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By Frank F. Poland

TEE purpose of this paper-is to describe a new process for the refining of secondary copper-base metals and a specially designed high-temperature electric-resistor furnace used in the process for the distillation of zinc from these metals. The process was used for the conversion of nickel silver to cupronickel and to recover the zinc content in metallic form. It also proved applicable and economical for the treatment of scrap brass for separating and reclaiming the copper and zinc. The relatively large furnace developed for the distillation of zinc is described in detail, for it made economically possible the direct recovery of metallic zinc from scrap brass, which is a new step in the processing of such material. Considerable interest has been shown in the utilization of the distillation furnace for other metallurgical processes, where it is of advantage to operate in a controlled neutral or reducing atmosphere, or to avoid having the processed metal in contact with refractories other than carbon, or to operate at temperatures between 3000 and 4000°F. PURPOSE OF DEVELOPMENT It was recognized early in the war effort that nickel would become a critical metal, therefore all nickel stock and alloys containing relatively high percentages of nickel were frozen immediately. Among these alloys were considerable quantities of various grades of nickel silver, an alloy containing copper, nickel, zinc, and in some grades lead, also minor amounts of iron, manganese and other constituents. At the time there was no existing plant or process to eliminate the zinc, lead, and minor constituents so as to convert this metal to cupronickel, one of the important alloys needed by the U. S. Navy for condenser parts. Therefore the Bureau of Industrial Conservation of the War Production Board requested the executives of the leading nonferrous metal companies to have their metallurgical staffs study the problem of converting this metal to cupronickel conforming to U. S. Navy Specification 44T40. The composition specified therein is as follows: nickel, 29 to 32 per cent; zinc, 1.00; iron, 0.00 to 0.60; lead, 0.05; tin, 1.20; manganese, 0.00 to 1.00; total of other elements (maximum), 0.50; copper, remainder. The problem in converting these alloys to cupronickel was the elimination of zinc, lead, iron, manganese, and other elements without appreciable loss of nickel to slags or other by-products. Revere Copper and Brass Incorporated, through its Research and Development Department, undertook to solve this problem. A Government-owned plant was built at Rome, N. Y., and there the con- version was successfully made.

Jan 1, 1946

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.' The porous-pellet model is found to give a better description than the dense-pellet one for McKewan's measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.''' However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.' One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed' to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967

By Sandip K. Mitra, John E. Dorn

The Basinki-modified Seeger equation for deformation of metals by means of thermally activated intersection of dislocations was used to ascertain the various factors responsible for the strain hardening of poly crystalline aluminum and a series of a solid solutions of magnesium in aluminum. The analyses were based principally on the rate of change of strain rate with stress and the Cottrell-Stokes ratio. From measurements of these quantities on a series of strain-hardened states, the force displacement diagram for intersection, the density of dislocations in the entanglements, and the contributions of the athermal local stress and long-range stress interactions were deduced. Poly crystalline aluminum was observed to have the same force-displacement diagram for intersection as single aluminum crystals, and the corresponding diagram for the magnesium alloys differed in a manner that suggested that small amounts of magnesium may decrease slightly the stacking fault energy of aluminum. Although poly crystalline aluminum had about the same initial density of dislocations as the single crystals, the density of dislocations increased much more rapidly with strain in the polycrystals. This factor and the higher back stresses generated in the poly crystalline aluminum were the major factors responsible for the higher strength of the poly crystalline aluminum, As the magnesium content of the alloys was increased, the initial density of the dislocations also increased. Most of the alloy strengthening arose from this factor; alloying effects due to short-range order strengthening, Suzuki locking, Cottrell pinning, and so forth, were estimated to be quite small. The gveater rate of strain hardening in the alloys was deduced to be due primarily to the greater increase in the density of the dislocations with strain as the magnesium content was increased. It is the purpose of the present investigation to shed additional light on the average plastic behavior of a grain in a polycrystalline aggregate, by analyses, based on dislocation theory, of appropriate experimental test results. These deductions when compared with those from single-crystal data will then serve to illustrate the major items of difference between the plastic behavior of single crystals and the average behavior of a grain in a

Jan 1, 1963

By C. S. Samis, J. C. Mitchell

Sodion activity data have been obtained for the Na-A1 system for sodium concentrations in aluminum between NN, = 25 . 10-and 300 x 10'. This concentration intert-a2 encompasses those sodium concentrations nor1)zally encountered in aluminum reduction cell operation. The sodium activity data were measured by a two-phase equilibration of sodium between a lead and an aluminam rich phase. The Na-Pb system was emplojed as a reference for the determination of the actiz7itj 0.f sodium. The activity of sodiin in aluminuwz exhibits large positi2.e deviations frorn ideality and a strong dependence, on concentration below NN, = 100 x 1K6. The inteated data indicate that the activity of aluminium is equal to its mole fraction over the range of miscibility of the Na-A1 sgstem. The data on the Na-A1 binary have been combined with experimental data on the cryolite-A1 system at 1025°C to obtain the activities of Na F and AlF, in liquid cryolite oz2er the cornposition 1-ange encountered in aluminum cell operation. The results are in agreement with activities calculated from the NaF-AlF, phase diagram. ALUMINUM is produced commercially by the electrolytic reduction of aluminum oxide dissolved in molten cryolite. There is considerable controversy over the actual mechanism of the discharge processes, but sodium potentials in the systems appear to play an important role in the reduction mechanism. The metal-salt reaction involving NaF and aluminum to produce A1F3 and sodium is responsible for the presence of sodium in the aluminum metal phase. Additional sodium may be produced from the simultaneous deposition of sodium and aluminum at the cathode as a result of a cathodic overvoltage. runert' has suggested that sodium gas at atmospheric pressure would be the result of reaction between cryolite and aluminum at 1000°C. Subsequent investigations have shown that production of sodium at atmospheric pressure does not occur. These later investigations can be conveniently separated into two categories. The first involves sodium, aluminum, and cryolite, in which the sodium activity was measured. The second includes a lead phase for sodium activity measurement. Jander and errmann,' studied the reaction: at 1090°C in alumina crucibles under an atmosphere of dry, oxygen-free nitrogen. The equilibrium constant for the reaction was expressed in terms of concentration. Their results in Fig. 1 show an increase in sodium content of the aluminum with increasing NaF/A1F3 weight ratio. Pearson and waddington3 performed similar experiments at 1000°C. Their results are included in Fig. 1. Dewing and ollinshead have measured the sodium content of aluminum as a function of the NF/AF, ratio at 1025"C, Fig. 1, and ewin' measured the sodium content of the aluminum in a system involving the solid reactants NaF, cryolite, and liquid aluminum. This reaction is different from those discussed above. Two solid phases, NaF and Na3A1F6, and a liquid aluminum phase were present. The sodium concentration in the aluminum was determined by the temperature. Dewing's measurements covered the temperature range 679" to 896°C. Omo, Matsushima, and 1t02" investigated the equilibrium 6NaF ential thermal analysis. Stokes and Frank6 determined sodium activities by

