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By Maurice Ewing

THE purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for, this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data sum-marized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the oppor-tunity for checking results so thoroughly is given. In the second place, the fact that recent commentators 1.2.1 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1922, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

By David T. Peterson

Calcium metal was found to deoxidize thorizcm at 1000° to 1200° C. The reaction kinetics were determilled and related to the diffusion coefficients of oxygen in thorium. The solubility of oxygen in thorium, the minimum oxygen concentration, and the diffusion coefficient were determined from 1000° to 1200°C. This firocess results in the lowest oxygen concentrations zohich have been reported for thorium metal. FOR many years it has been known that calcium metal will reduce thorium oxide to thorium metal. This reaction has been the basis for several methods of preparing thorium metal. From the equations giv-by Kubaschewski and vans, ' AF" for the reaction Cao, + Tho,(,) - CaO(,, + Th(,) was calculated and found to be -3.4 kcal at 1000°C, -2.5 kcal at llOO°C, and -2.0 kcal at 1200°c. Thorium is very slightly soluble in liquid calcium, and the solubility of calcium in solid thorium is very low. Consequently these metals would be in essentially their reference states. If thorium containing oxygen were equilibrated with liquid calcium between 1000° and 1200°C, the oxygen content of the thorium would have to be below the solubility limit in thorium. Oxygen is one of the impurities most difficult to remove from thorium and is the most abundant impurity in metal prepared by almost all known methods. Fortunately, oxygen does not have a large influence on the properties of thorium because the solubility in solid thorium is very low. EvenT in thorium containing 100 ppm of 0, particles of thorium oxide can be observed in the microstructure. In view of the incompatibility of thorium oxide and liquid calcium and the low solubility of thorium oxide in thorium, the deoxidation of thorium by this method was investigated. For thorium containing an amount of oxygen well in excess of the solubility limit, the reaction should proceed in the following sequence. The oxygen content of the thorium matrix near the surface would be depleted by the diffusion of oxygen to the surface. At the surface, the oxygen would react with calcium to form calcium oxide. To maintain equilibrium within the thorium, thorium oxide would dissolve to keep the matrix saturated. Consequently, the thorium-oxide particles would disappear first at the surface and then the particle-free rim would grow in thickness. If the rate-controlling step were the diffusion of oxygen through this layer of thorium which was growing in thickness in direct proportion to the amount of oxygen removed, the well known parabolic time law should be observed. If the oxygen concentration at the surface of the thorium and at the inner surface of the deoxidized rim were known, the diffusion coefficient of oxygen in thorium could be calculated from the parabolic rate constant. EXPERIMENTAL PROCEDURE The thorium metal used in this study was prepared by calcium reduction of ThF, by the method described by Wilhelm.' The analysis of this metal is given in Table I. The carbon was determined by combustion, the oxygen by the HC1-insoluble residue method, nitrogen by the Kjeldahl method, and the other elements by emission spectroscopy. A section of this ingot was hot rolled at 600°C to 1/4 and 1/8-in. thick plates. Specimens approximately 7/8 in. square were cut from these plates, and all surfaces of the specimens were cleaned and smoothed by filing with a clean file. Individual specimens were placed in 1-in. diam by 2-in.-long tantalum capsules. Approximately 1 g of clean, high-purity calcium was placed in the capsules and an end closure arc-welded in place. The tantalum capsules were sealed in Inconel crucibles to protect the reactive metals from oxidation. The entire loading procedure was done in a glove box filled with pure argon. The loaded crucibles were placed in a muffle furnace, controlled within 2OC of the desired temperature, for a measured length of time. After the specimen had cooled to room temperature, it was sectioned perpendicular to the large faces and through the mid-point of two of the sides. The sectioned specimen was mounted and polished through Linde A abrasive. The rim which was free of thorium-oxide particles could be clearly observed microscopically as mechanically polished. Twenty measurements of the thickness of the rim were made at equally spaced points far enough from the end of the

Jan 1, 1962

By William A. Johnson

IT was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomogeneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot he obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yields information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most important types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in a gold-lead

