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Jan 1, 1953

By Edmund M. Wise

NATURE has provided us with many metals, but with few really good ones, and frequently the better metals are the rarer. It is to this circumstance that many physical metallurgists, inventors, and just plain experimenters owe their employment, for much of their work is directed, consciously or otherwise, toward the alleviation of some of the more serious shortcomings of the cheaper, less noble, and weaker metals; by alloying, age-hardening, passivating, cladding, plating, and other useful dodges, which sometimes permit the substitution of one of the less gifted metals for one of the really good ones. As a matter of fact, the varied needs of our complex civilization could be quite well met with only five metals, if they were sufficiently abundant, and one of the five would certainly be platinum, the most noble and versatile that nature provides. Many metals are difficult to handle and seem to take pleasure in defying their investigators to find good uses for them, and finally when a use is found it is frequently quite a specific one; in other words, a hole has to be found--or perhaps made-to fit the peg. It is for this reason that a large amount of research must be con- ducted before the more recalcitrant metals become really useful. In platinum, however, we have a metal that inherently possesses so many valuable attributes that it became useful as soon as methods for producing it in massive ductile form were devised, and once its complicated chemical behavior was understood it became principally an aid to research rather than the subject thereof. In recent years, much research has been done to further improve

Jan 1, 1953

By J. L. Taylor, Pol Duwez

THE present knowledge of the Ti-Al system is limited to the portion of the diagram extending from pure aluminum to the intermetallic compound TiAl3' A preliminary investigation of the titanium-rich Ti-A1 alloys revealed that the solubility of aluminum in titanium is quite extensive and that the transformation temperature of titanium is raised by alloying with aluminum. From an X-ray diffraction study of alloys containing up to 75 atomic pct Al (TiAl3), the phase boundaries at 750°C were located as follows: the a titanium solid solution extends from 0 to about 36 atomic pct Al, a two-phase region exists from 36 to 46 atomic pct Al, and an intermediate phase of varying concentration extends from 46 to 62 atomic pct Al. The purpose of the present paper is to describe the crystal structure of this new phase. The alloys were prepared by melting in a helium arc furnace on a water-cooled copper plate, using a furnace essentially the same as that described in ref. 2. The titanium metal was of the iodide type furnished by the New Jersey Zinc Co., and a piece of pure aluminum (99.99 pct) was obtained through the courtesy of the Aluminum Co. of America. After melting, the samples, weighing approximately 5 g, were sealed in evacuated fused silica tubes and homogenized for 4 hr at 1000°C. The specimens were then held for 10 days at 750°C and rapidly cooled to room temperature. Filings were then taken from each sample, sealed in evacuated vials, annealed at 750°C for 4 hr, and rapidly cooled to room temperature by quenching the vials in water. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using K copper radiation filtered through a nickel foil. Structure Determination The X-ray diffraction patterns of the alloys containing 46, 50, 55. 60, and 62 atomic pct Al were identical, except for a slight shift in the positions of the reflections. The alloy containing 55 atomic pct Al was chosen far structure determination. The powder pattern contained 37 reflections and the a, doublets were well resolved in the back-reflection range. The relatively small number of reflections and the sharpness of the pattern were considered as an indication of a simple atomic arrangement in a relatively small unit cell of high symmetry, and an attempt was therefore made to solve the structure without single crystal work. A satisfactory fit was found on a large scale Hull-Davey tetragonal chart for an axial ratio of approximately 1.45. All the reflections were readily indexed and the tentative unit cell dimensions were computed to be a - 2.81 kX, c - 4.07 kX, and c/a = 1.448. The indices (hkl) and the values of d and sin2 A are given in Table I. The agreement between observed and computed sin2 is quite satisfactory. Once the unit cell was known, the details of the structure were readily found. First, it is obvious that the number of atoms per unit cell cannot exceed two, since more than two atoms would lead to a density greater than that of pure titanium. The next logical step is to assume that the two atoms occupy the corner and center of the cell. If this assumption is correct, the structure may be described as follows: space group D1, - P 4/mmm; one titanium atom in a: 000; one aluminum atom in d: 1/2 1/2 1/2: and no extinctions. Assuming this structure to be the correct one. intensities were computed by means of the usual equation: sin2 0 cos 0 where F is the structure factor; 8, the Bragg angle. and p, the multiplicity factor. The calculated values of intensities are compared in Table I with the visually estimated intensities. The agreement is quite satisfactory and the structure is therefore confirmed. The crystal structure of TiAl just described is the same as that of AuCu ordered. The AuCu ordered