Jan 1, 1970

By Waldemar Lindgren

No one would maintain that all ore deposits or all deposits of useful minerals have been formed by the same processes. Generally they have originated by special processes of concentration but these may be of many different kinds. Some deposits have their origin in chemical or biochemical processes of concentration in rivers, lakes or seas, others developed on land by means of chemical reactions of surface waters on various forms of rocks. Certain insoluble substances remained behind; others were dissolved and precipitated in favorable places. This action proceeded in the realm of the oxidizing surface waters or in the deeper zones to which the waters from the surface could find their way. Examples of the latter kind may be found in the extensive copper and vanadium deposits of some sedimentary beds or in the lead and zinc deposits of certain broad limestone strata. In these instances the evidence for any other mode of origin would seem to be very weak indeed.' Nor does it seem possible to deny that circulating waters may form deposits of the more common metals along fissures after having dissolved many constituents from paths traversed. Another very large class has been formed by magnetic processes of concentration. The last 40 years have been a period of intense activity in the investigation and description of a vast number of deposits; all modern methods have been employed and the result is an accumulation of data, difficult or impossible to master. It has been a period similar to that in petrography. The generalizations, the able deductions, have lagged behind. Evidently several geologists have become weary of this "infinite detail" and a mistrust of the microscope seems to have arisen. Although this feeling of being swamped in microscopic detail is a painful experience, nevertheless only through the detail in combination with the large features, and only by utilizing all the related sciences shall we

Jan 1, 1927

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By K. Mukai, M. Ishihara

This report is a brief discussion of the impurity levels both in primary aluminum and super-purily alnminim in connection with raw materials and proc-essing methods. Particularly, truce amounls of im-purities were analyzed by introducing nittss-speclro-gruphy and nenlron-aclivalian analysis techniques. Vanadium and gallium content in primary aluminum metal corresponded to theor amounls in anode coke. but the nickel content in primary aluminum was hide-pendent oj its amount in the anode cake. Sulfur in the anode colic might result in an increase of the iron content in the molten metal in the reduction cell. The content of sodium and calcium increased with increasing bath ratio. In the holding furnacc sodium content decreased rapidly, and nonmetallic inclusions merit separated front the mollen metal. Three-layer elctrolysis was effectire in eliminating many impuri-ties with the exception of copper, aluminum oxide. aluminum nitride, and some rare-earth elements. THE amount of impurities and nonmetallic inclusions in aluminum metal depends on impurities in the raw materials and various production processes. This paper presents an investigation of the behavior of impurities and nonmetallic inclusions in aluminum during the electrolysis process, the period in the holding furnace, and the process of three-layer electrolysis. Chemical analysis and emission spectrometric analysis have generally been used as methods to determine small amounts of impurities in both primary aluminum and super-purity aluminum; however. mass spectrography and neutron-activation analysis have been recently introduced into this field, and trace amounts of impurities can accurately be determined by these latter methods. EXPERIMENTAL WORK Common impurities were determined by means of absorptiometric. polarographic, flame-photometric. and emission-spectrometric methods. However, in the determination of trace amounts of impurities and non-metallic inclusions, the following methods were applied. In the analyses of trace impurities by mass-spec- trographic analysis, samples were exposed in the vacuum spark of double-focus ing Mattauch-Herzog type mass spectrograph (Japan Electron Optics Laboratory, Ltd.). Ilford Q2 photographic plates were used as ion detectors. Fe was used as the internal standard, and the atomic concentration of each element was calculated by the following expression and converted into the weight concentration: where E, and Ei are the exposures (coulomb) when isotopes of the internal standard and impurity elements (on which the estimate is based) show the same density, X is the percent (atomic) concentration of the standard, IF and Ii are the percent abundances of the isotopes of the standard the impurity elements (on which the estimate is based), and Ms and hfi are the mass of the isotopes of the standard and impurity elements (on which the estimate is based). The coefficient of variation in this method is about 40 pct in the range of 0.1 to 1 ppm. In neutron-activation analysis, irradiations were done in the nuclear reactors TRIGA-I1 (neutron flux: 4.7 x 10 11 n per sq cm per sec; Rikkyo University) or JRR-2 (neutron flux: 2 x 1013 n per sq cm per sec: Japan Atomic Energy Research Institute). After the chemical separation, a NaI (3 by 3 in.) scintillator connected to a 256-channel y-ray spectrometer (R.C.L.) was used for counting and recording various activated impurities. The coefficient of variation in this method is about 20 pct. In the analyses of nonmetallic inclusions, aluminum-oxide determination was carried out according to Fischer's method, 3 as follows. A slice of sample was cut off and the surface was cleaned. It was dissolved in bromine-methanol. The solution was filtered and the residue was washed. The residue was fused with potassium bisulfate flux. Then it was dissolved in weak acid, and oxine solution was added. The aluminum oxinate was extracted with benzene. Finally, aluminum was determined absorptio-metrically. Aluminum nitride determination was carried out as follows. A slice of sample was cut off and the surface was cleaned. It was put in the distillation apparatus and decomposed with sodium hydroxide solution. The solution was distilled. Then ammonia was absorbed and