Jan 1, 1942

By E. H. Burdick

The difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals— pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of I .o per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1943

By E. H. Burdick

The difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals— pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of I .o per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1943

By L. B. Harris

Continuous cyclic unloading during tensile work hardening of polycrystalline zinc at room temperature enables specimens to sustain greatly increased extension. Such enhanced ductility is associated with creep-type extension, during which the cyclic component appears to promote relaxation of internal strains. It is possible to trace the transitions from tension, through enhanced cyclic extension, to fatigue and relate the observed behavior to simpler types of deformation. DISTINCTIVE deformation behavior has been shown to occur when loading includes both cyclic and unidirectional components. For aluminum and copper extended by a sequence of progressively biased strain reversals, coffin1 observed greater fracture ductility and lower flow stresses than during monotonic tension. This may be compared with the reduction in hardness obtained from conventional fatigue softening. But fatigue softening is accompanied by enhanced fatigue life,' whereas Benham3 found that fatigue life was reduced when copper continuously extended during axial load cycling. The corresponding specimen elongation, for large cyclic load amplitudes, was greater than during normal tension. Under different conditions, Bendler and wood4 found that torsional fatigue initiated extension in copper under low tensile loads previously in equilibrium with the specimen; fatigue life was again reduced. Thus there is a type of cyclic softening which is associated with reduced fatigue life and which occurs when the cyclic loading is accompanied by a unidirectional strain component. Further, the fracture ductility or extension obtained from the unidirectional component can exceed that obtained in the absence of cyclic load. Specimen extension was not initiated by axial fatigue at small load amplitudes;3 hence Benham's work distinguishes between fatigue at large and small amplitudes, the former often being linked with unidirectional deformation because of similarities in strain Structure. The initiation of tensile extension during torsional fatigue,4 however, occurred with small amplitudes. Comparable changes in behavior have been ob- served during creep. kennedy' found that combined cyclic and creep stresses on lead at 32°C increased the rate of elongation over that for simple creep, the consequence being a reduction in creep life. It was also demonstrated that small cyclic stresses applied after creep deformation initially increased recovery, but that prolonged application produced only normal fatigue hardening. It is clear that physical properties can be changed by interaction between the cyclic and unidirectional deformations, but owing to the number of different ways in which the deformations can be combined and the large number of possible variables for each combination, trends of behavior become easily obscured. One definite conclusion is that enhanced ductility or increased extension can be obtained by cyclic action, and it is this process that has been investigated for the tensile test by measurements of the extra tensile strain produced by the addition of a cyclic tensile component. EXPERIMENTAL PROCEDURE Material. Specimens were 99.99 pct Zn wire of 1.6 and 2.0 mm diam. Mean grain diameter was 0.02 mm, sufficiently small to give a ductile necked-down fracture under all loading conditions. All experiments were conducted at an average temperature of 20°C. Normal Tension. Unidirectional tensile curves at different strain rates were obtained from an In-stron testing machine, on which load-time curves were recorded autographically, using gage lengths of 5 and 10 cm. Straining was at constant cross-head velocity, and quoted strain rates are with reference to initial specimen length. Measurements of total elongation under simple tension were also made on the tensile machine that had been modified to incorporate an added fluctuating load. Combined Tension and Rapid Cyclic Load. An electromagnetic vibrator was coupled to the elastic beam of a Hounsfield ensometer- and driven sinus-oidally from a power amplifier at frequencies from 20 to 360 cps, the flexible connecting links on the tensometer being replaced by rigid fixtures to eliminate lateral vibration in the specimen. One end of the specimen was pulled by the normal extension drive of the tensometer while the other end, fixed to the elastic beam and vibrator, was subjected to rapid oscillations of load. It was thus possible to apply cyclic load to a tensile test without altering the rate of extension of the specimen

Jan 1, 1964

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neilll observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in inter-granular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle3 in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1942

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neilll observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in inter-granular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle3 in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1942

