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By Cyril Stanley Smith, Earl W. Palmer

StKip of any of the metals used for deep drawing operations occasionally yields cups that are defective because of a rim that varies in height around the cup in a wave-like manner. Some such defects are traceable to tools or other press factors, but when the protuberances formed (usually four in number on brass and other copper alloys) are symmetrically disposed with respect to the rolling direction of the strip, they are invariably attributable to the metal. The effect is known as "earing" and the protuberances are called "ears." Other terms frequently heard are "tips," "scallops," and "corners." It is recognized that the effect is most commonly a result of a directional crystal structure produced by rolling and annealing operations in the manufacture of the metal strip. Numerous papers dealing with various aspects of the earing effect have appeared in the literature, those listed in the references1 being especially interesting and valuable. An investigation of the factors influencing earing of brass cups has been in progress in the laboratories of the American Brass Co. for several years, and it was thought desirable to make some of the results generally available in summarized form. The present paper discusses many factors that do and do not contribute to ear formation. In addition, a section is devoted to methods of minimizing the earing tendency of brass sheet by proper selection of the cold-rolling and annealing schedule by which it is produced. In the space available, it is impossible to quote detailed experimental procedures and numerical results. However, the authors make no statement that they do not believe to be properly substantiated, either by experimental evidence obtained under laboratory conditions or by experience in the actual production of deep-drawing brass in the brass mill. Mechanism of Ear Formation It must be clearly understood that the formation on cups of symmetrical ears, four or more in number, is attributable solely to the strip metal, and results from the strip having different deformation characteristics in different directions. The tools used in the drawing process, or the type and completeness of lubrication of the strip, have nothing to do with the problem of ears, although they do, of course, greatly affect the "drawing quality" of the strip and the general appearance of the cup. A single tip may be drawn up on the rim of a cup because of misalignment of the tools, or because the gauge of metal varies from side to side of the strip. The two-ear form that sometimes appears is also traceable to gauge variations. However, the four-ear and six-ear symmetrical forms that we are concerned with here are caused by factors inherent in the structure of the metal itself.

Jan 1, 1942

By John L. Miles

John L. Miles (Arthur D. Little, 1nc.)—Pollack and orris" have reported measurements on electron tunneling through A1-A12O3-A1 sandwiches in which the oxide was formed by gaseous oxidation in a glow discharge. From these measurements they deduced the asymmetry of the barrier and, since this is small, conclude that the mechanism suggested by Mott19 for the growth of oxide in thin A12O3 films is inapplicable. In earlier papers20 Pollack and Morris report similar work for oxide films grown thermally. In this case they find a greater asymmetry and conclude that the Mott mechanism is valid. I would like to point out that both these conclusions are quite unjustified. Mott suggests that the growth of the oxide film on aluminum results from the passage of ions through the already present film of oxide under the action of an electric field. This field results from a constant voltage which is in effect a contact potential between metal on one side of the barrier and adsorbed oxygen ions on the other side of the barrier. The theory does not require that the oxide grown is nonuniform either in stoichiometry or structure. It does however specifically assume that the partial layer of ionized oxygen on the surface remains adsorbed on the surface of the growing oxide. In other words, the so-called "built-in field" remains in the oxide only as long as the ionized oxygen is present. When a counter electrode of aluminum is deposited on the oxide, it will react with the adsorbed oxygen on the surface of the oxide, thus forming a small additional amount of oxide. It is clear, then, that there is no requirement in the Mott theory of oxide growth which would necessitate tunneling currents through an Al-A1203-A1 sample to be different when the polarity is reversed. Neither does the theory eliminate the possibility that some additional mechanism could cause the tunneling barrier to be asymmetric and hence tunneling currents to be a function of polarity in such a sandwich. Thus these tunneling-currents measurements are not germane to the question of whether the Mott mechanism is the true method of growth of aluminum oxide films. In fact, it is not surprising that there should be a difference between the oxide properties at the two interfaces (with resulting asymmetry in the tunneling barrier) since the growth conditions and growth rates must have been quite different at these two positions. S. R. Pollack and C. E. Morris (authors' reply)— The point raised by Miles above is one has caused some confusion in the past. The following is an attempt to clarify this point. The built-in field which is responsible for the growth of the thermal oxide at low temperatures arises, according to Mott, because of the passage of electrons from the Fermi surface of the oxidizing metal to surface states introduced by the adsorbed oxygen. It is assumed that the energy of these surface states lies below the Fermi energy of the metal. Electrons therefore continue to flow from the metal to the surface until the built-in electric field raises the potential energy of the surface states to the value of the Fermi energy in the metal, at which time equilibrium is obtained between the surface states and the metal. That is in equilibrium as many excess electrons pass from the metal to the surface per unit time as vice versa. The surface of the oxide prior to deposition of a metallic counterelectrode can then be pictured as follows. The Fermi energy lies in the energy gap of the oxide and is essentially pinned at the energy of the oxygen surface states. The vacuum work function of the oxide is then given by the sum of the electron affinity of the oxide (i.e., the difference in energy between the vacuum and the conduction-band minimum) plus the energy difference between the conduction-band minimum and the Fermi energy. The deposition of a metal onto the surface of the oxide can result in a transfer of electrons across the extremely thin oxide only if there is a contact potential difference between the deposited metal and the parent metal or oxide. That is if the vacuum work function of the deposited metal differs from that of the parent metal, then charge can be redistributed across the oxide in order to equilibriate the Fermi energy across the structure. (It should be

Jan 1, 1965

By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.' It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.' The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:' A similar treatment has also been reported to apply to zinc sulphide ores.' It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.' The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

By C. G. Dunn, J. L. Walter

Either (100) (001] or (110) (0011 oriented secondaries, or both, depending on annealing atmosphere and material composition, grew in a matrix of 2-dimensional grains. The growth dependence of secondaries of(hkl) orientation in the iron and 0.6 pct Si-Fe is explained in terms of surface energy driving forces and the dependence of these driving forces on both (hkl) orientation and amount of oxygen at the surace. (100) [001] grains grow when suflicient oxygen is present at the gas-metal interface to make y100 the lowest (hkl) surface energy. When little or no oxygen is present at the gas -metal interface, making Y110 the lowest surface energy, (110) (001 1 grains grow. When Y100 and y110 are approximately equal but lowest among (hkl) surface energies, both (100) (0011 and (110) (0011 grains grow simultaneously. An excess of surface oxygen produces complete grain growth inhibition in high-purity iron; i.e., a 3-dimensional grain structure is retained over long annealing periods. However, a small amount of silicon in the iron reduces the growth inhibiting tendency of oxygen without altering the (hkl) surface energy relationships. Some information on annealing twins is presented. SECONDARY recrystallization in high-purity a iron, cold rolled to strip a few mils thick, was reported recently.' The present paper provides additional information on this subject, also furnishes similar information on both zone-refined iron and a high-purity 0.6 pct Si-Fe alloy, and treats the more important surface phenomena that determine to a large extent whether one or more secondary recrystallization textures will appear during annealing. Previous studies on high-purity 3 pct Si-Fe2,3 have shown the importance of (hkl) and impurity-atom dependent gas-metal surface energies on the formation of secondary recrystallization textures in high-purity material. For example, either (100) or (110) oriented grains may have the lowest surface energy depending on the amount of oxygen at the gas-metal interface, and hence the highest driving force for growth if other growth factors are the same. Another important phenomenon in high-purity material is stabilization of the matrix structure; neither impurities nor a strong matrix texture seem to be necessary when recrystallization and normal grain growth occur, developing a stable two-dimensional type grain structure. The average grain size in such a structure is usually between one and two times the specimen thickness. Consequently, most of the grains have grain boundaries terminating at exposed surfaces, and this results in gas-metal interfaces (or hkl surfaces) as well as