Jan 1, 1967

By Robert E. Bush, E. S. Mardock

The objective of this paper is to present practical methods of applying radioactivity logs to problems of interest both to those engaged in evaluating fundamental reservoir data as well as to those engaged in subsurface structural work. The basic theories underlying the operation of radioactivity logging methods are briefly discussed along with some of the problems arising in the interpretation of the log. Relative methods of quantitative interpretation are described, with a discussion of relative reference lines and specific examples are given showing the application of these relative quantitative interpretation methods. To show the variation of the methods described, specimen wells penetrating formations widely divergent in point of geologic age were selected to demonstrate the application. A relative reference line is determined for the Neutron Curve and by comparison to known petrophysical data such as porosities from diamond cores, a direct quantitative relationship is developed. The application of this relative calibration curve to logs of unknown wells will permit a reasonably accurate determination of porosity in limestone and dolomite formations. Specific examples are given showing the application of these relative methods of interpretation to logs of the Smackover limestone in Louisiana, the Edwards limestone and dolomites of South Texas, and Permian dolomites of West Texas. Radioactivity logs have been used extensively by the petroleum industry for a number of years and recognition of their value has grown steadily, not only as tools to aid in the solution of specific stratigraphic problems, but also as potential sources of the basic data necessary for the estimation of net pay and reserves. The value of radioactivity logs for stratigraphic work has been pointed out in the literature,1,2,4,5,6 and now has long been recognized by the industry, but the quantitative application of the logs has advanced but little beyond the stage of a strong conviction that radioactivity logging curves will some day provide the information on such important quantities as the porosity and the liquid saturation of the formations. During the past few years the staffs of the Lane-Wells Company and Well Surveys, Incorporated, have devoted a great deal of time, thought, and experimentation to the relationships existing between radioactivity curves and the lithologic conditions encountered, and this paper is, in a manner of' speaking, intended as a progress report of this work and includes suggestions which the authors have found useful in the interpretation of radioactivity logs. The section on theory is not intended as a complete exposition of the physical processes involved, but rather as a brief introduction to the reader of these processes so that he may acquire a better understanding of the behavior of the radioactivity curves under the varied conditions encountered in normal well logging. Three relative methods for using neutron logs for the quantitative estimation of porosity in limestone or dolomite are presented. These methods are based on the comparison of logs and porosity data from wells in Louisiana, South Texas, West Texas, and New Mexico. These areas were selected because not only were there more core data available from these areas but also the majority of these data were from limestone or dolomitic zones. The correlation between core data and logs is simpler for limestones and dolomites than it is for sandstones due to the fact that sandstones are more complex than limestones and differ more widely among themselves as to composition of cementing materials, siltiness, etc. When data applicable to the various types of sandstones are available, the authors hope to present a discussion similar to this paper covering sandstones or possibly a more general discussion covering all types of reservoir rocks. The relative methods for estimating porosity which are presented in this paper fall short of the absolute method sought. However, these methods possess the advantage that they can be applied to almost any neutron log as long as the range of application is held within the limits imposed by the local lithologic conditions which prevailed during calibration, i.e., these methods are for short range application only. THE THEORETICAL BASIS FOR RADIOACTIVITY LOGGING The two redioactivity logging curves commercially available today are the

Jan 1, 1950

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By C. D. Wiseman

THE concept of alloying to increase the strength of metals originated during the bronze age. However, at the present time there is no single theory capable of explaining all of the observed strengthening effects of alloying elements on the mechanical properties. In general, it may be said that solid solutions are stronger than the pure metal and that the strengthening effect increases with increasing alloy content. Various theories for solution hardening have been proposed, the first of which was presented by Rosenhain who suggested that the alloying elements roughened the slip planes, thereby requiring a higher stress to initiate slip. Recent work by French and Hibbard2 confirmed Norbury's3 conclusion that those alloying elements which cause a greater change in lattice parameter have larger effects on hardness. However, a given change in lattice parameter produced by different alloying elements does not cause the same change in hardness. A further refinement was suggested by Dorn, Pietrokowski, and Tietz4 who considered differences in valence between the solute and solvent with the change in lattice parameter to explain the plastic properties of aluminum alloys. Allen, Schofield, and Tate5 further investigated the valency contribution to solution strengthening by testing some copper-base solid-solution alloys having constant electron densities. Tensile tests performed on these alloys gave identical stress-strain curves even though the atomic size effect, which varied by a factor of two, was neglected. The advent of dislocation theory6-8 provided a new and powerful tool capable of explaining many phenomena of plastic deformation and indicated new approaches to solution hardening. The basic con- cept of recent theories is that solution hardening is not due to stresses associated with randomly dispersed solute atoms, but rather to a nonuniform distribution of the solute. This conclusion was reached by consideration of the effective tension present on each dislocation line and the ability of a dislocation to pass an obstacle. cottrell suggested the possibility that the internal stresses due to randomly distributed solute atoms would offer essentially no resistance to the passage of dislocations. He reasoned that an edge dislocation may be considered as a rigid line discontinuity. As the dislocation moved through a crystal, the random stress fields would be equally distributed along its length. Since half of the stress fields would be acting to move the dislocation forward and the other half trying to move it back, the net effect on the dislocation would be zero. Thus the randomly distributed solute atoms would not contribute appreciably to solution strengthening. Mott and Nabarro10 considered the dislocation as a flexible, rather than a rigid, discontinuity. They obtained a simple model for a dislocation moving in a lattice having precipated particles, where the dislocation would actually bend around the obstacle until it would loop back onto itself to rejoin and then continue onward. Their work indicated that the minimum radius of curvature of the dislocation line, under the action of an external stress and in the region of an internal stress, would be such that the dislocation would be unable to pass through a matrix containing small closely spaced precipates by the looping process. The dislocations would tend to remain rather straight, approaching the condition of Cottrell's rigid dislocation. Hence, the strengthening must not be due to random solute atoms; however, it might be due to the concentration of atoms, either as clusters of like atoms or as short-range ordered regions, or to the concentration of solute atoms around dislocations. To date, four mechanisms of solution strength-