JULY was a month of great turmoil, both economic and political, in many parts of the world. Instead of conditions improving, they seem to have been getting worse. In Ireland, civil war is still in progress. Germany was in the throes of a political upheaval. The meaning of the assassination of Rathenau became clear. It evinced the development of a class struggle between the bourgeois and socialistic parties which may rock the country to its foundation and will increase the difficulties of arranging things with the French and solving the reparations problem. In Poland, a similar contest is developing. Austria is already so completely contaminated by the socialist element that it is unable to get outside assistance and is thus falling into a state of despair but little short of what prevails in Russia. The conference at the Hague came to an abortive end for the reason that it was impossible to discuss affairs with the Russians in any reasonable way. The Germans declared their inability to meet the reparation payment that fell clue on July 15 and the Commissioners for the Allies granted them an abate-ment of a portion thereof and are listening attentively to the supplication of the Germans for a moratorium of one or two years. In the United States, July was a month of widespread labor troubles, accompanied by a great deal of disorder and violence, which led to detachments of the National Guard being called out in several states. The railway shopmen, about 400,000 in number, struck on July 1. The road maintenance men decided not to strike, but many thousands of them quit work without the sanc-tion of their union. There were more strikes in the textile industry in New England and in similar industries all over the country. Early in July, it was estimated that about 1,250,000 men were out on strike. The coal strike continued. Early in the month the President summoned operators and miners to Washing-ton and submitted a plan for the compromising of disputes. After a week's consideration the miners re-fused flatly to agree to anything. The majority of the operators consented to accept the proposed arbitration, but a minority refused. Following this abortive at-tempt the President dismissed the conference with the injunction "to return to your mine properties and resume operation." Production has not increased.

Jan 8, 1922

By George K. Foster, Charles D. Borror

THE Jeffrey mine of the Canadian Johns-Manville Co., Limited, is in the town of Asbestos, situated approximately 100 miles northeast of Montreal and about the same distance southwest of Quebec, in Richmond County, Quebec. Mining operations were started in 1881 on outcrops on a hill, as a side-hill cut, followed by a second and third cut. This development was the forerunner of the present large open-pit operations, the mine now ranking as the largest openpit asbestos mine in the world. Operations were first carried on by hand, then by horsepower and later by stem cableways. By 1924 the derrick spans, 2000 ft. or more long, became unwieldy. To overcome this, and also to eliminate hand labor as much as possible, steam shovels and railroad haulage were introduced. The steam shovels were replaced in 1928 by larger electric shovels of the full-revolving type. THE ORE BODY The ore body is a serpentinized peridotite rock mass. The chrysotile fibers form a network of veins throughout, varying from microscopic width to two or more inches measured across the veins (Fig. I). These veins may be continuous for a few or many feet; they may increase or decrease in width within a few feet. The veins in which the fibers occur perpendicular to the veins are known as cross fiber. Those in which the fibers lay parallel to the veins are known as slip fiber. The cross fibers are of better quality, and more in demand. The majority of the fiber [ ]

