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By H. J. Gerritsen

From presently available components a portable, rugged, reliable apparatus can be built which will be able to detect methane concentrations of 0.1% and lower in air. Sensitivity and design considerations of the apparatus are given. Ways to build even simpler and cheaper apparatus in the future are indicated. Traditionally the problem of detecting and monitoring the presence of dangerous gases present in small concentrations in air has been a difficult one. Whether canaries,' or sophisticated chemical or thermal conductivity methods are used, they seem to be either slow, cumbersome, or otherwise not completely satis factory. A seemingly natural way of gas detection is to measure the strength of absorption undergone by light of a wavelength that the gas to be detected absorbs. This method has been difficult to apply in view of the low power output over a narrow wavelength range in the infrared from traditional glow bar light sources. Besides, the apparatus to select such a narrow band of wavelengths is quite costly and complex. The use of a laser solves these problems simultaneously. Although a variety of lasers are available to detect a variety of gases (such as carbon monoxide or methane) whose early detection would be desirable, this paper deals exclusively with the use of lasers for methane detection. ABSORPTION SPECTRUM OF METHANE IN AIR The absorption spectrum of pure methane is very well known.2-4 There are four fundamental vibrations, all occurring in the infrared of which only two absorb strongly. They occur at 3.3 µ and 7.7 µ. The absorption spectrum is quite complicated due to the fact that the methane molecule can rotate in a variety of rotational quantum states. These rotational states are furthermore split by anharmonic forces such as the Coriolis force.4 When methane is present in air at atmospheric pressure, much of the very fine structure due to the anharmonic force is washed out since the pressure broadening is of the same magnitude as the splitting due to anharmonicity. For most of the spectrum at 3.3 µ, the rotational lines are typically separated by 0.01µ while the individual linewidth is 0.0001 µ. It is thus very important that the laser emit at a wavelength that coincides with one of these rotational lines. Before elaborating on the point that such a laser exists and how it performs, it is necessary for later discussion to point out that in the

Jan 1, 1967

By A. N. Holden, W. E. Seymour

DURING the last several years, the U-Zr system has been studied at many laboratories as one of the research programs sponsored by the Atomic Energy Commission. The equilibria in part of this system have been difficult to determine, although the phase diagram from 0 to 60 atomic pct Zr has been established with reasonable certainty. Existing diagrams of the system vary appreciably beyond 60 atomic pct Zr, particularly with regard to the existence of an intermediate phase. Most existing diagrams show a transformation or reaction horizontal near 600°C. In 1955, a collection of uranium phase diagrams' was prepared at the Battelle Memorial Institute and the U-Zr diagram in that collection contained a questionable region in the vicinity of 60 to 80 atomic pct Zr. Summer-Smith" has published a phase diagram of the system that shows no intermediate phase. Summer-Smith did his work with powders and found only the uranium and zirconium eutectoid mixture from X-ray patterns of material annealed below 600°C. Mueller3 at Argonne National Laboratory did similar work with filings, and he found that initially there was a pattern of an intermediate phase, but on long-time annealing

Jan 1, 1957

By Lucien Eaton

THE use of filling in mines is less common in the United States than it is in Europe, where in some places it is required by law. In most cases the filling is placed by hand, and the material used for this purpose is the waste from development and that sorted from the ore in the stopes. When these sources provide an insufficient supply, additional rock must be quarried on surface or mined underground, or some other material :st be used. In different parts of the world sand, clay, gravel, culm, nulated slag, mill tailings, and even ashes, have been used as filling material in place of or in conjunction with rock. Of all the materials used for filling the best is probably clean sand. Gravel, finely crushed rock, granulated slag and coarse mill tailings are almost as good, and the methods used for placing and confining sand will apply equally well to any of these. The advantages of sand are its comparatively slight compressibility and the ease, economy and convenience with which it may be placed. On account of the voids, which necessarily occur in fills made of coarse waste, such fills will compress 10 to 25 per cent before they develop their full strength, whereas clean sand seldom compresses more than 5 per cent. Sand is especially desirable when practically complete filling is required, and sand derived from mill tailings, especially when not thoroughly cleaned, has been remarkably effective in sealing off and extinguishing mine fires. When natural sand is available on surface, or when it can be obtained from the mill tailings or tailings dump, the cost of using this material for fill will probably be considerably less than that of rock. In this paper it is not proposed to discuss all methods of filling, butt to describe some of the methods used for placing sand fill and to make a brief comparison of their merits.