Jan 1, 1959

By Henry Lloyd Smyth, J. Ralph Finlay

The most important area of the so-called Keewatin rocks of northern Minnesota is that which runs westerly from Lake Saganaga, near the national boundary, and finally disappears beneath the drift (or has not been farther traced), in the neighborhood of Vermilion Lake. With this belt we have a general acquaintance, extending back some four years. During the past year we have had the opportunity of studying in considerable detail a small part of it, embracing an area of about 12 square miles on the south and east shores of Vermilion Lake. In this paper we desire to record our observations and conclusions, which seem to us important. II.—Literature. Outside the Minnesota Geological Survey, the list of the investigators who have studied the geology of the Vermilion Lake area is not long. Whittlesey, in 1876,* mentioned the occurrence, in the area about Vermilion Lake, of rocks resembling the Canadian Laurentian. Chester,? in 1884, described the iron-ore at Vermilion Lake as occurring in connection with jasper and quartzite, intimately bedded with the country-rock, chiefly sericite schist, and standing in a nearly vertical attitude. The Vermilion iron-bearing rocks, and those of the Mesabi range, he says, are of the same age.

Jan 1, 1896

By J. M. Woodall

GuAs crystals which have been grown in quartz boats by the horizontal Bridgman method in the pvesence of Ga20 vapov have beetz found to have carrier and donor distributions which do not correspound to those expected from simple dopant seg-vegation during directional freezing; Instead, the carrier distribution is determined by the heat-trentnzent history of the crystal, while the donor distribution, zohiclz is principally due to silicon, is fixed by the pozuth rate, the geo)tlet.ry of the crystal growth vessel, and tlze initial Ga20 pressure. WHEN semiconducting materials are made into doped crystals by the normal freezing method,&apos; they usually exhibit doping variations along the growth axis. If a) there is no dopant diffusion in the solid, b) the dopant is distributed uniformly in the melt, and c) the distribution coefficient, k, does not vary with composition, then the doping variation along the growth axis is represented by the equation: where C is the doping level in the solid at a point where a fraction g of the original liquid has frozen, and Co is the mean concentration. When the dopant is either a singly ionized shallow donor or shallow acceptor, C also represents the carrier concentration. Even though this equation accurately describes the dcping profiles of a large number of normal freeze systems, there are several special systems for which Eq. [I] does not apply. One such system is the horizontal Bridgman method for preparing oxygen-grown GaAs crystals using quartz vessels. Several workers2"* have shown that GaAs crystals grown by the horizontal Bridglnan method using quartz vessels are generally contaminated with silicon in concentrations in excess of 5 < 10lG atoms per cu cm. This contamination is ascribed to a reaction: occurring at the walls of the crystal-growth vessel which liberates silicon into the melt and Ga2O vapor. It has been shown4 that this reaction, and, hence, the silicon contamination, can be suppressed by the addition of oxygen to the crystal-growth apparatus. It is the purpose of this paper to describe a special apparatus capable of yielding single crystals of GaAs grown in the presence of oxygen and to describe both the kinetics of silicon suppression in this system and the relationship between the carrier concentration profile and the silicon concentration profile. EXPERIMENTAL-CRYSTAL GROWTH A schematic diagram of the apparatus used in the oxygen addition experiments is shown in Fig. 1. The most important features of this apparatus are: a) the use of a sand blasted quartz boat, h) a quartz rod of length 1, with a hole of cross section A, that is placed near the boat to limit the free space volume V, over the melt during the growth, and c) the temperature gradient at and near the solid-liquid interface. Sand blasting the boat is necessary to prevent wetting of the melt. The quartz rod retards the diffusion of the GazO vapor away from the melt to the colder portions of the ampoule. A crystal is prepared by first loading a 5.5-in. boat, which has been cleaned in aqua regia, with 40 g of 99.9999 pct Ga along with 1 to 8 mg of Ga203 powder. GazO3 is a convenient source of oxygen since it reacts with gallium at the melt temperature to form Ga20 vapor, the species which apparently controls the suppression of silicon contamination. The loaded boat, the quartz rod, and the 99.9999 pct As are placed in the ampoule as shown in Fig. 1. Generally, GaAs seeds were not used since most of the unseeded growths resulted in monocrys-tals. The ampoule is evacuated to 10-5 Torr and sealed off. The GaAs melt is synthesized by placing the ampoule into a two-zone horizontal Bridgman furnace. The two zones are separated by several sandwiched layers of -in. Fibre-Fax board drilled with holes slightly larger than the OD of the ampoule. This causes a very large temperature gradient between the two zones, which is necessary for single-crystal growth. The two-zone furnace is mounted on a stand fitted with a roller bearing which allows uniform motion of the furnace in a horizontal direction. A uniform velocity of the stand is achieved by the use of a windlass device which winds up a wire attached to the stand. Movement of the solid-liquid interface is accomplished by fixing the position of the ampoule and moving the stand. Growth rates investigated in this experiment were between 0.4 and 1.2 in. per hr. The composition of the melt is fixed by maintaining an arsenic reservoir at 618°C. The stand is moved away