Jan 1, 1962

By E. R. Buchanan, R. E. Reed-Hill

Cylindrical magnesium single crystals were deformed in torsion. The axis of torsion was the basal pole. Five crystals were deformed to different strains between 0.08 and 1.03 and then sectioned in order to determine their dislocation densities using the transmission electron microscope. The work hardening rate of all specimens was at least an order of magnitude higher than that normally associated with easy glide in a tension test and comparable to that obserzed in stage B of a tension test. The correspondence between stage B in a tension test and the initial stages of a torsion test is believed to result from the fact that in both cases deformation occurs in a structure containing roughly equivalent densities of the dislocations associated with the three basal slip vectors. THERE are three basic ways of changing the shape of a crystal using slip dislocations. The crystal can be sheared along a slip direction in a slip plane; it can be bent about an axis in the slip plane normal to the slip direction; and, if the slip plane contains multiple slip directions, it can be twisted or rotated about the slip plane normal. Of the three processes, generally known as translational, flexural, and rotational slip, only rotational slip has not been extensively investigated. The object of the present research was to obtain basic information about this phase of crystalline plasticity. This paper is concerned with some aspects of the stress-strain curves obtained by twisting magnesium crystals about their basal poles. Magnesium was selected for four reasons. One, its recovery rate at room temperature is relatively low. Two, single crystals may be easily grown. Three, at room temperature the critical resolved shear stress for basal slip is about two orders of magnitude lower than that for nonbasal slip, so that rotational slip might be expected to occur primarily by basal slip. Finally, relationships between flow stress, shear strain, and dislocation density have been determined for tensile deformation of magnesium crystals,' thereby providing a basis of comparison for the torsional results. EXPERIMENTAL PROCEDURES Crystals were grown from 0.5 in. diam extruded sublimed magnesium rod furnished by the Dow Chemical Co. who reported that it contained in weight percent less than 0.0003 Al, 0.01 Ca, 0.01 Cu, 0.0012 Fe, 0.001 Mn, 0.0005 Ni, 0.003 Pb, 0.001 Si, 0.01 Sn, and 0.02 Zn, with the balance magnesium. All crystals were grown in a dried argon atmosphere using Jill-son's2 modified Bridgman technique. Two different methods were used to obtain crystals with the basal plane normal to the specimen axis. These included direct growth from seeds of the proper orientation, and spark machining (trepanning) of 0.5 in. diam cylinders from larger (1.5 in. diam) randomly grown crystals. The crystals thus produced were polished in a 20 pct HC1 water solution and then etched in a 1 pct HC1 water solution to develop etch pits lying in rows parallel to the basal plane trace. The crystals were then revolved about their axes on the stage of a low-powered microscope. Torsion specimens were prepared only from those crystals whose axes were normal to the rows of etch pits. It is estimated that this simple orientation method was accurate to about 51 deg. 1.625 in. long cylinders were next cut from these selected crystals and then acid machined in a 20 pct HC1 water solution into torsion specimens with a 1 in. long by 0.30 in. diam reduced gage section. Following this, they were annealed in air at 400°C and furnace cooled to room temperature. The specimens were given a final polish in a 10 pct HC1 water solution, rinsed in ethanol, dried, and cemented into brass grips with an epoxy resin. In addition to the torsion specimens, several tensile specimens with their basal planes at 45 deg to the stress axis were also prepared with similar dimensions except that the gage sections were increased to 4 in. in length. The torsion specimens were tested in the apparatus

Jan 1, 1970

By N. P. Goss

Asterism appearing in X-ray Laue diagrams is an extremely sensitive index of changes in the internal structures of individual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.l-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not conclusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made between mosaic and distorted grain structures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example: has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-l4 to 10-l5 c.c., or 10-15 cm. in size. These crystallites, or blocks, appear to survive the most drastic cold-working, for it has been shown, and more elaborately by Wood's recent work," that cold-working cannot reduce the size of these crystallites smaller than of the order 10-5 cm. The interesting correlation brought out by the experiments of Goetz and Wood is that the block size after severe cold-working is of the same order of magnitude as the groups that formed in the metal just before crystallizing from the molten state. The work of Ewald and Rennenger17 and the now classical experiments of Darwin and James12,13 all strongly suggest the existence of a periodic structure of crystal. lites smaller than the grain itself. Related to this effect is the appearance of veinlike markings in the microstructures. Ammer-man and Kornfeld,16 in their experiments, did not observe any evidence of veining in specimens of alpha iron annealed below A3 and believed that veining was not due to impurities in the iron, as Northcott16 suggested; veining was observed by them only in specimens annealed above A3. Hanemann,16 Schrader and Tangerding found that annealing in hydrogen did not diminish veining and so it could not be caused by oxides. They concluded that veining was due to a slight difference in the orientation of ferrite lattice blocks. This viewpoint is well supported by the evidence presented here.

Jan 1, 1941

By N. P. Goss

Asterism appearing in X-ray Laue diagrams is an extremely sensitive index of changes in the internal structures of individual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.l-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not conclusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made between mosaic and distorted grain structures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example: has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-l4 to 10-l5 c.c., or 10-15 cm. in size. These crystallites, or blocks, appear to survive the most drastic cold-working, for it has been shown, and more elaborately by Wood's recent work," that cold-working cannot reduce the size of these crystallites smaller than of the order 10-5 cm. The interesting correlation brought out by the experiments of Goetz and Wood is that the block size after severe cold-working is of the same order of magnitude as the groups that formed in the metal just before crystallizing from the molten state. The work of Ewald and Rennenger17 and the now classical experiments of Darwin and James12,13 all strongly suggest the existence of a periodic structure of crystal. lites smaller than the grain itself. Related to this effect is the appearance of veinlike markings in the microstructures. Ammer-man and Kornfeld,16 in their experiments, did not observe any evidence of veining in specimens of alpha iron annealed below A3 and believed that veining was not due to impurities in the iron, as Northcott16 suggested; veining was observed by them only in specimens annealed above A3. Hanemann,16 Schrader and Tangerding found that annealing in hydrogen did not diminish veining and so it could not be caused by oxides. They concluded that veining was due to a slight difference in the orientation of ferrite lattice blocks. This viewpoint is well supported by the evidence presented here.