Jan 1, 1932

By H. David Swain

On Bougainville Island in Papua New Guinea, Bougainville Copper Ltd. (BCL) has successfully applied electronic data processing (EDP) techniques to pit operations and mine planning. Though the EDP program is not complete, BCL has realized significant improvements in short and long range mine planning, and equipment and manpower utilization. About 80% of BCL's 4000 employees are Papua New Guinea nationals, and most have little education or training. The operational characteristics of the computer equipment, however, have been quickly adapted by users with low educational standards.

Jan 3, 1979

By David R. Mitchell, Ernest M. Spokes

There is evidence that study of minerals now considered to have susceptibilities too low for magnetic separation should be continued. Present concepts may be false. INFORMATION on magnetic properties of minerals other than magnetite is scanty and sometimes erroneous. Often there is no information at all. W. R. Crane's table of tractive forces published in 1901 is still the best guide in the field, but Crane's data can be used as a guide only, since he ignored such important factors as impurities in the minerals, size, and packing effect. During the 1930's work by the U. S. Bureau of Mines added greatly to knowledge of the behavior of certain minerals in a magnetic field. The USBM bulletin gave for the first time complete magnetic characteristics for magnetite and fragmentary data for a few other minerals. The work reported here covers a study of the magnetic-susceptibility relationships of the wolframite series of minerals and sphalerites as related to their chemical compositions. Theories are proposed to explain divergences found from commonly accepted beliefs. Gouy Method for Determining Magnetic Susceptibility: The Gouy principle has been adequately described in the literature1-3 and applied in various ways.'- It may be summarized by stating that a body of material (gas, liquid, solid, or powder mixed with gas or liquid) of cylindrical shape changes in apparent weight if suspended with one end in a zone of higher magnetic field strength than is found in that portion of the field surrounding the other end of the cylinder. This may be expressed as K2 - K1 A (H2 - H2) - mg. [1] In determining the susceptibility of mineral specimens by the Gouy method, the mineral is reduced to a fine powder and packed in a glass weighing tube. Precise measurement of the bore and depth of the tube is made unnecessary by a calibration procedure. Using the basic expression of Eq. 1, Hoare"

Jan 1, 1959

By R. F. Rolsten

VAN Arkel 1 prepared ductile tantalum by the thermal decompoiition of tantalum pentachloride on a resistively heated wire (2000° C) in an evacuated bulb maintained at 100°C. Burgers and Basart2'3 observed the formation of a mixture of tantalum carbide and free metal when a carbon deposition base was used. campbel14 suggested the thermal decomposition of the iodide if a lower decomposition tem- perature was desired. To date, the details for preparing high-purity iodide tantalum have not been disclosed. EXPERIMENTAL The tantalum to be purified was symmetrically placed around the clear quartz deposition surface centrally located within a 64 mm cylindrical Vycor bulb. The deposition vessel usually employed5 was modified6 by incorporating a reentrant fin,mer in place of the customary metal filament in the head