Jan 1, 1968

By J. Chipman, N. J. Grant, H. L. Bishop

Lime and dicalcium-silicate crucibles were equilibrated with molten iron and liquid slags containing iron oxide and small amounts of sulfur. The oxygen content of metal, iron oxide activities, and desulfurization values of the slags were determined in the temperature range 1530 to 1700°C. The influence of magnesia in the slag and the temperature dependence of the solubility of lime in liquid iron oxide and the ferric oxide content were established. The temperature contour of the liquidus surface of iron-silicate slags saturated with lime and dicalcium silicate was also established at 1600°C. THE importance of the role that slag composition plays in the refining of steel has been known for many years. Numerous studies have been made using actual plant data in order to establish the relationship between the composition of the slag and metal during the refining of a heat of liquid steel. These results rarely represent equilibrium conditions since completion of the various chemical reactions involved in steelmaking is seldom realized. In order to establish quantitatively the equilibrium conditions existing between the slag and metal, several laboratory studies have been conducted in the past 20 years to determine the reactions important in slag control. These investigations have included studies of simple liquid basic and acid slags as well as more complex slag systems which approach those commonly found during the refining of a heat of steel. Since most of the previous studies of simple basic iron-oxide slags equilibriated with molten iron were made in magnesia crucibles, it was not possible to establish the distribution of sulfur and oxygen between molten iron and slags consisting only of the three essential components, lime, silica, and iron oxide. This investigation was undertaken to establish the equilibrium conditions for simple lime-iron oxide and lime-silica-iron oxide slags. Accordingly, it was expedient to prepare crucibles both of lime and dicalcium silicate to establish the equilibrium conditions between molten iron and iron-oxide slags saturated with the refractory materials and free from other components. The only other studies of the equilibrium between molten iron and lime-saturated slags are those of Fischer and vom Ende, 1, 2 in which the solubility of oxygen was determined in an air atmosphere. The

Jan 1, 1959

By S. L. Lopata, E. B. Kula

A variation of yield and tensile strength with direction has been noted in heat-treated 4340 steel which had been warn-worked by rolling in the austenitic condition prior to quenching. Measurements by X-rays showed a preferred orientation of martensite crystals. Various ideal preferred orientations of martensite were calculated by assuming a preferred orientation for austenite and transforming this to martensite by the Kurdjumov -Sachs and Nishiyama relationships. Comparison with the measured preferred orientation showed that the ideal rolling texture for austenite in 4340 steel could be expressed as a (112) [111] texture with a component of (110) [112]. No evidence was found for any fiber axis in the rolling direction, or fop- a (123) [412] texture. The observed martensite pole figures can be adequately accounted for by these ideal austenite textures and by the Kurdjumou-Sachs or Nishiyama transformation relationships between austenite and martensite. ALTHOUGH preferred orientations are found in cold-rolled steel sheet and in many nonferrous metals, they are not generally encountered in wrought, heat-treated high-strength steels, since such steels are generally not cold worked sufficiently to develop a strong texture, and any texture that is present is removed during heat treatment by the phase transformations taking place. This report gives details on a preferred orientation found in warm-rolled and hardened 4340 steel. In a recent study, a special combination heat-treating and working technique was used in which 4340 steel was deformed in the austenitic condition, and before re crystallization of the austenite could occur, quenched to form martensite.&apos; Since the austenite was unrecrystallized, it was cold worked and hence could have contained a preferred orientation which could be transmitted to the martensite on quenching, and this in turn could be manifested as a directionality of mechanical properties. Such a directionality of properties was found as a result of working, and this prompted an X-ray study of the preferred orientation. Literature Survey— Rolling Texture in Face-Cen-tered-Cubic Austenite—M a preferred orientation is found in a rolled and hardened steel, it is first appropriate to consider what texture existed in the austenite as a result of the rolling but prior to the transformation to martensite. The changes taking place as a result of the austenite-martensite transformation are then considered. In view of the instability of austenite in 4340 steel at low temperatures, no direct determination of the austenite texture was made. However, an estimate of the texture for austenite in 4340 steel may be made by considering the textures found for other face-centered-cubic metals. Barrett&apos; has reviewed the rolling textures for many materials. The most common orientation in face-centered-cubic metals has the (110) planes parallel to the rolling plane and the [112] directions parallel to the rolling direction, or (110) [112]. Other orientations found are (112) [111], as well as (100) [001], (110) [001], and others. Beck and his co-workers, using quantitative pole figures, report that (123) [121],3 later corrected to (123) [412],4 better describes the ideal orientation. smallman5 reported that the ideal preferred orientation for high-purity face-centered-cubic metals is (123) [121], but that there is a transition to (110) [112] as solid solution elements are added. The latter texture tends to occur more readily at lower temperatures. This transition between the two textures was explained by differences in the slip characteristics with concentration or temperature. More recently, Jones and Fell6 concluded that the (123) [412] texture for face-centered-cubic metals could equally well be represented by a mixture of (110) [112] and (112) [111] textures, and hence it had no physical reality. From the above results it can be seen that there is no agreement on the "ideal" texture for fcc metals and, hence, no firm basis for assuming a texture for austenite in 4340 steel. Therefore, the orientations (110) [112], (123) [412], and (112) [111] have been considered in the following.* *The (123) [4121 is identical to the (123) [121] rotated 90 deg. Orientation Relationship between Austenite and Martensite—When martensite forms from austenite, certain crystallographic planes of the martensite are parallel to planes in the austenite. This orientation relationship was first determined by Kurdjumov and