Jan 1, 1953

By R. I. Jaffee, R. M. Evans

IN recent years, the interest in liquid metals as heat-transfer media for power plants has been very great. The possibility of the development of nuclear power plants has increased this interest and served as the impetus behind much research on low melting metals and alloys for such purposes. The principal reasons for consideration of liquid metals as heat-transfer media lie in their high thermal conductivity and consequent high heat-transfer coefficients, stability at high temperatures, and the high ranges of temperature possible. The element gallium possesses some of the requisite properties for a heat-transfer liquid. It is a unique material, having a low melting point and a high boiling point. Pure gallium melts at 29.78oC, and suitable alloying will produce a metal which melts below room temperature. The boiling point is about 2000°C. As it is a liquid metal, the heat-transfer characteristics would be good. Gallium is not now readily available, due in part to a lack of uses for the metal. Nevertheless, it is not a rare element, and a sufficient supply of gallium exists to permit its consideration for this use. Since gallium has some promise as a heat-transfer liquid, owing to its unique properties, research on the subject was carried on at Battelle Memorial Institute at the request of the Bureau of Ships, U.S.N. The research had as its objectives the determination of the effect of alloying on the melting point of gallium, and the study of the corrosion of possible container materials. In this research, alloys were found which had significantly lower melting points than pure gallium, but none which simultaneously fulfilled other additional requirements, chiefly the corrosion problem. Neither was it found possible to reduce the melting point of certain otherwise suitable alloys appreciably by small additions of gallium or gallium alloys. The results gave little hope that gallium alloys can be developed which enhance the good properties and minimize the undesirable characteristics of elemental gallium. Thus, gallium now appears less promising than other metallic heat-transfer media. The experimental thermal-analysis techniques used in this work have been described.' Experimental Results As a first approximation, the development of low melting gallium alloys was based on alloying elements suitable for use in a nuclear power plant, which also lowered the melting point of gallium. Information from the literature, summarized in Table I, indicates that. tin, aluminum, and zinc are the only suitable elements which cause a lowering of the melting point of gallium. Indium and silver also lower the melting point of gallium, but are of little interest for use in nuclear power plants. Of the elements reported not to lower the melting point of gallium, there is some ambiguity on the behavior of copper. Weibke3 obtained solidus arrest temperatures of 29°C for Cu-Ga alloys from 60 to 90 pct Ga, 0.8C lower than the generally accepted melting point. This may be the effect of a eutectic close to gallium, or, more likely, the result of impurities, or experimental error. The seven elements listed in Table I whose effects were not known were of potential interest if they lowered the melting point of gallium. Their effects were determined experimentally for this reason. Binary alloys containing nominally 2 pct of each of these elements were prepared in the form of 2-g melts by placing the components in a graphite crucible and holding them in an argon atmosphere at 370°C for 5 hr. These melts were then subjected to thermal analysis. In all cases. the solidus temperature was the melting point of gallium. Since these elements (As, Ca, Ce, Mg. Sb, Si, and T1) did not lower the melting point of gallium, they were not considered further as components of a eutectic-type alloy. Ga-Sn-Zn Alloys Preliminary considerations of this system for low-melting alloys were encouraging. All three binary systems were of the simple eutectic type. The composition and melting points of the eutectics were as follows: Sn-9 pct Zn (199°C), Ga-8 pct Sn (20°C), and Ga-5 pct Zn (25°C). Therefore, the probability of a ternary eutectic was high. For reasons to be discussed later, aluminum could not be used as an alloying constituent, leaving the Ga-Sn-Zn system as the only one of interest for low-melting gallium-

Jan 1, 1953

By J. D. Warne

The ferberite district of Boulder County, Colo., has been an important producer of tungsten since 1900. During World War I, high prices for tungston concontrates resulted in a brief period of intense activity, and the production in 1917 was 2,707 tons of 60 percent W03 concentrates. Production declined thereafter, and in 19.2 the tungsten produced in Boulder County represented about 4 percent of the Nation's output, being exceeded only by the scheelite production in California, Nevada, and Idaho. Boulder County has boon an important source: of tungsten in the Korean emergency; the present report does not describe this recent activity, as it will be covered by a future publication. Tungsten occurs in small ore shoots of narrow and irregular veins. Most of the ore shoots have been found outcropping on the surface. Core drilling; has been used by the larger operators to explore for new veins and to locate extensions of known veins.

