion rates, preliminary tests established that the Cu-Te system is particularly stress-sensitive. The phase diagram for the system Cu-Te given in Hanssen1 shows that there is practically no solid solubility at either end of the phase diagram. Many areas of the diagram are not fully substantiated, but there appear to be three intermediate phases: Cu,Te—hexagonal in structure, having a grey luster; Cu4Te3—a tetragonal defect structure, having a red-purple luster; CuTe—orthorhombic in structure and having a golden-green luster. The existence of a fourth phase, the X phase at 37 at. pct Te, is considered doubtful. The composition ranges of the three stable phases are small, and are not accurately known. The phase diagram changes little with temperature up to 305°C, at which temperature a polymorphic transformation takes place in Cu2Te. The nature of the Cu-Te phase diagram indicates that the diffusion zone in a Cu-Te couple would consist of a series of layers of intermediate phases. The relative thickness of any one phase will depend on its diffusion coefficient and composition range.' In this type of diffusion couple it is often found experimentally that some phases are not visible at all in the diffusion zone due either to a small diffusion coefficient or to a restricted composition range.3 Since the composition ranges of the phases in Cu-Te are not known, it is not possible to determine diffusion coefficients in this system from a knowledge of the phase thicknesses. Several investigations have been carried out to determine the effect of compressive stress on diffusion rates in multiphase systems. Diffusion couples of Ni-A1 have been investigated by Storchheim et al.4 and by Castleman and Seigle.5 Two phases (ß and ?) appear in the diffusion zone under zero stress and the thickness of both phases is progressively reduced with increasing stress. According to Storchheim et al.4 a stress of 25,000 psi reduces the thickness of the diffusion zone by 50 pct. In a-brass—?-brass couples the thickness of the 0 phase formed in the diffusion zone was reduced by 20 pct at a stress of 20,000 psi.6 In other investigations the compressive load has been observed to increase the width of the diffusion zone. In A1-U, several investigators3,8 have found the width of the whase UA13 to increase with stress. According to casileman,8 the rate of formation of UA13 at 520°C is 75 pct faster at a stress of 20,000 psi as compared with a stress of 2500 psi. In Cu-Sb the effect of stress is greater than in the other systems described. According to Heumann9,10 only one phase (y) appears in the diffusion zone at a stress of 500 psi, but at a stress of 850 psi two phases (y and k) are present. If a diffusion couple containing both y and k phases is annealed at a low stress level, the y phase grows at the expense of the k phase. EXPERIMENTAL The diffusion couples were prepared from electrolytic copper bar stock with a nominal purity of 99.92 pct and from tellurium of 99.7 pct purity. The tellurium proved difficult to machine because of its brittleness and a technique was developed for casting the tellurium into a graphite slab mold and spark-machining specimens from this slab. Both the copper and tellurium were produced in the form of discs 2 in. diam by approximately 1/4 in. thick with surfaces ground flat to 3/0 emery paper. The diffusion apparatus is shown in Fig. 1. Auni-axial compressive stress was applied to the system through a simple lever system. A stainless-steel rod actuated by the lever arm lay inside a stainless-steel tube. The diffusion couple lay on top of the steel rod, and pressure was applied to the couple between the rod and a plug welded into the center of the tube. To ensure a uniform stress across the couple, a hemispherical boss and cup were used to transmit the load to the diffusion couple. A 400-w tube furnace with a uniform hot zone 3 in. long slid around the stainless-steel tube and maintained the assembly at temperature. A thermocouple situated 3 in. from the specimen operated a proportional temperature controller which maintained the specimen temperature constant to ±2°C. Most diffusion runs were carried out at 250C although a few tests were made at other temperatures in the range 235° to 300°C. The specimens were inserted and removed with the furnace at operating temperature, and took only 2 min to reach diffusion temperature—a time small compared with the total diffusion time. All the diffusion experiments were carried out in a hydrogen atmosphere, since consistent results were obtained in hydrogen and nitrogen atmospheres and in