Jan 1, 1960

By Thomas Watson

INTRODUCTION THE users of barite in the United States derive their supply partly from the domestic production and partly from the imports from foreign countries. According to the Mineral Resource division of the U. S. Geological Survey, the domestic production of barite in 1913 was 45,298 short tons, valued at $156,275, or $3.45 a ton, and the imports of crude barite were 35,840 short tons, valued at $61,409, or $1.71 a ton. These figures clearly show a decided advantage in cost of the foreign over the domestic barite to users in the United States. The difference in cost is the only advantage to the consumer of foreign barite, for there are large reserves of the mineral in the United States of good grade. The production of many of the operating mines is capable of decided increase, and it is believed that the operating mines together with the large reserves of undeveloped deposits of barite are entirely adequate to meet the demands of the users in the United States. Deposits of barite are known in California, Idaho, Nevada, and Alaska, but most of them are undeveloped because there is, apparently, no market for the .material in that region. The domestic production is derived from Missouri and the Appalachian States, the greater part being obtained from Missouri. Following the outbreak of war in Europe many users of foreign barite in the United States have been forced to seek their supplies at home. It seems opportune at this time, therefore, that a general review be given of the barite industry in the Appalachian States, one of the two areas from which the domestic supply of the mineral is derived, and that attention be directed to the undeveloped deposits in the region. Briefly, then, this paper reviews the barite industry in the Appalachian States, and describes the occurrence, preparation, and uses of the mineral.

Jan 2, 1915

By Nicholas J. Grant, Yoichi Ishida, Arthur W. Mullendore

An inert particle -marker technique was developed to provide a direct measurement of grain boundary sliding during creep in tile interior of aluminum specimens. Groin boundary sliding in the interior as measured by this technique was found to be nearly the same or slightly lower than that measured on the surface. These data disagree with those obtained by the grain-counting technique developed by W. A. Rachinger. In tests where both techniques were used, the grain-counting technique gave large and variable values of grain boundary sliding. It is shown that the grain-counting technique gines erroneozcs results because of a preferred direction of grain growth during creep. A question which has long plagued those who study grain boundary creep is whether or not surface measurements yield a true representation of the deformation in the interior of a specimen. The first attempt to measure grain boundary sliding in the interior of a creep specimen was made by Rachinger.1 His technique is based on the measurement of average grain diameters, both parallel and perpendicular to the tension axis, followed by a calculation of the grain elongation from these measurements. The difference between total elongation, Et, and the calculated grain elongation, Eg, is considered to be the result of grain boundary sliding, Egb. Surprisingly large values of Egb/ Et (90 pct) came out of creep tests of pure aluminum at temperatures above 250°C (480°F), utilizing the Rachinger technique. This value is very much larger than the values of 8 to 15 pct measured by numerous investigators on the surface of a specimen. Values obtained on the surface by Rachinger, however, were consistent with those measured by the displacement of reference scratches. Chaudhuri and Grant2 repeated the Rachinger method for A1-10 pct Zn, and found the same large values of Egb/Et inside the specimen. However, from purely geometrical considerations, grain boundaries cannot slide without grain deformation; therefore, they questioned the validity of Rachinger&apos;s grain-counting method. Several authors2,3 have suggested that grain boundary migration during high-temperature deforma- tion may tend to restore the equiaxed grain shape in order to minimize interfacial energy. Rachinger4 tested this hypothesis and found that it did not hold. Grains elongated by rapid extension retained their elongated shape during a subsequent slow creep test. It appears that some other factor was responsible for the abnormally high values of .Egb/El. McLean and Gifkins5 made a survey of the effect of grain size on the ratio Egb/ Et, and proposed that the high values were the consequence of a small grain size. They failed to explain the low value of Egb/Et which Rachinger observed on the surface of the small grain size specimens, and suggested that the surface effect on the value of Egb/Et does not always occur. Many of the disagreements arising from Rachinger&apos; s work stem from the fact that there was only one method of estimating grain boundary sliding in the interior of a specimen, and that method was of an indirect nature. If a marker line of some sort could be introduced inside of the specimen, one could make measurements just as clearly as on the surface. In the present investigation, the technique utilizes a layer of finely dispersed oxide particles inside the specimen introduced by hot press-bonding of two pieces of aluminum. Rachinger attempted a similar technique but with the oxide distribution he obtained there was so much interference with grain boundary motion that quantitative measurements were not attempted. MATERIALS AND EXPERIMENTAL PROCEDURE A) Materials Preparation. Two pure aluminum rods (impurity content in percent: Si, 0.002; Cu, 0.004; Fe, 0.002; Mg, 0.000: Zn, 0.000; V. 0.001) 1 in. diameter by 2 in. high were jacketed end to end in a 4-in.-diam cylinder of commercial-purity aluminum, 4 in, high, which had a l-in.-diam hole. The l-in.-diam mating surfaces of the two pure aluminum rods had been electropolished initially. This interface provided the oxide-film internal -marker plane after the hot press-bonding process, see Fig. 2. The composite was annealed for 1 hr at 900 F and hot upset more than 50 pct reduction in height in one step. The resulting slab was then rolled to 1/2 in. thickness; the pure aluminum test material was cut out and annealed at 900°F for 1 hr and cold cross-rolled to 1/8 in. thickness. The sheet was machined into specimens with a 1/8-in.-square cross section and a 1/2-in. gage length. The following heat treatment was given the specimens: Specimen 5A series: annealed at 1000°F for 5 min for grain-size control and then cooled to 700°F and held for 15 hr for stabilization.