Jan 1, 1960

By A. M. Khan, I. Fatt

A new type of steady-state thermal conductivity apparatus is presented and described. Results of measurements on Berea sandstone, Solehofen limestone, Bandera sandstone and Bakelite are presented. The measurements were made in a two-hour period at temperatures up to 80C and axial stress to 125 bars. Results show that the thermoelectric heat pump and tbermistor-controlled electric heater can be used in a steady-state apparatus for measuring thermal conductivity of mck. Steady-state is reached within two hours. With Urethane foam insulation, not more than 3 per cent of heat is lost by radial flaw. The apparatus can be used as a comparator or for absolute thermal conductivity determinations. INTRODUCTION Calculations of heat flow through the earth, both for scientific purposes and engineering design, require thermal-conductivity data on rock. However, the high variability of rock often makes handbook thermal-conductivity data of little value. For engineering purposes in particular, it is desirable to have measured data on samples of the rock mass under study. Laboratory methods for measuring thermal conductivity of rock use either time-dependent1-3 or steady - state temperatures .4,5 The time -dependent (transient) techniques give thermal diffusivity from which thermal conductivity can be calculated if the specific heat and density of the sample is known. Most transient techniques require lengthy and involved sample preparation. Also, the accuracy tends to be low. Steady-state techniques are more exact and are the most commonly used. The steady-state methods, however, also have their difficulties. A long time is often required to reach steady state, troubles have been encountered in establishing good thermal contact between the heating and cooling elements and the rock sample, and unaccounted-for heat losses are difficult to prevent. In this paper we present a description of a new type of steady-state thermal conductivity apparatus. With it, measurements have been made in two hours at temperatures up to 80C and axial stress to 125 bars. Sample preparation is simple and no thermal conductivity standard is needed.6 APPARATUS Our steady-state apparatus is an improvement . over the conduction pile used by Zierfuss and van der vliet4 and Somerton.5 A linear heat flux is established through a conduction pile consisting of the rock sample and a standard material of known thermal conductivity in series. The thermal conductivity of the sample is calculated from the ratio of the temperature drop across the sample

Jan 1, 1966

By J. E. House, J. L. Drobnick, R. R. Swanson, D. W. Agers

The paper describes an improved process for the recovery, purification, and concentration of copper values from acidic dump leach liquors. The process employs a new liquid ion exchange material (LIX® 64 reagent) capable of separating copper values from iron and other impurities common to dump leach liquors in the typical pH range of 1.4-3.0. Properties and performance of the reagent are discussed. Design scale-up information for both pilot plants and commercial installations, including preliminary economics, are presented. Economic considerations include the production of electrolytic copper from the purified copper aqueous concentrate. INTRODUCTION Since the commercial acceptance of the liquid ion exchange process in the mineral processing industry, it has been predicted that a wide selection of chemical reagents to efficiently and economically separate many metals in solution under a wide range of conditions would be commercially available. Several years ago, General Mills began a basic research and development program to determine if it were possible to develop a reagent to extract economically metallic ion from existing process streams. Progress toward reaching this objective was reported in late 1963, when development of quantities of LIX -63 reagent, a highly selective reagent for the extraction of copper, was introduced. The properties of this reagent are described in a previous paper.' The development work with this reagent indicated that perhaps the largest potential application for a copper extractant, the treatment of acidic dump leach liquors, would not be economically possible with LIX-63 because of limitations of the reagent to extract copper below a pH of 3.0. The relatively small pH adjustment required with LIX-63 would result in a significant processing cost and the undesirable precipitation of ferric hydroxide from the liquor. This pointed to the need for another copper extractant which would extract copper from dump leach liquors without pH adjustment. General Mills was successful in synthesizing a molecule which does not have the pH limitation of the LIX-63, yet possesses the selectivity-solubility properties required of a metallic extractant. The resulting LIX-64 reagent broadens the pH range from which copper can be effectively extracted and separated from other metallic impurities. Of special significance is the fact that the reagent, LIX-64 was developed by combining the technical requirements of a specific problem in hydro-metallurgy with theoretical organic and physical chemical principles.