Jan 1, 1967

By J. O. Betterton, D. S. Easton

A detailed investigation was made of the phase diagram of silver-zirconium, particularly in the region 0 to 36 at. pct Ag. The system was found to be characterized by two intermediate phases Zr2Ag and ZrAg and a eutectoid reaction in which the -zirconium solid solution decomposes into a-zirconium and Zr2Ag. It was found that impurities in the range 0.05 pct from the iodide-type zirconium were sufficient to introduce deviations from binary behavior, and that with partial removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. pct Ag was observed. The phase diagram of the silver-zirconium system is of interest as an example of alloying a transition metal from the left side of the Periodic Table with a Group IB element. Silver would normally act as a univalent metal, its filled 4d-shell remaining undisturbed during the alloying. However, there is a possibility that some of the 4d electrons might transfer to the zirconium. An insight into such a question can occasionally be obtained by comparison of phase diagrams. The silver-zirconium system forms part of a more complete review of various solutes in zirconium in which these valency effects were studied.' Earlier work on the silver-zirconium system was done by Raub and Enge1,2 who investigated the silver-rich alloys. After the start of the present experhents, work on this system was reported by Kemper3 and by Karlsson4 which for the most part agrees with the phase diagram presented here. EXPERIMENTAL PROCEDURE The alloys were prepared by arc casting on a water-cooled, copper hearth with a tungsten electrode and in a pure argon atmosphere. Uniform solute composition was attained by multiple melting on alternate sides of the same ingot. Progressive improvements in the vacuum conditions inside the apparatus during the course of the experiments reduced the Vickers hardness increase of the pure zirconium control ingot from 10 to 20 points, observed initially, to negligible amounts at the end of the experiments. Such hardness changes in zirconium are a well known indication of purity. For example, -01 wt pct additions of oxygen, nitrogen, and carbon increase hardness by 6, 10, and 3 VPN respectively. '9' Further verification that the final casting technique did not add a significant quantity of impurities was obtained when pure zirconium was arc cast and then isothermally annealed in the vicinity of the allotropic transition. The transition was always observed to take place over the same temperature range as in the original crystal bar. The alloy ingots were annealed in sealed silica capsules for times and temperatures which varied between 1 day at 1300°C and 60 days at 700°C. The best method found to prevent the reaction of the zirconium with the silica was foil wrapping of molybdenum or tantalum. With this method, samples of pure zirconium were found to be unchanged in hardness after annealing for 3 days at 1200°C. In most of the experiments the protection of these foils was supplemented by an additional layer of zirconium foil inside the molybdenum or tantalum foil. The alloys, foil, and the capsule were outgassed at pressures in the range 10 to l0-7mm Hg in the temperature range 800" to 1100°C before each anneal in order to remove hydrogen and other impurities, and to provide a suitable container for the high purity, inert atmosphere, which is essential in the annealing of zirconium. The temperature measurements were made with Pt/Pt + 10 pct Rh thermocouples calibrated frequently during the experiments against the melting points of zinc, aluminum, silver, gold, and palladium. For the longer anneals the sum of various temperature errors was generally well within ± 2°C. For short-time anneals and during thermal analysis the overall temperature error is considered to be within ± 0.5°C. The compositions of the alloys from the quenching experiments were determined by chemical analysis at Johnson Matthey and Company, Ltd., under the direction of Mr. F. M. Lever. The actual metallo-graphic samples were individually analyzed in every case, and prior to the analyses two or more sides of each specimen were examined to insure that the specimen was not segregated. The sum of the solute and solvent analyses was in each case within the range 99.9 to 100.1 pct. In the course of the experiments, minor impurities in the range 0 to 500 ppm were found to have significant effects on the zirconium-rich portion of the phase diagram. Similar effects had been encountered previously in other zirconium phase-

Jan 1, 1959

By R. S. Dean. J. R. Long T. R. Graham, Roberson A. H., Armantrout C. E.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig' ') has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