Jan 1, 1946

By P. W. Bennett, E. M. Elkin

A new technique for the recovery of palladium and platinum and sludge from go12 electrolyte eliminates many of the drawbacks of the zinc-dust cementation process. In the electrolytic refining of gold by the Wohwill method, the electrolyte contains about 100 gpl gold as AuCl, and 100 gpl free hydrochloric acid. Any palladium and platinum contained in impure gold dissolve and accumulate in the electrolyte. When their concentration approaches that of gold, it becomes desirable to discard the electrolyte and to recover the gold and the palladium and platinum. As practiced at Canadian Copper Refiners until recently, discarded electrolyte was treated with sulfur dioxide to precipitate the gold. 2AuCl3 + 6H2O + 3SO2 —2Au + 6HC1 + 3H2SO4 The gold precipitate was filtered off, washed with water, and melted with scrap anodes. The wash water was added to the gold-free filtrate and treated with zinc dust to cement the palladium and platinum. PdCl2 + Zn — Pd + ZnCl2 PtCl4 + 2Zn—Pt + 2ZnCl2 The precipitate was separated and sold as Pd-Pt concentrate, and the barren filtrate and wash water were discarded. The receipts of palladium and platinum at this company were too small to warrant their refining. The process suffered from a number of disadvantages. Handling the gold-free solution was disagreeable, as it was laden with sulfur dioxide even after blowing with air overnight. Subsequent treatment with zinc dust was also troublesome. A large excess of zinc dust was required. Spray, acid mist, and vigorous evolution of hydrogen accompanied the reaction. The Pd-Pt precipitate was grossly contaminated with occluded unreacted zinc and with yellow granules of sulfur, thought to be formed by the reduction of sulfur dioxide and its derivatives. Repeated boiling of the precipitate with hydrochloric acid and washing with water decreased somewhat, but did not eliminate, the zinc. After drying overnight, the precipitate hardened to a clinkerlike mass that was difficult to grind. Grinding, handling, and packing created heavy dusting. Even weighing in an analytical balance generated dust, indicating that the powder was easily charged with static electricity. The total palladium and platinum content of the powder varied from 56 to 72 pct, with an average of 65 pct. The powder dissolved in aqua regia with difficulty, leaving a small amount of insoluble residue. However, the main drawback of the process was the strongly hygroscopic Pd-Pt product. The powder showed a marked though erratic increase in weight and a corresponding decrease in assay on exposure to air, even during the course of laboratory analysis. Such changes were the source of disagreement between Canadian Copper Refiners and the buyers of concentrate. The cause of the change in weight is believed to be hydrogen, liberated by the action of zinc dust on hydrochloric acid. Some of this hydrogen was adsorbed so strongly by the precipitate that it could not be driven off during the drying. On exposure to air it oxidized catalytically, forming water. Experiments soon showed that the entire process of treatment of discarded electrolyte then in use would have to be changed. A small quantity of apparatus was moved into the gold room, and experimentation was held to a minimum compatible with the development of a new process. PALLADIUM AND PLATINUM PRECIPITATION It was thought that zinc could be replaced with a reagent other than a hydrogen-evolving metal. Semiquantitative experiments showed that platinum and palladium could be precipitated completely from the gold-free solutions with such well-known reagents as sodium formate, formic acid, formaldehyde, and paraformaldehyde. Sodium formate was the preferred reagent, since the other three are volatile and somewhat toxic. The gold-free solutions used were those saturated with sulfur dioxide, partly freed of sulfur dioxide by aerating overnight, completely freed by boiling, as well as strongly and weakly acidic, neutral, and alkaline solutions. The reactions are complex and can be represented by these over-all equations: PdC1, + HCOONa — Pd + NaCl + HC1 + Co2 PtCl4 + 2HCOONa — Pt + 2NaCl + 2HC1 + 2CCX, Strongly acidic solutions required as much as five times the theoretical amount of sodium formate as did solutions neutralized to pH 4.5. Increasing the pH decreased the consumption of