Jan 1, 1967

By T. Price, H. A. Holl, A. P. Greenough, A

UdIN, Shaler, and ulff' first used wires for the determination of the surface energy of a solid metal. A gage length was marked by tying knots in the wires, which were then suspended in a cylinder of the same metal, heated in an inert atmosphere for the appropriate time, cooled to room temperature, and finally removed from the furnace so that the lengths of the wires could be measured. With iron wires, difficulties associated with deformation during the phase changeszp3 made it necessary to measure the gage lengths at the tem-

Jan 1, 1964

By L. D. Keller

The application of hydraulic concentration to large scale operations has been effectively accomplished by the use of the SiphonSizer. Operation has been simple, automatic and essentially trouble free. The use of the primary desliming SiphonSizer on magnetic taconites has shown an improvement in grade of concentrate and an increase in recovery over conventional hydroseparators. Magnetic concentrates have been further deslimed and upgraded in SiphonSizers by floating a coarse middling product away from the heavier concentrate. The application of the Siphon-sizer to closed circuit grinding has met with only partial success to date. Hydraulic concentration of minerals has been practiced for a good many years. Until recently, however, the practice has been limited to equipment using a multiplicity of small pockets and relatively low tonnages and flows. The adaptation of the SiphonSizer to the concentration and classification of magnetite has changed this concept. Some fifty commercial units varying in size from a 16-ft diam circular unit to a 25x100-ft rectangular unit are currently in operation on magnetic taconites. Additional units up to 38 ft diam are under construction. Depending upon the application in the flowsheet, upgrading varies from 0.75% to 14% Fe in a single stage. To those not familiar with taconite processing, the importance of the struggle to remove economically as much silica as possible may not be fully appreciated. Perhaps some figures pertaining to transportation costs will underscore this important process. If the silica content of the concentrate from a 10,000,000 ton per year plant could be reduced by I%, a savings in boat freight, at $2.00 per ton, would amount to $200,000 annually! THE SlPHONSlZER The SiphonSizer, as illustrated in Figs. lA, 1B and 2, is a hydraulic classifier in which the hydraulic water is distributed uniformly across the bottom of the vessel by means of a system of headers (1 and 2), jet pipes (3), and nozzles (4). The depth of the teeter bed is automatically maintained by the siphon-float assembly. The feed is introduced through a feed well (5) and separated into two fractions by the effects of rising water and the density of the teetered bed. The magnetite fraction is discharged by the siphon (12) while the fine slime and light middling overflow a peripheral weir (9) to the overflow launder (6). The bed depth is controlled automatically by float valves (7), which are responsive to changes in the height of clear water supported in the superelevation tubes (8) by the density of the teetered bed. On top of the float (7) is a needle valve (10) which permits

Jan 1, 1963

By P. Somasundaran, D. W. Fuerstenau

This article presents the results of an analysis of grinding of 1:1 mixtures of 4x8-mesh quartz and limestone in laboratory ball and rod mills. From these experiments, the amount of energy consumed in grinding each component of the mixture was determined. In the ball mill, limestone consumes slightly more energy than quartz in the initial stages of grinding, but as the grinding proceeds quartz begins to consume a slightly greater fraction of the energy. The postulate that the fraction of energy consumed by any material in a ball mill is proportional to its volume fraction has been shown to be approximately true. On the other hand, in a rod mill energy consumption by quartz and limestone is equal only in the initial stages of grinding, with energy consumption by quartz greatly exceeding that by limestone as rod milling proceeds. Preferential energy consumption in tumbling mills has been discussed in a number of papers. For example, from an analysis of the kinetics of comminu- tion in ball mills, Arbiter and Bhrany' obtained rate equations based on the postulate that only coarse particles are ground, indicating that fine particles are protected from the action of the balls by coarser particles. In rod mills this protective action is much more pronounced than in ball mills. Recent studies on the rod milling of limestone-quartz mixtures have shown that this protective action causes the mineral with the lowest grindability (quartz in this instance) to consume the greater fraction of energy. 2 However, in the ball milling of mixtures it has been postulated that the consumption of energy by one of the constituents is determined by its volume fraction within the mill. 3 Possibly this hypothesis may be a simplification of the ball milling of mixtures since the protective action suggested by Arbiter and Bhrany may result in some preferential energy consumption by one of the constituents of a mixture. The objective of this study has been to determine preferential energy consumption in laboratory ball and rod mills by analyzing size distributions of each material in the products obtained from grinding 1:l mixtures of quartz and limestone. MATERIALS AND METHOD The procedure for carrying out the tests on wet grinding quartz-limestone mixtures has already been described.'r3 In the present investigation, 1:l mix-