Jan 1, 1965

By R. A. Meussner, C. T. Fujii

Chromium solution in wustite depresses the oxygen activity in a nonideal manner and expands the lattice slightly. Gravimetric measurements of the equilibrium compositions of wustite containing 0.00 to 1.38 wt pct Cr define the oxygen potential (CO2-CO atm) and the limits of the phase field at 1000°C. These data extrapolate to a maximum solubility of 2 wt pct Cr. The lattice parameter data, room-temperature measurements of quenched samples, differ significantly from those in the literature. Both pure and chromium wus-tites contract at uniform and equal rates as the oxygen content (metal deficit) increases. The a. US metal deficit relationships are straight lines showing none of the curvature previously reported. At constant metal deficit, the a. expands by 0.002? on alloying with 0.4 to 0.5 wt pct Cr but is insensitive to further chromium additions: a small expansion rather than a marked contraction. These results require a modification of the accepted alloying mechanism. IN the high-temperature oxidation of Fe-Cr alloys in Ha-H,and CO2-CO atmospheres the vapor transfer of oxygen from the continuous wustite outer scale to the porous inner scale/alloy interface sustains the high oxidation rates.1"3 The driving force for this transport is the difference in the oxygen activity of the outer wustite and that at the inner scale/alloy interface. In pure CO2, as well as in CO2-CO atmospheres, carburization of the alloy accompanies this oxidation. Current efforts to evaluate the parameters controlling this carburization have shown that the process is not simple; i.e., the carbon concentration in the alloy initially increases rapidly, reaches a maximum, and then decreases slowly as the oxidation time is extended. This is the same pattern reported by McCoy for the more complex oxidation-carburization of stainless steels and an Fe-Cr alloy in CO2 at lower temperatures.4 These changes in the carburization process occur while the overall oxidation rate and the lattice parameters of the scale layers remain constant. If this invariance of the lattice parameter is assumed to indicate a constant scale composition and thus a constant oxygen potential, the carburization results are not easily explained. Electron microprobe traces across the thickness of these outer scales, however, have revealed distinct chromium gradients penetrating 10 to 50 µ from the inner surface where the chromium concentrations were estimated at a few tenths percent. The variation of the chromium cmcentration on the inner surface of the scale, and the resulting change of the oxygen activity, during the oxidation process is considered to be important in defining the carburization process. Thus, to gain an understanding of the complex oxidation-carburization proc- ess, it was necessary to measure the properties of wustite containing known amounts of chromium (chromium wustite). Although the general features of the Fe-Cr-0 equilibrium diagram between 900° and 1300°C have been fairly well established by Richards and white: Wood-house and White,6 Seybolt,7 and Katsura and Muan,8 there have been no detailed studies of the limits of the chromium wustite phase field or the properties of these alloyed wustites. The recent results of a limited study of chromium wustite by Levin and wagner9 indicate that more than 0.67 wt pct Cr is soluble in wustite above 850°C and that this alloying is accompanied by a substantial lattice contraction. This change in the lattice parameter was not evident in the X-ray diffraction patterns of wustite layers from the oxidation experiments;1,3 the lines were sharp even though a chromium gradient existed in the scale. The present paper describes gravimetric equilibrium experiments which delineate the boundaries of the chromium wustite single-phase field at 1000°C and define the changes in the oxygen activity and the lattice parameter of wustite as functions of chromium and oxygen contents. The lattice parameter data of chromium wustite obtained from these equilibrium and special quenching experiments differ considerably from those reported.9 Those for pure wustite show significant differences from the widely accepted data of Jette and Foote.10 Since the causes of these differences are not easily assignable, and since the literature contains many sets of data on wustite which if not in conflict are at best not in harmony, the experimental procedures are discussed in the present paper. EXPERIMENTAL Oxide Preparation. The specimens used in these studies were porous pellets compacted from high-purity (Fe,Cr)2O3 or Fe2O3 powders. These powders were prepared from electrolytic chromium (99.8 pct purity) and electrolytic iron purified by consumable-electrode, vacuum arc-melting processing (299.9 pct purity).11 The oxides were produced by standard analytical procedures: solution of the metals in acids (HC1, then HNO3 added), coprecipitation of the hydroxides (NHaOH), and filtering and washing these precipitates. Initial dehydration of the coprecipitated hydroxides was done in a porcelain evaporating dish heated by a Meker-type burner, final dehydration by firing in a recrystallized alumina crucible at 1000" to 1050°C for 20 hr in an electrically heated furnace. Spectrographic analysis detected the following impurities: silicon, 0.01 pct or less; aluminum, 0.001 pct to trace; manganese and copper, 0.0001 pct to none. Each of these levels is at least one order of magnitude lower than in commercially available CP grade ferric and chromic oxides. Fluorescence analy-