Jan 1, 1965

By R. E. Ogilvie, E. T. Peters

The X-ray Kossel-line method has been used preaioz~sly for measuring lattice parameters to accuracies of 1 part in 100,000.5 A second application of this method is described for determining the crystallographic orientation of a randomly positioned single-crysta1 spherical volume that can he as small as 50 µ in diameter, within accuracy limits of ±1/2 deg. The theory, experimental procedure, and interpretation of Kossel-line patterns and an experimenta1 verification of the predicted orientation relationship of the cph k and fee a Cu-Si phases are presented. This orientation relationship can be described as (111)a, (00.1)k; [110]a [11.0]k. In addition, the lattice parameter of the a phase was found to he a. = 3.62154 ± 0.00014Å. The Kossel-line method when used in conjunction with electron microanalysis is shown to he capable of providing a complete chemical and structural analysis of a given crystal. THE most easily accomplished methods for determining the orientation of a single crystal are variations of the Laue X-ray diffraction method. Although certain materials can be oriented to within ± 1 deg accuracy by observation of exterior macroscopic features, such as etch pits, cleavage faces, or growth features, the Laue method is generally preferred for routine laboratory application. Both back-reflection and transmission patterns are coordinated by appropriate reference charts and are plotted in terms of reflection plane poles (normals) on a stereographic projection. Orientation is deduced by relating the pole distribution (which is fixed by the crystallographic symmetry of the specimen) to two specified external reference directions. The Laue method has several limitations. 1) Orientation can rarely be determined to better than ±l deg accuracy. Principal errors involve inaccuracy in specimen-to-film distance, measurement confidence of individual Laue spots, and stereographic plotting. 2) Because of the indeterminacy of the X-ray wave length diffracted to a given spot, it is not possible to determine supplementary crystallographic data, such as interplanar spacings and lattice parameters. 3) The method is generally limited to specimens of cubic symmetry or to specimens of high symmetry and known structure. 4) The relatively large cross-sectional area of the incident X-ray beam generally precludes the measurement of relative grain orientation in a polycrystalline material.* _____ Several of these limitations can be overcome by application of the Kossel-line method, which has been previously employed for precision lattice-parameter determinations.'-= For this method, a point source of divergent monochromatic X-rays is generated within the crystal by means of an incident electron beam. The divergent X-rays which fulfill the Bragg law are diffracted by the specimen and are recorded on a film placed either in transmission or back reflection. Analysis of the film yields a direct measurement of orientation and lattice-spacing values to an accuracy of ±1/2 pct. As analyses can be obtained from spherical specimen volumes as small as 50 µ in diameter, the method provides a means for structural analysis of second-phase or impurity precipitates within a given matrix. The primary limitation of the Kossel-line method is the requirement for an electron microanalyzer or similar apparatus capable of producing a finely focused electron beam. This paper is designed to present the theory, experimental procedure, and geometrical interpretation of Kossel patterns. The experimentally determined orientation relationship between the k and a phases occurring in the Cu-Si system and a precision measurement of the a lattice parameter are presented as a practical application of the method. THEORY OF KOSSEL LINES Divergent X-ray beam photography utilizes an effective point source of characteristic X-rays which, when diffracted from a single crystal, form numerous diffraction and absorption cones that are recorded on film.7 The cones generated from a source lying within the crystal are called Kossel lines.' Although the X-ray scattering from a divergent point source contained within a crystal is described in terms of Laue dynamical theory,9 the directions of the diffracted spectra can be ade-

Jan 1, 1965

By E. G. Leonardon, D. C. McCann

The search for oil has required, and without a doubt supplies, a tremendous amount of information on the structure, composition, physical properties, and history of sedimentary rocks. The earliest and most complete source of knowledge is the sample or core of the rock itself, the uses of which are well known. The purpose of this paper is primarily to discuss a new method for obtaining these cores, and to illustrate its use in connection with electrical logs. Most cores have been obtained through a special adaptation of rotary drilling, and the results have been remarkably good, considering the mechanical problems involved. Unfortunately, because of the time and expense, this method cannot be used for the entire length of the drill hole. Even though ingenious contrivances have been evolved in order to reduce the time spent in round trips, such as wire-line coring equipment, mechanical coring still remains too expensive to be carried out continuously. In practice, therefore, one is finally compelled to estimate the probable depths of the more interesting horizons and, allowing a wide margin of safety, to core through those sections only. It is true also that interesting results have been obtained by examining the cuttings brought to the surface by the mud circulated in the well during the process of drilling. Be that as it may, the inescapable fact remains that key horizons may be passed inadvertently, for one reason or another, while the drilling operations are being performed. The only continuous record of the formations encountered is that furnished by electrical surveys. Obviously, it would be desirable to make the electrical survey first and to take the samples from the wall of the hole according to the indications on the electrical log. In this way, it would be possible to core only the exact sections desired, eliminating the otherwise inevitable estimates as to the point at which to start coring, and thereby reducing to a minimum this expensive operation. At the same time this method would provide a maximum of useful samples. A device for taking samples of the formation from the walls of a hole therefore offers the possibility of recovering cores from zones otherwise lost as a source of this type of information. Furthermore, by coring