Jan 1, 1963

By Charles E. Locke

DEPRESSION in all lines of the mineral industry except gold, which began in 1930 and continued, even worse, through 1931, had its effect on ore concentration. Construction was limited to the completion of plants already begun. Every possible economy was adopted. Changes and improvements involving expense were postponed. Research was largely abandoned. Operations became highly efficient and costs were cut down, although this did not necessarily mean a lower cost per ton because of the greatly reduced capacity at which mills were run. Lower metal prices caused the operators to seek the optimum ratio of concentration and grade of concentrates looking toward maximum economic recovery; that is, net profit. In the crushing field no marked changes occurred. The Symons cone crusher for intermediate work is in use almost everywhere. Its manufacturers claim that 900 machines have been installed in 21 countries, replacing two previous steps of crushing and yielding a product sufficiently fine to form a satisfactory feed for rod mills and ball mills. A new Telsmith crusher has appeared which has curved jaws something like the Symons cone and consequently the same advantage as the latter.

Jan 1, 1932

By B. S. Gottfried

This paper is concerned with possible transport mechanisms which occur during segregated burning (i.e., burning in an oil reservoir in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas). ,Two analytical models are presented. In the first, burning is assumed to occur at the gas-oil interface, and the dominant mechanism is taken to be the rate at which oxygen diffuses to the interface. The second model assumes that combustion occurs within the clean zone, with the dominant mechanism being the mechanism of fuel deposition from the oil-bearing formation to the clean zone. ,Comparison of the results of the analyses with limited experimental data indicates that the latter mechanism is much more plausible. Both models are idealized representations of the actual process and are somewhat conjectural, however, owing to the lack of more definitive laboratory or field data. INTRODUCTION In recent years there has been considerable theoretical and experimental research directed toward understanding the recovery of crude oil by underground combustion. Although two different recovery schemes have been proposed, known as forward and reverse combustion, it is only forward combustion that shows promise of becoming a practical recovery technique.17 Most of the analyses of the forward combustion process have considered it to be pistonlike; i.e., oil is displaced by a vertical combustion zone which, with its ensuing gases, pushes die oil forward as the flame front is propagated through the reservoir.l-8,ll,l2,14-16 However, information gained in field pilot studies indicates that, at least to a certain extent, forward combustion proceeds in a segregated manner in oil reservoirs.10 An ideal segregated system is one in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas. The location of the combustion zone in such a system is not immediately evident, although combustion is believed to occur either at the gas-oil interface or within the clean zone. In either case, the combustion zone may be horizontal and it moves in parallel rather than in series with the produced oil. The purpose of this paper is to explore the likely mechanisms by which segregated burning can occur, and to determine the sensitivity of the resulting models to changes in various physical parameters. Two governing mechanisms are considered: the case of a horizontal combustion zone at the gas-oil interface with the rate of combustion governed by the rate at which oxygen diffuses to the interface, and the case of combustion within the clean zone with the combustion process controlled by the transport of fuel from the oil-bearing formation to the clean zone. Both models are somewhat hypothetical and involve considerable simplification of the actual process. However, the results allow some preliminary understanding of segregated burning which is useful in the absence of more definitive laboratory or field pilot data.