Jan 1, 1941

By N. A. Tiner

A study was made of the effects of temperature, type of loading, and electric polarization on the fracturing behavior of copper and zinc coated with mercury. Copper showed an em-brittlement only in cyclic loading, whereas zinc showed an em-brittlenzent in both static and cyclic loading. The embrittle-ment of zinc in static loading was prevented by sub-zero cooling to a temperatzcre of about -70°F. The emhrittlement of both metals was sliglztly reduced by cathodic polarization of mercury. The basic processes involved in fracturing were discussed in the light of these observations. When a solid metal is in contact with certain liquid metals possessing high wetting characteristics, a weakening effect is produced, and the solid metal fractures in brittle manner at a relatively low stress. This lowering of the fracture stress generally is considered different from the stress cracking caused by a corrosive liquid environment and is attributed to the lowering of the solid-liquid interface tension at the grain boundaries.1-4 The purpose of this paper is to describe a number of observations on the special features of fracturing of copper and zinc coated with a liquid mercury film, and to analyze the basic processes involved in fracturing in the light of these observations. EXPERIMENTAL OBSERVATIONS I) Effect of Type of Loading—The evidence appears to indicate that in static loading, metals usually fracture by the initiation of microcracks in the interior preferentially at the grain boundaries or at the intersection of slip bands.' In cyclic loading, cracks develop on the surface within the active slip zones, and gradually propagate with increasing num- ber of cycles.6'7 Because of this difference in the manner of initiation of cracks, a series of bare and mercury coated copper and zinc specimens was subjected to static and cyclic loading, and their fracturing behavior was examined. The specimens were machined to 0.25 in. in diam and 1 in. in length from a high-purity commercial bar stock, and annealed at an appropriate temperature. Mercury was applied to the surface of the specimens by rubbing with cotton wool soaked in a saturated solution of HgCl2 or by etching with a dilute solution of HC1 and rubbing with purified mercury and by washing in water. The static tension load-extension curves were obtained by means of a Riele Screw Power Universal Testing Machine. The room-temperature load-extension curves for copper and zinc are shown in Fig. 1. The deformation behavior of copper, as judged from the general configuration of the load-extension curve, was not affected by mercury coating. The maximum load to fracture and the elongation at the maximum load were practically the same for both specimens. The mercury coated copper, however, showed somewhat less localized necking and had smaller reduction of area than the uncoated metal. The behavior of mercury coated zinc was radically different from the behavior of uncoated metal. The load-extension curves were the same at the

Jan 1, 1962

By Robert Maes, Robert de Strycker

The Cu-Sn-As systeM was studied in the region near the Cu-42 and (214-As binary diagrams, where reactions in the solid state appear, resulting from the decomposition of the y(Cu-Sn) phase and from the formation of the 7 phase (Cu,As). The techniques used were microscopic observation, thermal analysis by dilatometry, and X-vay diffraction. The formation of the 7 phase gives rise to a ternavy pevitectoid veaction; the decomposition of the y phase gives rise to five transitional reactions. The temperatures of almost all these reactions could be determined; in the most favorable cases , the accuracy of this determination was of 11.5-C. The 7 phase is stabilized by tin additions, the arsenic atoms being replaced by tin atoms up to 35 pct; this has allowed the preparation of pure j) phase and the confirmation, by extrapolation, of the conrposition of this compound in the Cu-As diagram. In the first part of this work, the solidification reactions in the Cu-Sn-As phase diagram were studied. In the copper corner, the structure of the alloys presented the evidence of reactions in the solid state: on the one hand, all the alloys containing the y phase of the Cu-Sn diagram showed, under the microscope, that this phase had formed different decomposition products after complete solidification; on the other hand, the appearance of the 7 phase of the Cu-As diagram necessitated the introduction of a peritectoid formation reaction. The study of the decomposition of the y phase has been done by preparing about forty alloys that were homogeneous y at high temperature. The formation of the 7 phase has been studied by means of a few alloys with a composition near the homogeneity field of this phase at room temperature. The part of the Cu-Sn phase diagram of interest for this study is represented by Fig. 1, with the phase designation which will be used in the remainder of this paper; it is drawn after Hansen and Anderko.' The Cu-As diagram has already been presented in Part I of this work; the significant features of this study are the existence of the arsenides CusAs and Cu5Asz, and the formation of a compound CUEAS, designated as the 7 phase, by a peritectoid reaction at about 325°C. EXPERIMENTAL METHODS The fundamental technique for the investigation of this part of the Cu-Sn-As constitution diagram was microscopic observation; the greatest part of the observed alloys has also been subjected to thermal analysis by dilatometry; a few selected alloys have then undergone an X-ray analysis by powder diffraction. Alloy Preparation. The alloys were prepared from the same products as in Part I of this study: cathode copper, arsenic with a purity better than 99.5, and tin with a purity of 99.98. The fusion of the ternary alloys was realized from

Jan 1, 1967

By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.' The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.' It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By Milton Glicken