Jan 1, 1939

By E. G. Leonardon, D. C. McCann

The search for oil has required, and without a doubt supplies, a tremendous amount of information on the structure, composition, physical properties, and history of sedimentary rocks. The earliest and most complete source of knowledge is the sample or core of the rock itself, the uses of which are well known. The purpose of this paper is primarily to discuss a new method for obtaining these cores, and to illustrate its use in connection with electrical logs. Most cores have been obtained through a special adaptation of rotary drilling, and the results have been remarkably good, considering the mechanical problems involved. Unfortunately, because of the time and expense, this method cannot be used for the entire length of the drill hole. Even though ingenious contrivances have been evolved in order to reduce the time spent in round trips, such as wire-line coring equipment, mechanical coring still remains too expensive to be carried out continuously. In practice, therefore, one is finally compelled to estimate the probable depths of the more interesting horizons and, allowing a wide margin of safety, to core through those sections only. It is true also that interesting results have been obtained by examining the cuttings brought to the surface by the mud circulated in the well during the process of drilling. Be that as it may, the inescapable fact remains that key horizons may be passed inadvertently, for one reason or another, while the drilling operations are being performed. The only continuous record of the formations encountered is that furnished by electrical surveys. Obviously, it would be desirable to make the electrical survey first and to take the samples from the wall of the hole according to the indications on the electrical log. In this way, it would be possible to core only the exact sections desired, eliminating the otherwise inevitable estimates as to the point at which to start coring, and thereby reducing to a minimum this expensive operation. At the same time this method would provide a maximum of useful samples. A device for taking samples of the formation from the walls of a hole therefore offers the possibility of recovering cores from zones otherwise lost as a source of this type of information. Furthermore, by coring

Jan 1, 1939

By George R. Mansfield

Interest in the reserves of phosphate rock in the United States and their proper conservation has recently been aroused by hearings held in different parts of the country by the "Joint Committee to investigate the adequacy and use of phosphate resources of the United States." This committee was appointed within a few days after a Presidential message to Congress on the same subject, dated May 20, 1938, and began to function almost immediately. Hearings were held in Washington, D. C., Pocatello, Ida., Wilson Dam, Ala., Knoxville, Tenn., and Lakeland, Fla. The resulting testimony, when published, comprised a volume of 1182 pages.l At the earlier hearings held in Washington and Idaho the seeming disparity between the great reserves of the West and the smaller reserves in the East led to some suggestions as to the desirability of curtailing or even prohibiting the exportation of phosphate rock so that eastern producers, becoming alarmed, cooperated in making available for the use of the committee information hitherto closely guarded. This information has provided an opportunity for new studies by official agencies, for a restatement of the reserves of Florida and Tennessee, and for some modification of figures for the Western States. The writer, representing the Federal Geological Survey, was given free access to the Florida material and has prepared for publication a report,² some features of which are summarized in this paper. The Tennessee material was studied by Dr. G. I. Whitlatch,³ of the Tennessee Division of Geology. Prof. J. Stewart Williams,* of the Utah State Agricultural College at Logan, has published a recent study of the phosphate resources of Utah and the writer has given some further study to reserves of western phosphate from the viewpoint of including material of lower grade than that hitherto considered. Technologic advances in the phosphate industry must be credited with a large share in the expansion of reserves by making available for

Jan 1, 1942

By George R. Mansfield

Interest in the reserves of phosphate rock in the United States and their proper conservation has recently been aroused by hearings held in different parts of the country by the "Joint Committee to investigate the adequacy and use of phosphate resources of the United States." This committee was appointed within a few days after a Presidential message to Congress on the same subject, dated May 20, 1938, and began to function almost immediately. Hearings were held in Washington, D. C., Pocatello, Ida., Wilson Dam, Ala., Knoxville, Tenn., and Lakeland, Fla. The resulting testimony, when published, comprised a volume of 1182 pages.l At the earlier hearings held in Washington and Idaho the seeming disparity between the great reserves of the West and the smaller reserves in the East led to some suggestions as to the desirability of curtailing or even prohibiting the exportation of phosphate rock so that eastern producers, becoming alarmed, cooperated in making available for the use of the committee information hitherto closely guarded. This information has provided an opportunity for new studies by official agencies, for a restatement of the reserves of Florida and Tennessee, and for some modification of figures for the Western States. The writer, representing the Federal Geological Survey, was given free access to the Florida material and has prepared for publication a report,² some features of which are summarized in this paper. The Tennessee material was studied by Dr. G. I. Whitlatch,³ of the Tennessee Division of Geology. Prof. J. Stewart Williams,* of the Utah State Agricultural College at Logan, has published a recent study of the phosphate resources of Utah and the writer has given some further study to reserves of western phosphate from the viewpoint of including material of lower grade than that hitherto considered. Technologic advances in the phosphate industry must be credited with a large share in the expansion of reserves by making available for