Jan 1, 1967

By R. M. Waterstrat

X-ray diffraction and metallographic examination of binary Mn-rich alloys with Ti revealed the presence of intermediate phases in this system. A binary R phase has been identified and also a phase having an a-Mn type structure. The X-ray pattern of the phase TiMn3 is presented and a tentative phase diagram for the Mn-rich portion of this binary system has been constndcted. MANGANESE-rich alloys with titanium have been subjected to thermal analysis at temperatures down to 1100°C by Hellawell and Hume-Rothery.1 Their results indicate the existence of an intermediate phase TiMn3 in this binary system. This phase appears to coexist with the Laves phase TiMn2, and with terminal solid solutions based on the allotropes of manganese, at least down to 1100°C. The above investigators did not attempt to determine the crystal structure of this phase, however. Since, by analogy to the binary systems Mn-V and Mn-Cr3 one might expect to find a phase in this region of the diagram, it seemed desirable to obtain X-ray diffraction patterns of alloys in the concentration range in question, in order to ascertain whether the sigma phase or related structures occur. EXPERIMENTAL PROCEDURES Alloys were prepared by arc-melting electrolytic manganese and iodide titanium in a water-cooled copper crucible under a helium atmosphere. Excess manganese was added to each melt in order to allow for losses incurred during melting. The alloys were then wrapped in molybdenum foil and sealed in evacuated quartz tubes for annealing at various temperatures, as shown in Table I, followed by quenching in cold water. Although the inside of the tubes showed evidence for some loss of manganese from the specimen during annealing, there was no evidence of any reaction between the specimen and either the molybdenum foil or the quartz tube at these temperatures. It was later found that the manganese loss was considerably reduced by annealing these alloys in sealed quartz tubes containing one atmosphere of purified argon. As an added precaution the surface of each specimen was ground off before crushing the alloys to -270 mesh powder, using a hardened steel mortar and pestle. X-ray powder patterns were obtained using either FeKa or CrKa radiation in an asymmetrical focusing camera, which gave excellent dispersion of the closely spaced lines. Pictures were also obtained using a Debye camera of 5-cm radius which provided data in the angular region not covered by the focusing camera. The alloy specimens were polished and examined metallographically, using an etchant consisting of 60 pct glycerine, 20 pct nitric acid, and 20 pct hydrofluoric acid. The 10-g buttons were in each case broken in half and found to be well-melted and free of any gross segregation. One half of certain alloy buttons was submitted to chemical analysis in the "as-cast" condition. No appreciable change in composition seemed to occur during annealing . RESULTS The X-ray pattern of alloy Ti1.17Mn0.83 was found to agree well with that of the ternary R phase which was first found in the Mo-Cr-Co system,' and re-

Jan 1, 1962

By Edna A. Dancy, Gerhard J. Derge

Jan 1, 1963

By R. N. Edmondson, L. Mair, M. Tenenbaum

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhord Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chipmon, Vice President; T. D. Jones, Treosurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. w. Thornton, Chairman; Dennis Carney, John Chipman, J. C. Fulton I. H. Hollomon H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supenision of the following Publications Committees: Extractive Metallurgy Division: T. 0. King Chairman; S. J. Dickenson, R. P. Hermsdorf R. Schuhmann. Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman F. Lincoln Vogel Jr., Vice-chairman, W. A. Baikofen, R. W. Boliuffi J. H. Bechtold M. B. Beyer. R S. Busk, C. G. Gaetzel, Paul Gordon C. D. Groham, Jr., Robert F. Hehe-mann,' R. I. Joffee, F. c. Joumot Jr lrving R. Kramer A. J. Lena Harold Morglin, C. J. McHargue, Russell A: Meussner, J. B. Newkirk H. W. Paxton, G. E. Pellissier, I. S, Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. 0.. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephon: pEnnsvlvanio 6-9220. Subscription 522 Per year for non-AIME members in United States and North South and Central America; $25 foreign;, $5 for AIME members. Single copies, 54.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed In its publications . . . Copyright 1958 by the American lnstltute of Mining Metallurgical and Petroleum Engineers Inc. . . . Registered cable address AIME New York , . . lndexed in Engineering Index Industrial Arts Index and Chemical Abstrats . . . Application for second class mail privileges ii pending at New York, N. Y. Volume 212, Number 4.