THE airborne geophysicist is a busy man these days. In his plane he may have the airborne magnetometer, the airborne scintillation counter, and the airborne electromagnetic surveying system. Each of these is an independent tool, but all require additional auxiliary equipment for locating the aircraft in space: recording altimeters and Shoran or aerial cameras. Now there is still another piece of equipment, the airborne magnetic gradiometer, an accessory to the magnetometer. To understand its uses, consider the function of the magnetometer itself. Aside from detecting magnetic ore, the airborne magnetometer finds greatest use in spotting intrusions of igneous material. Where there is enough contrast in magnetic susceptibility of igneous rock and adjacent formations, it outlines the intrusion. Certain minerals also influence the magnetometer directly, but with the exception of magnetite and possibly one or two others, their effect is weak and can be detected only when there is sufficient ore and the magnetometer flight passes very close to it. An igneous intrusion of infinite depth with vertical sides is represented on a magnetometer record by an anomaly, as in Fig. 1. Amplitude of the high depends on susceptibility contrast of the igneous rock. Generally speaking, the edge of the intrusion lies below the point of inflection of the curve, and this point, where the curvature changes from positive to negative on the magnetometer profile, would be near A in Fig. 1, with a counterpart, of course, on the other side. Location of the contact is one of the principal objects of the survey, but finding the precise point is not always easy, as inspection of the curve near A will show. Mineralization is often found at the contact zones, as at B. Magnetic effects, if detected, may be small, as in B', and when superimposed on the anomaly due to the instrusion they are very difficult to discern and analyze. Furthermore, if these small fluctuations are to be perceived by the magnetometer the vertical scale should be large. This increases the slopes of the anomaly and makes detection of small deviations and inflection points even more difficult. The airborne magnetic gradiometer was designed to help overcome these difficulties. What it presents is the first derivative of the magnetometer record with respect to time, that is to say, the slope at any point. Fig. 2 represents an actual magnetometer record (solid line) with the corresponding gradiometer record (dashed line) superimposed. Both records read from right to left. Vertical lines on the original magnetometer record are automatic steps designed to keep the pen from going off scale. The slope of any curve is greatest at the point of inflection or point where the curvature changes sign, and this point is a maximum (or minimum) on the gradi- ometer. The chief advantage of the gradiometer is that maxima or minima are much easier to see and to locate precisely; hence an accurate location for the point of inflection can easily be found. Note that points C and D are more sharply defined than C and D'. Similarly the small fluctuations of the original record, so important to the interpreter, are far more clearly shown at E, F, and G, than on the original record at E', F', and G'. Though not necessarily highs and lows on the gradiometer, they do show up clearly what would take a painstaking analysis to detect on the original magnetometer record. Will the gradiometer have a particular configuration which indicates an orebody? Not necessarily. The total intensity curve, or original magnetometer record, can display an orebody in various ways, depending on dimensions, orientation, latitude, and composition, as well as on direction, flight height, and instrumental sensitivity of the traverse. Where the total intensity can take on so many different shapes the gradiometer must vary too. It is generally recognized that interpretation of total intensity magnetometer records requires an expert analysis; the gradiometer can be of considerable assistance to the expert but it does not replace him. Mechanism of the gradiometer is simple. A Leeds & Northrup recorder in the aircraft records the magnetic gradient simultaneously with the total intensity, which is on another recorder. Fiducial marks are put on both records simultaneously and the speed of the paper through the recorders is kept the same on both. This makes it possible to place one record over the other for direct comparison. In the laboratory the flights are positioned on a map. Maximum and minimum points on the gradiometer, which can then be posted on the map at their proper locations, may be expected to fall along a trend crossing the direction of flight. Trends should indicate the edge of an intrusion, or some other important features, and when superimposed on the total intensity contour map help greatly to locate the points of inflection, or line of zero curvature.

Jan 1, 1956

By J. E. Graham, A. H. Glenn

Oil operators engaged in drilling on the Continental Shelf of Louisiana and Texas are in agreement that adverse weather and wave action are two of the greatest hazards to the safety and efficiency of their work. It was ami-pated when the offshore operations commenced that such would be the case, and experience to date has verified this assumption. Because atmospheric conditions and wave action involve tremendous amounts of energy it is highly unlikely that it will be possible to control any but the most localized weather and wave phenomena within the foreseeable future. Thus. as long as the offshore operations involve the movement of small craft and barges over exposed waters, and the transfer of personnel and heavy equipment from these craft to either fixed structures or larger craft at close quarters, the weather and wave problem will remain. Taking into consideration the persistence of the wave and weather problem and the improbability of achieving a direct solution, the Humble Oil & Refining Company, in planning its offshore campaign investigated the possibility of forecasting wave and weather conditions in order to provide warnings of dangerous conditions and increase efficiency in day-to-day planning of work. It was recognized that predictions of wave and weather conditions based on meteorology and oceanography, both geophysical sciences, are not 100 per cent accurate and application of forecasts in the offshore work was dependent on whether they provided information which was sufficiently greater in accuracy than the layman's guess to be worth the expenditure involved. During World War 11. meteorology and oceanography were used with success in reducing danger resulting from environmental conditions and increasing efficiency of operations exposed to the elements. This success was partially the result. of improvement in the scientific techniques involved and the procurement and distribution of observational data, and partially due to the large scope of the military operations which meant that a reduction of losses of a relatively small percentage of the total cost amounted to a large figure expressed in terms of dollars. Since the offshore drilling involves an extremely large financial investment, it was considered that the experience of the Armed Services in successfully employing meteorology and oceanography might be duplicated in the oil industry. In addition. the oil industry's successful experience in utilizing seismology, geology, and terrestrial magnetism; all geophysical sciences, indicated that meteorology and oceanography, also of the family of geophysical sciences and sharing their scientific assets and liabilities, might be profitably put to use. Since the immediate problem involving the sciences of meteorology and oceanography in the offshore campaign is wave action, a program was inaugurated within the Humble Oil & Refining Company during June 1947. the purpose of which was to ascertain the applicability and limitations of wave forecasting in the offshore campaign. A summary of the effective wave forecasting techniques developed during the war was prepared in the form of a forecasting manual for the Continental Shelf off Grand Isle, Louisiana, by Bates and Glenn. After completion of this manual, experimental forecasts were prepared daily over a two-month period by Graham and Thompson to determine the accuracy of the forecasts. It was considered that the accuracy of the experimental forecasts justified a more extensive test under actual operating conditions in the offshore work and the firm of A. H. Glenn and Associates was set up under the sponsorship of the Humble Oil & Refining Company to work with the Humble Grand Isle District in providing forecasts of wave and weather conditions over a one-year period. This paper discusses the service now provided to the Grand Isle District, its applicability and limitations. TYPE OF FORECASTS REQUIRED It was apparent before the commence-mence of the forecasting service that a specialized type of forecast was required. Many of the weather elements of interest to the general public, such as rain and temperature, are of minor concern to offshore operators. On the other hand, such elements as wave height and wind speed and direction are of great concern in the offshore operations since variations in wave height of a few feet in the critical range divide safe from hazardous working conditions. To be of utility. a forecasting service for the offshore work must provide detailed forecasts of the elements which affect the operation. With this in mind, it was decided that forecasts would include the following information: average wave heights to the nearest foot, wind speeds within a range of approximately 5 miles per hour, and wind directions within 221 degrees. Since the procedure for forecasting these elements involves thorough analysis of weather data, it was decided to include a generalized forecast of weather conditions such as rain and cloud cover, although these are of secondary importance.