Jan 1, 1942

By John Devine

DURING the past few years the Bureau of Mines has been studying hydrogen-sulfide corrosion in the petroleum and natural-gas industries. Early work was confined to investigating the various practical, or operat-ing, factors that control the corrosion reaction when ordinary mild steel is being attacked. In that work it was shown that, if the optimum operating conditions1 are obtainable, . gas containing hydrogen sulfide can be handled at ordinary temperatures without serious corrosion resulting. However, frequently "sour" gas must be handled under other than optimum operating conditions, and combating corrosion then becomes a problem to be considered more during the construction of a system than during its subsequent operation. That is, where economi-cally practicable in such cases the designer will seek to substitute for mild steel other steels or ferrous metals more resistant to corrosion by hydro-gen sulfide. The comparative resistance of various commercial steels and alloy steels to corrosion by hydrogen sulfide at elevated temperatures has been reported systematically by previous investigators,2 but similar information for corrosion at ordinary temperatures is available only from scattered sources, representing different methods of testing. As the value of comparative corrosion tests depends largely upon the use of a

Jan 1, 1934

By J. H. Bucher

The effect oj strengthening by the precipitation of CbC on the toughness offerrilic steel (0.11 pct C, 0.74 pct Mn, 0.02 pct Cb) was stlrdierl. A g-veater degree of pvecij~itatiotz strengthning is ohtaznable by aging the so11ution-treated steel rtt velaticely Low temperature was (1050" to 1l0O3F) than at higher temperatures (I150" to 1200°F). Tlzis ),eslrlts because a finer dispersion of CbC is obtained. However, the ductile-brittle transition te~ripertltlo.e is raised approximately tlzjeee tirues as IFLIIC~ perv a given yield stress increase) by aging in the lower tempareture range, as opposer1 to the Irigher temperaturee range. This is proposed to result pl-iir~avily because different precipitation distributions ar-e associated with the different aging -treaments. For tile steel aged at 1050" and 1100 F, heavy: precipitation on disloccctions occurs resulting in a high degree of rlislocution pinningh tl~us lowevirzg- the toilguiess. in tll c(.rise of the steel aged at 1150 'a?zd 1300"F, Pvecipitatiol~ is irzove g-enerally distributed throughout the matrix rather limn preferentially on dislocations.; and Ike detlsitj, oj mobile dislocations is not sttyong-ly affected. THE most effective means of strengthening hot-rolled ferritic steels are grain refinement and precipitation hardening. It is well-known that grain refinement increases both the strength and the toughness. However, the upper limit of yield strength obtainable by grain refinement alone is about 60,000 psi,'12 i.e., without the formation of acicular structures of lower toughness. The most economical means of obtaining higher strengths is the addition of small amounts of elements such as columbium, vanadium, and titanium which form carbonitrides. These precipitates are very effective in increasing the strength, but the ductile-brittle transition temperature is is Although it is agreed upon that precipitation decreases the toughness, there has been little effort to isolate the causative aspects of embrittlement. The purposes of this research are to assess quantitatively the embrittlement associated with different precipitate distributions and morphologies, and to correlate the degree of the embrittlement with the microstruc-ture. In this manner, a more fundamental insight into the mechanism of embrittlement may be gained. The steel selected for this purpose was a low-carbon, columbium-bearing steel which, after solution treatment, was aged in various time-temperature cycles while attempting to hold all other microstructural variables constant. MATERIALS AND PROCEDURE The composition of the steel used in this investigation is given in Table I. Starting with commercially hot-rolled material 0.074 and 0.280 in. thick, tensile blanks were cut from the thinner material and sub-size Charpy blanks from the thicker stock. The steel had been rolled using a low finishing temperature and rapid cooling after hot rolling to produce grain refinement. Also, chemical-extraction analysis and electron-microscopic examination revealed that the cooling was rapid enough to suppress any significant precipitation of CbC. Therefore, the as-rolled steel is essentially in the solution-treated condition in terms of the precipitation reaction, and it was used as the base material in this investigation. The room-temperature tensile properties of the as-rolled steel aged at 1100", 1150", and 1200°F for various time intervals were determined, see Table 11. The ductile-brittle transition behavior was studied for smooth and notched tensile specimens, and longitudinal half-size (0.200 in. thick) Charpy V notch specimens aged at 1100" and 1150°F for various times, also Table 11. In addition, tensile specimens aged for single times at 1050" and 1200°F were evaluated with respect to their ductile-brittle transition. Only one 1050°F treatment was used because of the extremely slow kinetics of precipitation at this temperature and because no significant difference between 1100°F aging was observed. Only one treatment at 1200°F was used because aging at this temperature alters the shape of the grain boundary cementite particles present in this steel and complicates analysis. The design of the tensile specimens is given in Fig.1.