By R. C. Ku, A. J. McEvily, T. L. Johnston

The microplastic response of a series ofas-quenched Fe-Ni-C martensites has been measured at 77°K. At strains less than JO'3 the flow stress is governed primarily by the transformation-induced dislocation structure of the martensite. Only at strains in excess of 10-3 is the influence of carbon manifested in the flow stress. At these macroscopic strains, typically 10-2, the solid-solution hardening is proportional to (wt pct C)1/3, and, in an alloy containing 0.39 wt pct C, amounts to 50 pct of the flow stress. THE technological significance of high-strength ferrous martensite has stimulated many investigations of its structure and properties. Although our knowledge of the characteristics of martensite has increased immensely, especially with the advent of high-resolution techniques, an understanding of the basic strengthening mechanism still remains elusive. The purpose of the present paper is to consider certain aspects of micro-plastic behavior of Fe-Ni-C martensite which we feel can help to resolve this important problem. Such alloys are particularly suitable for experimental investigation because their compositions can be adjusted to reduce the M, to a temperature low enough essentially to eliminate the diffusion of carbon in the freshly formed martensite.1 The mechanical properties in this condition are of interest inasmuch as they reflect a state that is free of the important but complicating influence of precipitation processes. In this virgin martensite the carbon is distributed as it was inherited from the parent austenite; i.e., it is present interstitially, and gives rise to tetragonality through strain-induced ordering.' In order to determine the source of strength of such alloys, Winchell and Cohen1 investigated the low-temperature macroscopic stress-strain behavior of a series of virgin martensites of increasing carbon content but of common M, temperature (-35°C). They found that the flow stress increased rapidly with carbon content up to 0.4 wt pct; beyond this point the flow stress increased at a much slower rate. It was concluded that martensite is inherently strong. To account quantitatively for the strength of virgin or as- quenched martensite in terms of the role of carbon, Winchell and cohen3 suggested that the carbon atoms, trapped in their original positions by the diffusionless martensite transformation, interfere with dislocation motion according to a model akin to that of Mott and Nabarro. 4 In this treatment, individual carbon atoms are considered to constitute centers of elastic strain and thereby generate an average stress resisting the motion of dislocations throughout the lattice. The additional stress necessary to move dislocations, over and above that necessary for motion in a carbon-free martensite, is given by where L is an effective length of dislocation capable of motion. L was assumed to be limited to the spacing between the twins that are an essential structural element of Fe-Ni-C martensites. They assumtd the spacing to be invariant and of the order of 100A. However, recent work5 has shown that L is variable and can be in excess of 1000Å, so that the assignment of an appropriate value of L is not straightforward. In contrast to the above conclusion that there is an intrinsically high resistance to plastic flow, it has been suggested by Polakowski6 that freshly quenched martensite is in fact "soft" in the sense that dislocations are initially free to move upon application of stress. The high indentation hardness and macroscopic yield stress of ferrous martensites are then a consequence of rapid strain hardening that depends upon carbon in solution. Consistent with this point of view are the results of Beau lieu and Dubé who measured the rate of recovery of internal friction as a function of aging (tempering) temperature in a freshly quenched steel containing 0.90 wt pct C, 0.37 wt pct Mn, 0.1 wt pct Cr, and 0.07 wt pct Ni. The kinetics were clearly consistent with the idea that many dislocations are unpinned in the as-quenched state and that during aging they become progressively pinned by carbon at a rate controlled by carbon diffusion in the body-centered martensite lattice. In order to provide a basis upon which to distinguish between the "hard" and "soft" interpretations indicated above, we have made studies of the initial stages of plastic deformation in Fe-Ni-C martensites similar to those'used by Winchell and Cohen. It will be shown that the results support the contention that dislocation segments in as-quenched material are indeed