Jan 1, 1969

By F. S. Young, K. E. Gray

Drilling tests with a 11/4-in. diameter roller bit were performed on Berea and Bandera sandstones and Leuders limestone using water and two conventional drilling muds as circulating fluids to evaluate the influence of dynamic filtration on penetration rate. The muds possessed widely differing API fluid-loss properties. Mud filtrate was constrained to flow beneath the bit; no filtrate flowed radially through the borehole wall. Rock pore pressure at three different locations ahead of the bit, cumulative filtrate volume, borehole pressure and bit location were monitored during drilling. The rock samples, cored in three orientations with respect to bedding planes, possessed a wide range of liquid permeabilities. and were drilled at borehole-to-formation pressure differentials of 0, 250, 500 and 1,000 psig. The effect on penetration rate of API fluid loss, borehole pressure and rock permeability was studied. Rock permeability damage and pore pressure gradients beneath the bit were evaluated. The importance of borehole-to-formation pressure differential was illustrated for each drilling fluid and rock permeability combination. Penetration rates decreased with increased borehole pressure and reduced fluid loss. The observed penetration rate reduction due to changing fluid Ioss was attributed to decreased filtrate flow and improved mud cake plastering hy the low fluid-loss mud. The reduction in filtrate flow could not be related to spurt-loss phenomena. Rock permeability influences penetration rate through particle invasion ahead of the hit, which damage leads to high pressure gradients. Penetration rate variance with sample orientation was evident for water-drZled samples but less obvious for mud-drilled rocks. Permeability damage beneath the bit ranged from 1 to 3 cm. Maximum damage occurred in the first 0.1 cm. Pressure gradients varied with API fluid 10.s.s and could be correlated with penetration rate. The pressure gradient was found to influence penetration rare in rocks of all permeabilities tested. INTRODUCTION Early microbit and small-scale drilling experiments proved to be invaluable contributions to understanding the mechanics of drilling at depth. For example, the effect of borehole-to-pore pressure differential on drilling rate was demonstrated conclusively by Murray and Cunningham&apos;, Eckel&apos; and others .&apos; However, the effects of various drilling fluid properties on drilling rate, particularly filtration, have not been studied extensively on a laboratory basis. Microbit correlations of penetration rate with different viscosity and API fluid-loss muds led EckelV o conclude that viscosity and density. more than API fluid loss, were the most important fluid properties in controlling drill bit penetration rates. Ferguson and Klotz6 studied filtration beneath the bit and stated that the maximum amount of filtrate which could conceivably flow beneath a drilling bit could be described by a potential function associated with flow from a moving disc source. and be characterized by a depth-of-filtrate invasion. Invasion depth is a function of penetration rate, formation porosity and permeability, flooding efficiency, pressure difference between borehole and formation and borehole radius, assuming that no filtrate flows through the borehole walls. Electric analog and experimental measurements were obtained, assuming no plugging of the formation pores. Theoretically, filtrate invasion was predicted to extend from 1- to 15-hole radii beneath the cutting surface; experimental results indicated that the extent of invasion was only Y2 in. Comparing these data with results of core-plugging experiments by Norwak and Krueger&apos; led Ferguson and Klotz to state that the drilling operation apparently contributes to higher filtration rates than are observed in nondrilling core filtration tests in which the core face is jetted and scraped. Glenn and Slusser: in describing a linear filtering system in which a rotating bit continuously scraped mud cake from the surface but did not penetrate Alundum cores, stated that mud-solids invasion and permeability damage of the cores were most severe in the first 2 to 3 cm. The filtrate flow rate through the core was found to stabilize after sufficient time had elapsed for the formation of an internal mud cake whose effective permeability was estimated to be 50 to 300 times as high as that of bulk filter cake. Krueger and Vogel reported core permeability damage depths up to 12 in. during a 5-day exposure period in which filter cake buildup was prevented. Havenaar pointed out that the discrepancy between reported and calculated values of filtrate volume obtained in the experiments of Ferguson and Klotz was due, among other things, to failure of the reported API fluid loss to truly represent filtration beneath the bit. Williams," Pro-koplz and others"" have shown that dynamic filtration tests (where a flow of fluid parallel to the filter surface continually erodes the deposited filter cake until a dynamic equilibrium between wall-shearing forces and normally directed compaction forces is attained) yield higher filtration rates than do static tests. Cunningham and Goinss reported results of drilling tests in impermeable shales. They found that by reducing

By S. H. Williston

IT is not often that bore hole surveys can be checked by actual civil engineering methods. A recent Arizona survey was checked by normal surveying methods and the comparison of the results should be of value to both oil and mining men. During the summer of 1948 the Phelps-Dodge Corporation, at its Copper Queen property near Bisbee, Ariz., drilled a 1245 ft, 8 in. diam, churn drill- hole in a mineralized area and cased part of it, intending to use it to transfer mill tailings for stope fill. The hole, as frequently occurs, was not straight, and, in endeavoring to locate the bottom in- the underground workings, they found no evidence of the hole at the underground coordinates directly below the surface location. The noise of the drilling tools was reasonably clear, but the direction of sound was uncertain. Preliminary tests with available equipment were not successful in locating the bottom of the hole. Be- cause of the mineralized character of the area and the fact there was some casing in the hole, any magnetic method of well surveying would give results &apos; of doubtful value.

Jan 1, 1950

By David R. Mitchell, B. M. Bird

DENSE-MEDIA processes utilize the familiar laboratory float-and-sink procedure on a commercial scale. Just as wood chips float on water and sand sinks, so coal floats and refuse sinks when placed in a medium intermediate in specific gravity between the coal and refuse. Liquids intermediate in specific gravity between coal and refuse used in commercial plants are of four types: (1) organic liquids of high specific gravity-halogenated hydrocarbons; (2) dissolved salts in water; (3) pseudo liquids obtained by suspending solids, such as sand or magnetite, in water, and, (4) fluidizing a mass of sand or other solids by air currents. Those most widely used for cleaning coal are solutions of calcium chloride in water and a suspended sand or magnetite pseudo liquid. Laboratory float-and-sink testing is an intermittent operation during which every opportunity is given for particles lighter than the medium to float and particles heavier to sink. Commercial processes are continuous; vertical and horizontal currents of the separating medium occur as either part of the process or unavoidedly produced by the introduction of feed and withdrawal of products, &apos;so that the exact separation of the laboratory technique is not duplicated by commercial processes. However, separations close to the theoretical are obtained in commercial machines by careful technical control of the process. Most machines in commercial installations are crowded to get as much out of the equipment as possible, so that careful technical control is necessary is get the recoveries and grade of product desired. Sizes usually cleaned are plus ¼ in. or plus 1/8 -in. in the United States and plus 1/16-in. in Great Britain. Coal as small as 1 mm. has been cleaned in some experimental installations. The separation of coal from refuse in sizes finer than about 1/8-in. is made difficult by viscosity effects and hence at the present time cleaning is confined to the coarser sizes. Technical advances in the art of cleaning coal by dense-media processes is progressing rapidly and it is likely that equipment, media, and procedures will be developed to clean sizes down to 0.5 mm. efficiently and at low cost.

Jan 1, 1950