Jan 1, 1959

By Robert Bakish, William D. Robertson

AFTER more than fifty years of investigation and continuing failure in service, a satisfactory mechanism to explain stress corrosion cracking in homogeneous alloys is still lacking. The relative chemical activity of grain boundaries and adjacent grains, inferred from the boundary structure, has been used to explain intergranular cracking in a brass.' This concept is probably correct as a general hypothesis, but it requires much more extensive development in order to explain satisfactorily the observed phenomena. For example, the specific function of the solute in an alloy must be considered, because intergranular failure does not occur in pure metals,' which are structurally similar to homogeneous alloys. Also, in this connection, an inter crystalline fracture path in binary copper alloys can be changed to a transcrystalline path by relatively small ternary additions.' The fracture path in ß brass is predominantly transcrystalline,' in contrast with an inter crystalline path in a brass. Whether the two different fracture paths are the result of a difference in composition, crystal structure, or the state of long range order is unknown and cannot be determined with ß brass, because only the ordered state can be obtained at room temperature. The study of chemical activity at structural sites in the Cu-Zn system is restricted by the formation of opaque films in an ammonia environment in which stress corrosion cracking is generally observed. Furthermore, both components of the alloy are chemically active and the interpretation of observations is therefore relatively complicated. The Cu-Au system is a better choice for the purpose of studying structural factors. In particular, CuAu is very susceptible to cracking in ferric chloride and opaque films are not formed in this solution; it may be obtained in different states of long and short range order; and, finally, only copper is oxidized in dilute ferric chloride, which considerably simplifies the chemical problem. To provide information necessary for a more general explanation of stress corrosion cracking in homogeneous solid solutions, the following structural factors have been investigated in a Cu-Au alloy having a composition corresponding to Cu,Au: 1) the effect of long and short range order; 2) the structural sites from which copper is removed from the annealed and cold worked polycrystalline alloy; and 3) the effect of annealing time and temperature on structural reactions in the cold worked alloy. Experimental Procedure A Cu-Au alloy of nominal Cu3Au composition was cast from cathode copper and high purity gold and fabricated into sheet and wire. Chemical analysis for copper and gold indicated 48.92 wt pct Cu and 51.01 pct Au. Quantitative spectrographic analysis indicated 0.01 pct Ag, 0.002 pct Pd, 0.001 pct Pb, and 0.002 pct Fe, with traces of magnesium, silicon, and zinc. Presumably most of the remaining 0.055 pct corresponds to the limits of analytical precision. Heat treatments of wire and sheet were conducted in argon or vacuum. Wire specimens, 0.064 in. diam, were heated for 1 hr at 850 °C to establish a definite

Jan 1, 1957

By W. M. Peirce

COAL'S importance in the metallurgy of zinc may be gauged by the fact that approximately a million and a half tons is so employed annually in the United States. This brief paper will show in what way the various steps in the treatment of zinc ores utilize this fuel, either in its primary form or as coke or gas, and to what extent. The first step in zinc metallurgy that requires the use of fuel is roasting the sulphide ore, which is the type of ore in which zinc commonly occurs. Since the roasting is nearly or completely autogenous, however, this use of fuel is too minor to warrant further attention. Concentration of zinc ores is usually carried out by conventional milling methods, but a pyrometallurgical method, the Waelz process, is used to concentrate certain low-grade ores, and to recover the zinc content of certain residues in concentrate form. The Waelz process uses a continuous rotary kiln in which a mixture of coal and zinc-bearing material is heated to a