Jan 1, 1967

By F. J. Schuh

The drilling industry long has been plagued by failures in the bottom few joints of surface and intermediate casing strings. This paper presents an analysis of the various possible causes of failure and concludes that failures are caused by short-lived, high-energy torque impulses delivered from the drill string through the bit while drilling out the cementing plugs, cement and floating equipment. The magnitude of these torque impulses is shown to be a function of the rotational momentum of the drill string, and a method is derived to calculate the magnitude of these impulses. The available methods of strengthening the bottom joints are reviewed. It is concluded that, while present methods are ineffective, a combination of improved procedures for strengthening and minor restrictions on drillout practices will prevent failures. Introduction In most cases, failure in the bottom few joints of casing strings is not discovered until electric logs record that the bottom one, two or three joints have parted from the casing string and slipped down the hole. However, in some cases the parted section of casing uncovers a high-pressure or lost circulation zone, or shifts laterally restricting the passage of drilling equipment. In these instances extensive remedial work is required to realign the parted pieces and seal the exposed formations. Several methods used to strengthen the bottom joints of casing strings include locking set screws in the couplings, putting wedges in special collars, welding straps across the couplings, welding the couplings and, most recently, using epoxy resin-based, thread-locking compounds. Since none of these techniques has eliminated the problem, this study was initiated to find the cause of failures and to evaluate the available methods of prevention. Mechanics of Casing Failures An analysis of the various possible causes of failure indicates that the casing is unscrewed rather than broken and that therefore failure must occur before the shoe is drilled. Since there is no general agreement as to the causes of casing failure, some possible mechanisms were ATLANTIC RICHFIELD CO. DALLAS, TEX. considered in this analysis. Failure of the bottom joints of casing can occur by only one of three types of stress: tension, torsion or bending. The possible mechanisms of failure were evaluated by determining the forces required to cause casing failure by each of the stresses; and, where applicable, the possibility of failure by fatigue was considered. For casing to part under tension requires a downward load of more than the tensile strength of the casing. The lightest API weight H-40 grade casing requires a bit load on the bottom of the casing of 27,000 to 34,000 Ib per inch of bit diameter (Table 1). Since maximum drill collar weights seldom exceed 10,000 Ib per inch of bit diameter, it is apparent that casing strings cannot be parted by the downward load of the drill string. The second mechanism considered was failure by bending. This mechanism requires that the lowermost casing joints be free to be deflected laterally until the bending stress exceeds the strength of the pipe. To fail, the casing (at a height L above the shoe) requires a force and deflection' at the shoe of To deflect the casing shoe with the drill string obviously requires a dog-leg at the casing shoe. This dog-leg must have a rate of change equal to or greater than the change in curvature of the deflected casing, which is given by

Jan 1, 1969

1. What Is a Rock Burst? . . . . 569 Jack Spalding . . 569 A. F. Robertson . 569 W. R. Crane . 569 G. S. Rice......569 P. J. Shenon........... 569 L. C. Graton........... 569 2. What Are the Causes of Rock Bursts? 573 Jack Spalding..........573 A. B. Yates and P. J. Shenon 574, 578, 592, 596 A. F. Robertson . . . . . 575, 595 W. R. Crane. ... 579 G. S. Rice.........582 Oscar Weiss .........582 P. B. Bucky..........582 P. H. Bird.....588, 592, 593, 595 M. K. Hubbert.........593 G. Wheeler.......... .593 B. F. Tillson........593, 595 T. T. Read............594 3. How Can Rock Bursts Be Prevented?. 597 Jack Spalding..........597 A. B. Yates and P. J. Shenon ... 598 A. F. Robertson.......599 W. R. Crane....... .602 G. S. Rice............602 Page 4. How Can Rock Bursts Be Predicted?. 602 Jack Spalding.........602 A. F. Robertson.......602, 603 A. B. Yates and P. J. Shenon ... 602 W. R. Crane......602 G. S. Rice......602 B. F. Tillson...........603 5. How Can Rock Bursts Be Controlled? 603 Jack Spalding..........603 A. F. Robertson.......603 W. R. Crane...........604 A. B. Yates and P. J. Shenon 604 Oscar Weiss........605 G. S. Rice......- 604, 609 R.D.Hoffman..609, 610 R. D. Hall..........609 R. H. Cromwell . . 609 P. J. Shenon...........609 P. B. Bucky......609, 611 B. F. Tillson.........609, 611 A. B. Yates...610, 611 P. H. Bird.......610 6. General Discussion........ 611 Jack Spalding.......... 611 R. D. Parker....... . 616 C. Baring Horwood........ 618 P. B. Bucky........... 619 Foreword This symposium brings together points of view, experiences and ideas on rock bursts from a goodly portion of the globe. Some conceptions, particularly those regarding the necessity of depth, have been fairly well shattered, as we find that they are present in the water tunnels of New York, on the surface at marble quarries in Vermont, and in the coal mines of the United States, as well as in the deep mines of the South African and Kolar gold fields, and in the nickel, copper and gold mines of Canada. Their occurrence under such a variety of conditions is, therefore, a challenge, which, if successfully met and overcome,

Jan 1, 1946

By Armantrout C. E., R. S. Dean. J. R. Long T. R. Graham, Roberson A. H.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig' ') has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