Jan 1, 1949

By A. H. Glenn, J. E. Graham

Oil operators engaged in drilling on the Continental Shelf of Louisiana and Texas are in agreement that adverse weather and wave action are two of the greatest hazards to the safety and efficiency of their work. It was ami-pated when the offshore operations commenced that such would be the case, and experience to date has verified this assumption. Because atmospheric conditions and wave action involve tremendous amounts of energy it is highly unlikely that it will be possible to control any but the most localized weather and wave phenomena within the foreseeable future. Thus. as long as the offshore operations involve the movement of small craft and barges over exposed waters, and the transfer of personnel and heavy equipment from these craft to either fixed structures or larger craft at close quarters, the weather and wave problem will remain. Taking into consideration the persistence of the wave and weather problem and the improbability of achieving a direct solution, the Humble Oil & Refining Company, in planning its offshore campaign investigated the possibility of forecasting wave and weather conditions in order to provide warnings of dangerous conditions and increase efficiency in day-to-day planning of work. It was recognized that predictions of wave and weather conditions based on meteorology and oceanography, both geophysical sciences, are not 100 per cent accurate and application of forecasts in the offshore work was dependent on whether they provided information which was sufficiently greater in accuracy than the layman's guess to be worth the expenditure involved. During World War 11. meteorology and oceanography were used with success in reducing danger resulting from environmental conditions and increasing efficiency of operations exposed to the elements. This success was partially the result. of improvement in the scientific techniques involved and the procurement and distribution of observational data, and partially due to the large scope of the military operations which meant that a reduction of losses of a relatively small percentage of the total cost amounted to a large figure expressed in terms of dollars. Since the offshore drilling involves an extremely large financial investment, it was considered that the experience of the Armed Services in successfully employing meteorology and oceanography might be duplicated in the oil industry. In addition. the oil industry's successful experience in utilizing seismology, geology, and terrestrial magnetism; all geophysical sciences, indicated that meteorology and oceanography, also of the family of geophysical sciences and sharing their scientific assets and liabilities, might be profitably put to use. Since the immediate problem involving the sciences of meteorology and oceanography in the offshore campaign is wave action, a program was inaugurated within the Humble Oil & Refining Company during June 1947. the purpose of which was to ascertain the applicability and limitations of wave forecasting in the offshore campaign. A summary of the effective wave forecasting techniques developed during the war was prepared in the form of a forecasting manual for the Continental Shelf off Grand Isle, Louisiana, by Bates and Glenn. After completion of this manual, experimental forecasts were prepared daily over a two-month period by Graham and Thompson to determine the accuracy of the forecasts. It was considered that the accuracy of the experimental forecasts justified a more extensive test under actual operating conditions in the offshore work and the firm of A. H. Glenn and Associates was set up under the sponsorship of the Humble Oil & Refining Company to work with the Humble Grand Isle District in providing forecasts of wave and weather conditions over a one-year period. This paper discusses the service now provided to the Grand Isle District, its applicability and limitations. TYPE OF FORECASTS REQUIRED It was apparent before the commence-mence of the forecasting service that a specialized type of forecast was required. Many of the weather elements of interest to the general public, such as rain and temperature, are of minor concern to offshore operators. On the other hand, such elements as wave height and wind speed and direction are of great concern in the offshore operations since variations in wave height of a few feet in the critical range divide safe from hazardous working conditions. To be of utility. a forecasting service for the offshore work must provide detailed forecasts of the elements which affect the operation. With this in mind, it was decided that forecasts would include the following information: average wave heights to the nearest foot, wind speeds within a range of approximately 5 miles per hour, and wind directions within 221 degrees. Since the procedure for forecasting these elements involves thorough analysis of weather data, it was decided to include a generalized forecast of weather conditions such as rain and cloud cover, although these are of secondary importance.

Jan 1, 1949

By D. H. Henley, F. F. Craig, W. W. Owens

The oil recovery performance of systems producing entirely by bottom-water encroachment has been experimentally determined in a series of scaled laboratory-model tests. The effects of well spacing, fluid mobilities, rate of production, capillary and gravity forces, well penetration and well completion techniques on the oil recovery performance have been investigated. The laboratory tests were performed using two uniform, un-consolidated sand-pack models. The models have ratios of the interwell distance to the formation thickness of 12 and 2, respectively. Tests at constant total fluid production rate were performed simulating a range of uniform reservoir characteristics and operating conditions encountered in field operations. The performance was determined by material balance and by observation of the encroachment of dyed fluids into the models. The results of the model tests agreed with those obtained mathematically when the conditions previously considered in theoretical studies were simulated, that is, when the oil and water are of equal density and no capillary forces exist. The model study of bottom-water drive indicated that certain variables can aoect the oil recovery performance to a greater degree than can be predicted by present analytical methods. In one comparison, the oil recovery at a water-oil ratio of 20 (obtained at a wide well spacing) varied as much as threefold, depending upon the system's properties and the production rate. Lesser effect of mobility ratio and no eflect of capillary forces over the range studied were observed. The test 'results also showed that the deeper the well penetration into the oil column, the greater the total water production to a producing WOR of 20. However, the ultimate sweep efficiency, and so the oil recovery to this level of WOR, did not vary significantly with well penetration. Horizontal fractures at the top of the formation did not significantly change the sweep characteristics of the reservoir models when values of radius and fracture capacity encountered in actual reservoirs were used. Impermeable pancakes at the bottom of the well moderately increased the oil recovery efficiency both at water breakthrough and at high water-oil ratios. A method is outlined by which the oil recovery performance of other uniform bottom-water drive systems can be estimated from the information obtained in these model tests. INTRODUCTION When oil is produced from a well which partially penetrates an oil zone completely underlain by water, the water rises directly beneath the well in a symmetrical cone when the system is uniform. Two different flow mechanisms can cause the water cone to form—coning and bottom-water drive. In coning, the aquifer is relatively inactive and the cone is formed beneath the well by the pressure gradients associated with the oil flow to the well. The oil can be produced by a solution-gas drive, an edge-water drive or other driving forces in the interwell area. In a bottom-water drive, the driving force for oil production comes from an upward encroachment of the underlying active aquifer. Two papers have analyzed the theoretical performance characteristics of bottom-water drive reservoirs. In the initial mathematical investigation, Muskat' established the equations which determine the pressure distribution in this type of reservoir and solved these equations for certain conditions. Specifically, it was assumed that the water and oil had equal mobilities and equal densities, there were no capillary forces, the pressure throughout the oil zone remained above the bubble-point pressure, a constant pressure existed at the initial water-oil contact and the oil was completely displaced by the encroaching water. These assumptions were used in obtaining analytical solutions. In general, Muskat found that the sweep efficiency to initial water breakthrough to the well was larger for the thicker oil zones, the closer well spacings, the lower ratios of vertical to horizontal permeabilities, the smaller the penetration of the well into the oil zone and the smaller the bore size of the well. The production history after water breakthrough was expressed as a volumetric sweep efficiency at a given producing water-oil ratio. The results indicated that cumulative oil production at producing water-oil ratios of 10 is less affected by the well spacing than is the water-free production history. Muskat studied well spacing which today would be regarded as close. The maximum value of his dimensionless well spacing (ratio of interwell distance to formation thickness) was 4.3. This would require the development of a 50-ft-thick oil sand on less than 10-acre spacing if the vertical and horizontal permeabilities were equal, with