Jan 1, 1968

By J. W. Mills

The strike and dip of bedded formations is readily determined by trigonometry if some marker horizon is intercepted by three holes. If no marker can be identified and if orientation of the cores is unknown, as is the usual case in diamond drilling, the determination still can be made readily by the use of a stereonet if the bearing, inclination, and angle the bedding makes with the core axis is known for each of the three holes. Such determination, valid only if the bedding orientation is fairly uniform within the area drilled, is considered simpler, faster, and more effective than any solution previously published. Method: The steps of this procedure are as follows: 1) Mark north and south poles on tracing paper placed over stereonet. 2) Plot the three diamond drillholes by drawing a line from the center of the net in the direction of the bearings of the holes. Then rotate the paper until each line, in turn, lies along the equatorial diameter of the net; the end of each line is determined by the inclination of the hole measured in degrees from the periphery toward the center of the net along the equatorial diameter. Fig. 1 illustrates a vertical hole and a hole inclined at -23° due east.

Aug 1, 1955

By Carl Zapffe

The object of the Bradley process is to free manganese oxide from its associated gangue and separate the contained iron oxide by dissolving the manganese and precipitating it from the solution. This results in producing two oxides as concentrates, the one to be converted into a manganese sinter and the other into an iron sinter. The manganese sinter may be made to contain as high as 70 per cent. inanganese and as low as 1 per cent. silica, with phos'phorus not to exceed 0.02 per cent, and from that figure downward to about 0.005 per cent., and with sulfur at 0.007 per cent. The iron sinter contains about 2.50 per cent. manganese, making the total recovery of the manganese 98 per cent. The method involves selective roasting, which converts the manganese into a form in which it is soluble in an aqueous solution of ammonium sulfate, then precipitating the manganese as a hydrate by using ammonia gas, then stabilizing and washing the hydrate, followed by sintering; concurrently most of the iron oxide is converted by roasting into an insoluble form and becomes a residue with magnetic qualities, which makes possible the recovery of much of the iron in the ore. Leaching manganese by using sulfur dioxide gas was shown possiblc Inany years ago. Mr. Bradley tried it for a year, working in conjunction with the original experimenters of that method, and found that while relatively pure inanganese oxide could be produced, the likelihood of developing a commercial process along this line was not very encouraging. He also attempted leaching with nitric and sulfur acids, but the cost of recovery mounted and the quality of the product was not as good Mr. Bradley tried nearly every leaching method proposed, and the expen-ments were made on a large scale in the spacious laboratories of John C. Wiarda & Co., in Brooklyn, N. Y. Insufficient encouragement was discernible in the results obtained. Upon the suggestion of N. Arthur Laury, of John C. Wiarda & Co., Bradley undertook using arnrnoniurn sulfate. Because a high rate of recovery appeared feasible, Bradley planned the erection of a 4-ton pilot plant at the State of Minnesota Mines Experiment Station, at Minneapolis. The results of that work are described in this treatise.

Jan 1, 1929