By Frederic E. Carter

There have been many attempts to prove that platinum was known to the ancients, but since no traces of the metal have been found in the relics of early times, it must be concluded that it was not known to them. As far as records go, it was actually first discovered in the 16th century in a Spanish mine on the Pinto River in South America; from which source it received its name of Platina del Pinto (little silver from the Pinto). It was more or less of a rarity and was a subject of interest to a few chemists only, until the year 1822 when the metal was first discovered in Russia. In 1819 there were noticed in the washings of the gold sands of the southern part of the Ural Mountains, grains of a heavy white substance, but it was not until three years later that this substance was found to contain platinum. While at first the amounts of platinum brought from the Urals were meager, prospecting soon disclosed rich deposits extending over a considerable area, and nuggets from 10 to 20 lb. were by no means rare. This discovery assured to chemists an ample supply of platinum for their crucibles, etc. The ore is now found in various parts of the world but the richest deposits are still found in the Ural Mountains. The platinum of commerce is obtained entirely from alluvial deposits at depths varying from 6 to 40 ft. The sand and gravel of former river beds are subjected to a series of screenings and washings to effect the separation of the ore. Actually, probably all gold-bearing gravel beds of the world contain platinum, and it is more than likely that large quantities of platinum ore have been thrown away with the black sand washings from gold placer deposits. This is especially true of the alluvial deposits of the Pacific Coast in California and Oregon. Platinum ore is usually found in the form of rounded or flattened grains of "sand," and occasionally in irregular lumps of the size of peas. Large nuggets are very rare. The ore has a metallic luster and is distinguished by its steel gray color, but shows light gray streak when rubbed on a hard white surface; it has a high specific gravity, 16 to 19; is infusible in the hottest blast furnaces, and insoluble in any single acid. Platinum ore is a complex body consisting of the metal in combination with varying proportions of the other members of the platinum group; iridium,

By A. T. Chatas

A description of the geometrical characteristics of spherical reservoir systems, a discussion of unsteady-state flow of such systems and examples of engineering applications are presented as backgmund material. The fundamental differential equation, a description of average spherical permeability and the introduction of the Laplace transformation serve as theoretical foundations. Engineering concepts are investigated to indicate particular solutions of interest, which are analytically obtained with the aid of the Laplace transform. These are numerically evaluated by computer, and presented in tabular form. INTRODUCTION A tractable mathematical analysis of unsteady fluid flow through porous media generally requires incorporation of a geometrical symmetry. The simplest forms include the linear, cylindrical (radial) and spherical. Most analytical endeavors have concentrated on cylindrical symmetry because it occurs more often in petroleum reservoirs. Nevertheless, some reservoir systems do exist that are better approximated by spherical geometry. Review of technical literature revealed but a single reference to unsteady spherical flow in petroleum reservoirs.l The motive and purpose of the present work was to remove this gap in technical information, and to provide the practicing engineer with some useful analytical tools. The mathematical details associated with the particular solutions of interest involved use of the Laplace transformation. Hurst and van Everdingen previously demonstrated the efficacy of this operational technique, and in many respects the present treatment was patterned after their earlier work.2 PRELIMINARY CONSIDERATIONS GEOMETRICAL CHARACTERISTICS Geometrically, a spherical reservoir system is defined at any instant of time by two concentric hemispheres whose physical properties of interest vary only with the radial distance. Every physical property is thus restricted to be a space function of only one variable: the distance along a radius vector emanating from the center. Such a system is composed of an outer region and an inner region, separated by a defined internal boundary. The inner region simply extends inward from this boundary, whereas the outer region extends outward from it to an external boundary. The position of the internal boundary is presumed fixed, so that the size of the inner region remains constant. On the other hand, the position of the external boundary at any given instant of time is determined by the distance into the system that a sensible pressure reaction has occurred, Thus, the external boundary may change position with time. It initially emerges from the inner region and advances outward to its ultimate position. When this ultimate position coincides with a geometric limit, the reservoir system is said to be limited. When it coincides with points subject to pressure gradients furthest removed from the internal boundary, yet short of a geometric limit, the system is said to be unlimited. In this investigation two different boundary conditions are imposed at the ultimate boundaries of limited systems. The first requires that no fluid flow occur across this boundary; the second that the pressure remain fixed at this boundary.3-5 UNSTEADY-STATE FLOW In a strict sense virtually all flow phenomena associated with a reservoir system are unsteady-state. The transient behavior of these phenomena requires accounting, however, only when time must be introduced as an explicit variable. Otherwise, steady-state mechanics may be used. Analytically, steady-state conditions prevail in a reservoir system only over that portion of its history when this relation is satisfied:

Jan 1, 1967