By J. M. W. Mackenzie, C. J. Wood

In attempting to describe the size classification performance of a hydrocyclone, most workers have elected to use either an equilibrium orbit theory or an non-equilibrium orbit theory. The equilibrium orbit theory has been used by the majority of workers including Lilge,' Bradley; and Yoshioka and Hotta. In applying this theory, it is argued that particles in the body of a hydrocyclone attain an equilibrium radial position where the drag force on the particle resulting from the inward radial fluid velocity is balanced by the outward centrifugal force caused by the tangential component of fluid flow. When considered over the full height of the hydrocy-clone, attainment of this radial equilibrium orbit results in the particle following a conical equilibrium envelope. It is then argued that if this envelope lies outside the envelope of "zero vertical velocity," the particle will report to the underflow, while if the equilibrium envelope lies inside the envelope of "zero vertical velocity," the particle will report to the overflow or vortex finder product. The d50-sized particle which reports in equal quantities to the underflow and overflow is assumed to correspond to particles whose equilibrium envelope is coincident with the envelope of "zero vertical velocity." In considering the equilibrium orbit theory, it is apparent that the horizontal position of the particles in the feed inlet pipe should have no effect on their ultimate destination on the hydrocyclone. Each particle should attain an equilibrium position which depends on the density, size, and shape of the particle; the density and viscosity of the fluid; and the flow patterns within the hydrocy-clone. The nonequilibrium orbit or unsteady state theory has been largely developed by Rietema4 and Mizrahi.6 Mizrahi has listed four main objections to the equilibrium orbit theory. These objections center on the short residence time in the hydrocyclone, the fact that the experimental classification curve is much less sharp than is theoretically predicted, and the absence of negative efficiency conditions in hydro cyclones operating on a feed material which is much finer in size than d50. Proponents of the nonequilibrium orbit theory argue that for a particle to discharge with the underflow it must have sufficient outward radial velocity to reach the downward-flowing region close to the hydrocyclone wall in which the flow lines are parallel to the wall and the ratio of vertical to radial velocity is constant. It is then postulated that a d50 particle entering the cyclone at the center of the feed inlet will just reach this downward-flowing region as it reaches the apex. Thus for uniform distribution of particles across the feed inlet, half the d50 particles—that is, those injected in the half of the inlet area nearest the cyclone wall —will report to the underflow while those injected in the other half will not reach the downward-flowing region and will be carried inward to the center of the cyclone and thus report in the overflow. The exact thickness of the down-ward-flowing region of fluid adjacent to the outer wall of the hydrocyclone is uncertain but Mizrahi considers it to be equal to the apex radius minus the air core radius. Particles larger than d50 have a greater outward centrifugal force acting on them than the d50 particles and may reach the wall even if injected at a distance from the wall greater than Di/2 (Di is inlet diameter). Conversely, particles smaller than d50 may not reach the wall even if injected at a distance less than Di/2 from the cyclone wall. Since the equations put forward by the proponents of both theories yield approximately the same values of d50, it is not possible to decide between these theories by measurement of d50. It should be possible however to examine the theories by injecting a small stream of solids into the feed inlet of a hydrocyclone running on clear water. If the efficiency or classification curve is measured for various horizontal injection positions, then the curves should be coincident if the equilibrium orbit theory holds. If, however, the unsteady state theory describes the cyclone operation, then the classification curves should show finer d50 sizes for particles injected close to the cyclone wall. Experimental A 6-in.-diam hydrocyclone with geometry as in Figs. 1 and 2 was used. Quartz particles were injected as a 50% by wt pulp via an 1/8-in. steel probe. For each in-

Jan 1, 1971

By C. L. Prokop

A laboratory investigation has been made of the effects of mud hydraulics upon the formation and erosion of mud filter cakes. The tests were conducted to simulate drilling conditions as nearly as possible. The formation of mud filter cake in a drilling well does not proceed at a uniform and unbroken rate. Instead, the rate of cake accumulation depends upon whether or not the mud is being circulated. If the mud column is quiescent, filter cake formation is a smooth function of the filtration characteristics of the system. If the mud is being circulated filter cake formation depends not only upon the filtration characteristics of the mud but also upon the erosive action of the flowing mud column Filter cakes formed during continuous mud circulation were observed to reach an equilibrium thickness after several hours' circulation. Mud circulation was maintained at a constant volumetric rate throughout each experiment. The fluid velocity at equilibrium cake thickness was dependent upon the thickness of the filter cake. Muds having exceptionally high water loss deposited thick filter cakes in spite of very high eroding velocities. The muds having good filtration characteristics deposited thin filter cakes at equilibrium circulating velocities well within tile range of those in a drilling well. It was observed that filter cakes deposited during stagnant filtration were quite difficult to erode by mud circulation. The - rate of crosion computed from the rate of filtrate accumulation after equilibrium cake thickness had been reached was in reasonable agreement with the rate of erosion obtained by direct observation. Continuous mud circulation usually caused the permeability of the filter cake to decrease with time. INTRODUCTION Many of the difficulties encountered during tile drilling of a well have been attributed to the loss of water from the mud and the attendant deposition of solids upon the walls of the hole. Past experience has shown that a reduction of the filtration rate of the drilling fluid eliminates or greatly reduces these difficulties. Definite filtration requirements, however, are hard to establish for a given set of conditions. This is due. in part, to the fact that the usual filtration test performed upon mud doe? not simulate well conditions as closely as desirable. The filtration characteristics of a mud are customarily determined by means of the standard low-pressure API wall-building tester.' In this instrument a filter cake is deposited upon a horizontal bed under a pressure differential of 100 psi. The rnud is quiescent during the filtration period. In actual practice. mud filtration occurs within a well under quite different conditions. One of the major differences is that mud flows upward across the filter bed as the filter cake forms. This undoubtedly produces a change in the filter cake which cannot be reflected in the results of the API test. The laboratory work described in this paper had as its primary objective a better understanding of the influence of mud circulation upon the thickness and ,characteristics of the filter cakes deposited under conditions similar to those existing in a drilling well. ANALYSIS OF PROBLEM Once a permeable formation is penetrated by the bit, filtrate from the mud flows into the formation. 'he mud solids plaster against the walls of the hole, forming a filter cake. If the mud column is stagnant, that is, if it is not being circulated. the filter cake will increase in thickness until the hole is filled. Prior to the time that the hole is filled, the thickness of filter cake existing at any given time will be a function of the filtration characteristics of the mud, the temperature, and the pressure differential. The effects of these variables have been investigated in the past for both flat bed filtration2'3 and for radial filtration.' When the mud is circulated in a hole in which a filter cake i. being deposited. some of the solids that would ordinarily deposit in the filter cake will be carried away by the eroding action of the mud. This will limit. filter cake thickness. Some work has been done to determine the effect of flow upon the filtration rate in a circulating mud system' but little work has been done upon the factors which determine the filter cake thickness existing in a circulating system. On first sight it would appear that the major factors controlling filter cake formation in a circulating system should be: 1. The rate of deposition of solids from the mud. 2. The erosive force that the flowing mud exerts upon the filter cake. 'A. The erodabilitv of the filter cake. 4. Any change in filter cake characteristics attributable to the scouring action of the mud. The rate at which solids are deposited from the mud will be controlled to a large degree by the filtration characteristics of the mud, the pressure differential. the temperature under