Jan 1, 1948

By Olav Mellgren

Part I. The interaction between potassium ethyl xanthate and lead salts has been studied thermo-chemically. It is shown that ethyl xanthate reacts with lead carbonate, basic carbonate, thiosulfate and sulfate according to principles of simple chemistry, whereas reactions with lead sulfite, metasulfite, basic thiosulfate and hydroxide at high pH are associated with secondary reactions. A new compound "xanthogen thiosulfate" is postulated. Part 11. Adsorption of ethyl xanthate on galena has been studied quantitatively and thennochemi-cally. It is shown that an ion-exchange mechanism governs the adsorption process and that the heat of adsorption of xanthate on galena is equivalent to the heat of reaction of ethyl xanthate with bulk lead salts. It is concluded that the entropy content of the surface "compound" on galena is different from that of a corresponding bulk lead salt. Alkali depression is in part shown to be due to the instability of the xanthate-galena system at high pH and to the formation of basic lead salts. Sulfate and carbonate ions are shown to have a stabilizing effect on the xanthate-galena system. PARTI. THERMOCHEMISTRY OF ETHYL XANTHATE AND OF ITS REACTION WITH LEAD SALTS In the past little attention has been paid to the chemistry of lead xanthate. It is known that xan-thates form slightly soluble compounds with lead and that suspensions of lead xanthates in alkaline solution decompose rather readily.' The solubility of lead ethyl xanthate is of the order of 2.6 x 10-6 moles per 1. At increasing pH the xanthate concentration of a saturated solution contains more xanthate. Thus at pH 11 this xanthate content is about 100-fold larger than at pH 7.1 Xanthates are known to be consumed when added to a suspension of slightly soluble lead salts such as lead sulfate and lead carbonate. It is unknown to what extent this xanthate consumption is due to a simple chemical reaction because, frequently, observations are made which reveal secondary reaction products in such reactions. Thermochemical study of the reaction between xanthate and lead salts offers a means to clarify the significance of these reactions as the enthalpy changes can be accurately predicted from heat of formation of lead salts in pure solution reactions. In the present work the heats of formation of lead ethyl xanthate from potassium ethyl xanthate and lead salts are determined and some thermochemical aspects of xanthate in solution are studied. The results of these investigations are presented in Part I. In Part II the heat of adsorption of ethyl xanthate on galena surfaces is presented. All enthalpy changes were measured directly in a microcalorimeter. Calorimeter: The calorimeter used for measuring enthalpy changes was similar to that used by Redinha and Kitchener2 which was based on a description by Derbyshire and Marshall.3 Other useful references4,5 are listed. A sketch of the calorimeter

Jan 1, 1967

By R. P. Harvey, J. E. Walstrom, A. A. Brown

In view of the large number of wells directionally drilled from offshore platforms and urban drillsites, greater interest is being focused on the directional survey and on the uncertainty inherent in calculating the position of the bottom of the hole, or other benchmarks in the wellbore. Of the two methods presented here for evaluating this uncertainty, the first is analytical and uses the principles of probability and statistics. The second method uses Monte Carlo simulation to generate a pattern of the scatter of possible bottom-hole locations. Both methods are based on a model for which the usual assumption is made that the curvilinear axis of the wellbore is adequately represented by a large number, M, of linear segments joined end to end from the top to the bottom of the hole and closely following the course of the hole. The errors due to this approximation are assumed to be negligible and are not studied here. One form of the model is to consider that for a given hole there exists a perfect set of data describing it, of the above form. Each linear segment has an angle of inclination with the vertical 7, in radians, an azimuthal angle from true north xi in radians, and a length Si, in feet. The subscript variable, i, extends from 1 to M. Each of the M linear segments representing the axis of the wellbore has three components in the X, Y, and Z directions. These components are calculated from the equations: The bottom-hole coordinates as determined from the reference set of data for the wellbore are given by the following for i = 1 to M: X=SX, Y = Sy, Z=SZ; . (2) A directional survey instrument, lowered into the wellbore to the M segments, or stations, measures the values of the 7; and the 3,. In general, because of errors from various sources, the resulting angular measurements will not be precisely equal to the 7" and xi. Random variables l, and Ai are therefore considered with associated probability density functions fi(li) and gi(Ai), respectively, which represent the distributions of potential survey measurements for this hole. Since it is assumed that the values Si are accurately measured they are treated deterministically. The random variables corresponding to the surveyed bottom-hole coordinates are given, for i = 1 to M, by:

Jan 1, 1970