Jan 1, 1952

By John G. Tate, George W. Nicolson, James L. Bruce

FOR more than 25 years modern mining has been carried on in the Island of Cyprus, Mediterranean Sea, by the Cyprus Mines Corp. of Los Angeles, Calif. The general features of these operations have been described.1 From 1935 to June 30, 1940, top slicing in the Mavrovouni mine produced in excess of 2,000,000 long tons. The rate for the last part of this period was approximately 50,000 tons per month. DESCRIPTION OF ORE BODIES The shape of the ore body now being top sliced in the Mavrovouni mine is an inclined irregular pyritic pipe or chimney of large dimensions, extending from unknown depths below the bottom level at elevation 250 ft below sea level, to the highest level at elevation 400 ft above sea level. The present surface above the ore body lies between 550 and 650 ft elevation. Undoubtedly the ore body extended to surface and was mined by the ancients by opencast and underground methods. The old pits were gradually filled up by erosion until now they show as slight depressions in the topography. The largest area of the ore body is at elevation 170 ft below sea level, where the horizontal section is almost elliptical, with a width of 600 ft and a length of 1000 ft. Below this elevation the shape of the ore body continues to be elliptical but with reduced dimensions. Above this elevation it rises flatly towards the south with a substantial depression in the upperside of the chimney and irregular ridges or wings rising on each side. It gradually grows smaller as it rises. The ore body is a pyritic replacement of andesitic extrusives which occur as flows and pillow lavas. With the exception of the upper portions of one or two small offshoots rising from the main ore body, all ore is completely surrounded by andesite. Most of the andesite lying above the ore body is covered by marl and clay sedimentaries of Miocene and later age. The Miocene is presumed to be older than the ore mineralization. That portion of the andesites which lies between the sedimentaries and the ore body has been broken by slumpage, and weathered, and iron-stained by the descending meteoric waters. It is a mass of crushed material that caves and follows downward readily as the top-slice stopes retreat. The main ore body is a heavy cupreous pyrites mass assaying on the average about 4.0 pct Cu; 48.0, S; and 42.0, Fe. In places the copper drops below 1.0 pct. On the borders of this heavy sulphide ore body lie disseminated cupreous pyrites ore deposits of large dimensions. Some portions of these appear to be closely related to the heavy sulphide ore, as the ratio of copper to pyrite is about the same. The greater part of the disseminated ore, most of which lies immediately to the east of the main ore body, contains less than 0.10 pct Cu and about 25.0 to 30.0 pct S. This probably can

Jan 1, 1947

By D. D. Pollock

Many constitution diagrams do not indicate the limits oJ solid solubility of the silver-rich solid solutions below 200°C. Thermoelectric measurements were employed to determine this limit in the nieighborhood of room temperature. The appearance of a second phase causes a discontinuity to occur in the tkevtrroelectric power as a function of cornposition at constant temperature and pressure. This discontinuity was employed to determine the limits of the silver-rich terzinal solid solutions of the Ag-A l, Ag-As, Ag- Bi, Ag--Ge, Ag-In, Ag-Pb, Ag-Sb, and Ag-Sn systenls at 30°C. CONSIDERABLE work has been done on the constitution of binary alloys of silver. The available data have been compiled by Hansen1 and Elliott.2 However, many of the binary diagrams do not show the limits of solid solubility of the silver-rich solutions below about 200° C. This work was undertaken in an attempt to extend these limits to the neighborhood of room temperature . PREPARATION OF ALLOYS All of the alloys were made with silver containing less than 0.014 pct (by weight) of impurities. The materials were weighed out into 225-g heats and melted in a high-frequency induction furnace. The indium, tin, and antimony alloys were melted in A1203 crucibles, under a boric anhydride cover, and were poured into split graphite finger molds. The aluminum, germanium, arsenic, lead, and bismuth alloys were melted in machined graphite crucibles; they were also covered with boric anhydride and poured into split graphite finger molds. The $-in.-diam ingots were heated to 750°C and were forged and hot-rolled down to 0.1 by 0.1 in. The wires were pickled in a 25 pct HNO3-75 pct H2O solution to remove any oxygen-rich surfaces. The wires were then annealed at 550°C for 2 hr in a dissociated ammonia atmosphere. They were then furnace-cooled for 20 hr to room temperature in this atmosphere. The wires were cold-drawn to 0.0808 in. diam. The finished wires were again annealed at 550°C in the same manner as in the first anneal. Thermoelectric Power. The thermoelectric power of a single specimen of each alloy was determined against pure silver which contained a maximum impurity content of 0.014 pct by weight. The wire specimens were straightened and then cleaned with ethyl alcohol. They were then reannealed in the same way as the finished wires to assure that any residual stress would be at a minimum level. Previous work has shown that the presence of small amounts of stress has the effect of decreasing the thermoelectric power. The alloy specimen was soldered to the pure silver wire to form the measuring junction. A standard set of copper leads was then soldered to the reference junctions of the thermocouple. These junctions were maintained in separate dewar flasks which contained finely shaved melting ice during the test. The thermal electromotive forces of the thermocouples were measured at four temperatures between 15° and 45°C. A known source of electromotive force was balanced against the output of the thermocouple until a null balance was reached. The data were then expressed in terms of the thermoelectric power at 30°C. The results were then converted to absolute thermoelectric power, s303.3 These data have an average error of less than ±0.2 pct. RESULTS AND DISCUSSION All of the experimental data are given in Table 11. Since the electromotive forces of the binary alloys of silver were determined against the pure silver from which they were made, the resultant thermoelectric powers are only a function of the intentionally added binary elements at the constant test temperatures. This provides a direct measure of the effects of the alloying elements. The absolute thermoelectric power of an alloy of silver is given4 by:

Jan 1, 1968

By H. B. Probst

Mechanical twins were produced in zone-refined tungsten single crystals by explosive working at room temperature. These twins are parallel to (112) planes and have irregular boundaries rather than the classical plane twin boundaries. These boundaries aye grooved surfaces in which the grooves themselves are parallel to a <111> direction and the sides of the grooves appear to be par-allel to (110) planes. TWINS were produced in tungsten single crystals by explosive working at room temperature. These twins differ in character from any previously reported for tungsten; however, they are similar to those found in molybdenum after compression at -196°C.1 Deformation twins "resembling Neumann bands in ingot iron" have been observed in tungsten by Bech-told and Shewmon.2 This observation was made with sintered polycrystalline tungsten pulled in tension to fracture at 100°C and using a strain rate of 2.8 x 10-4 sec-1. More recently Schadler3 found deformation twins in zone-refined tungsten single crystals pulled in tension at -196"&apos; and -253°C. These tests were conducted using a strain rate of 3.3 x l0-4 sec-1, and the twin bands were found to be parallel to a (112) plane. Deformation twins in tungsten&apos;s sister metal, molybdenum, were observed by Cahn.4 These twins were produced by compressing small (0.7 mm) vapor-deproducedposited molybdenum single crystals at -183°C. The compression was performed &apos;by impact." By the use of precession X-ray techniques, Cahn was able to identify the twin plane as {112} and the shear direction as <1ll>. Mueller and Parker1 produced deformation twins in polycrystalline electron-beam-melted molybdenum by compression at -196°C. Their "loading rate" was 5000 psi per min which, judging from their stress-strain curve, corresponds to a strain rate of approximately 0.3 x 10-4 sec-1. These twin bands were found to be parallel to (1 12) planes; however, they differed in appearance from previously observed twins. In place of straight and parallel twin boundaries they were found to be irregular, jagged, and sawtoothed. The sides of the saw teeth were identified as (110) planes and irrational planes of a (111) zone. The twins observed in the present work in tungsten single crystals are similar in appearance to those of Mueller and Parker in polycrystalline molybdenum. The starting material used in this investigation was 3/16-in. diam commercial tungsten rod produced by powder-metallurgy techniques. This material was converted to a single crystal by the electron-bombardment floating-zone technique.= The process was carried out in a vacuum of 10-5 mm of Hg using a traversing speed of 4 mm per min. Segments (=2 in. long and 3/16 in. in diam) of two crystals (A and B) produced in this manner were studied. Crystal A received one zoning pass, while crystal B received two passes. The two crystals were explosively worked at Bat-telle Memorial Institute in the following manner. A 1/2-in.-thick layer of plastic was applied to the crystals to serve as a buffer in an attempt to prevent cracking. The composite, crystal and buffer, was then wrapped with 1/8-in.-thick DuPont sheet explosive EL506A2 and detonated in water at room temperature. Metallographic samples of the worked crystals were prepared, and back-reflection Laue X-ray patterns were obtained using unfiltered molybdenum radiation. RESULTS AND DISCUSSION Blasting the crystals as described above failed to prevent cracking. The crystals fractured into several fragments about 3/16 to 1/2 in. long; however, the fragments were of sufficient size to be useful for the subsequent study. The diamond pyramid hardness of the crystals after blasting was in the range 430 to 450 as compared with 340 for the as-melted material, which shows a definite hardening resulting from plastic deformation. These hardness values were obtained using a 1000-g load and taking readings only in sound portions of the crystals free of cracks. The crystals exhibited profuse twinning as shown in Fig. 1. No such structure is present in the as-melted condition. Most of these twins have jagged twin boundaries and are similar in appearance to those found in molybdenum by Mueller and Parker. The twins in both crystals were found to be parallel to {112} planes. This identification was made by using the conventional two-trace method. Subsequent efforts to describe these twins more fully were carried out on crystal A. If the longitudinal axis of crystal A is placed in the (001)-(011)-(Il l) basic triangle of the standard cubic stereographic projection, as in Fig. 2, then the two sets of twins shown in Fig. 1 are parallel to the (112) and (121) planes. Fig. 3 shows a schematic representation of a twin with jagged boundaries. This type of twin with a <111>

Jan 1, 1962

By H. I. Aaronson, C. Laird

Although the past results of X-ray experiments indicate that the broad faces of 0&apos; plates are coherent with their matrix, dislocations lying in arrays have frequently been observed at these boundaries by transmission electron microscopy. Critical experiments employing the latter technique have been carried out in order to determine the origin of these dislocations. It is concluded that 8&apos; plates are essentially coherent with the matrix at their broad faces throughout the aging temperature/time envelope studied. Virtually all of the dislocation arrays observed are deduced to have been formed by plastic deformation accompanying transformation. The proportion of dislocations arising from convexity of the plates is shown to be negligible by comparison with that from plastic deformation. At the higher aging temperatures, a[001] dislocations appeared in moderate numbers. These dislocations were traced directly, however, to the ledgewise dissolution of 0&apos; occasioned by the formation nearby of 0 crystals. On the other hand, since there is a parametric difference normal to the broad faces of the ?&apos; plates, mismatch dislocations do form at their edges. A previous conclusion that these dislocations have Burgers vectors of type a[001] was confirmed directly. The edges of 0&apos; plates were observed to develop octagonal shapes when growing, but circular shapes during dissolution. 1 HIS paper presents the results of an investigation of the interfacial structures of plates of the transitional phase, 8&apos;, formed in an A1-4 pct Cu alloy. In a companion paper, Part 11, the effects of these structures upon the migration kinetics of a:?f boundaries are reported. This work is pa.rt of a general program designed to establish the basis of precipitate morphology. The present authors in Al-Ag,1 and whitton2 previously in U-C alloys, have used transmission electron microscopy to examine directly the vander Merwe3-6 networks of dislocations anticipated7 to compensate the small amount of lattice misfit normally founda at the broad faces of Widmanstatten plates. Since the broad faces of 0&apos; plates are considered to be perfectly coherent with the corresponding habit planes in the a matrix,&apos; no dislocations should be present at these faces. Many reports have been published, however, giving evidence to the contrary.10-18 The primary objective of this investigation was therefore to ascertain the nature of these dislocation structures. An attempt to do this is described in the first three sections of this paper. Inspection of the matching of the a and 8 &apos; lattices at the orientations of the 0:0&apos; boundary corresponding to the edges of 0&apos; plates raises the possibility that these edges may be made up of rather closely spaced edge- type misfit dislocations oriented so as to be sessile with respect to the lengthening or shortening of the plates. Since this structure should severely inhibit migration of the plate edges (Ref. 7, Part II), a situation not originally anticipated,&apos; an experimental determination of the interfacial structure of the edges of 8&apos; plates was clearly in order, and is reported in Section III. Those aspects of the experimental procedure applicable to both Parts I and I1 are presented in the next section. Specific procedures applicable to individual aspects of each investigation, and also the relevant surveys of the literature, are then individually reported in the appropriate sections. I) GENERAL EXPERIMENTAL PROCEDURE The material used in both parts of these studies was the same as that of a previous investigation:" strips of A1-3.93 pct Cu, 0.009 in. thick, prepared as before, solution-annealed at 548°C for 6 hr, and quenched. Details of subsequent aging, and in some cases deformation treatments, are given in the Experimental Procedure sections of the individual parts of both papers. Specimens of the heat-treated strips were electro-thinned as beforeLg and examined in a Philips EM 200 microscope equipped with a goniometer stage. A commercial hot stage, of the grid-heater type and capable of * 30-deg tilt about one axis in the plane of the specimen, was also used for kinetic studies. The usual precaution of calibrating for the additional heat supplied by the electron beam was taken.19 A 16-mm cine cam-I era mounted outside the viewing window was frequently used to record the transformations. Conventional selected-area diffraction and dark-field viewing techniques were used to identify the precipitates in the foils. Normal bright-field images corresponding to two-beam diffracting conditions or dark-field images were employed to characterize the dislocations observed at the interfaces of the precipitates. The application of these techniques to the study of an interphase boundary, and the interpretation of the images,20&apos;21 has been fully described in a previous paper.&apos;

Jan 1, 1969