Jan 1, 1953

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.'.' It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.' Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By Helen E. Edwards

The Bureau of Mines is engaged in a systematic evaluation of the thermodynamic properties of combustion gases. These studies are designed to provide basic thermodynamic information of high accuracy facilitating the theoretical study of flame and combustion phenomena. This report is the third of a series3/ presenting results of the study for particular fuel-oxidant systems. The equilibrium composition of the products of combustion and the adiabatic flame temperatures of specified oxyacetylene systems have been computed.

Jan 1, 1953

By John Griffen

THE distinguishing principle of the Tromp process is the use of a medium in the bath which is not stable, i.e., the solids will settle and the density of the medium increases with depth. A medium of uniform density can most easily be effected by agitation or by means which increase the viscosity of the medium. Either of these works against the sharpness of separation of coal from its impurities. The Tromp process grinds the medium solids to relative coarseness, allows them to settle downward in the bath without hindrance, and introduces horizontal currents of medium at intermediate levels between top and bottom of the bath. This prevents any accumulation of particles denser than the upper layer of the medium from which the clean coal is conveyed away or an accumulation of particles lighter than the bottom layer or medium whence the refuse is removed. In a relatively shallow bath making a two-product separation, the intermediate horizontal currents sweep these intermediate gravity materials away to be discharged with the refuse removed by the conveyor. Such a system provides a number of advantages. The gravity of separation can be changed simply by changing the density of the medium without changing particle size of medium solids or other conditions, as would be necessary with a system requiring uniform or stable density throughout the bath. Some installations in Europe separate at 1.40 sp gr on one shift, producing a superclean coal, and on the next shift reclean refuse from dry cleaning units and effect a separation at 1.80 sp gr. Medium solids may be much coarser in size consist, which reduces the viscosity of the medium and promotes its fluidity and in turn the sharpness of separation. Coarser medium solids with a more rapid settling rate are much more easily recoverable from the dilute medium rinsed from the products. The Tromp process is not limited to the use of medium solids having magnetic properties. Instal-

Jan 1, 1953

By I. Fatt

Laboratory relative permeability data on reservoir rock are obtained on samples which are not subjected to overburden pressure during the permeability measurements. These data are then used for calculating the performance characteristics of reservoirs in which the rock is under the pressure of the overburden. Recent observations have shown that the permeability and porosity of reservoir sandstones are decreased by application of overburden pressure. These observations led us to a study of the effect of overburden pressure on the relative permeability characteristics of sandstones. A previous note from this laboratory1 showed that overburden pressure, simulated by applying hydraulic pressure to the outside of a plastic mounted core. caused a reduction in permeability of the core by as much as 50 per cent at 10,000 psig. In a multiphase fluid flow system, the relative permeability at a given saturation will change if the permeability or the effective permeability changes but not if both permeability and effective permeability change by the same ratio. The tests described in this note were made to determine the effect of overburden pressure on permeability and effective gas permeability in the gas-oil system. The gas-oil system was chosen because the available equipment was best suited for studying this system. The resultant data can be applied to other systems of interest because the gas permeability in the gas-oil system is the permeability of the nonwetting phase and, as such, is equivalent to the gas permeability in the gas-oil-water system and to the oil permeability in the oil-water system. EXPERIMENTAL METHOD Cylindrical test plugs, one in. in diameter and one in. long, were cut from sandstone core samples from three different reservoirs. After extraction in toluene, the plugs were mounted in Lucite by conventional core mounting methods.3 The core properties are given in the legend in Fig. 1. The mounted cores were machined to fit the apparatus shown in Fig 4. Air permeabilities as a function of overburden pressure were measured by connecting lines (1) and (2) to a conventional air permeameter. To measure porosity changes as a function of overburden pressure, the lines leading to (1) and (2) and the core were saturated with kerosene; line (1) was capped and a small bore precision calibrated pipet was connected to (2). Changes in pore volume of the core as overburden pressure was applied were noted by reading the amount of kerosene produced into the pipet. To correct for the change in volume of the lines inside the hydraulic cell as a function of pressure, a pressure-vs-volume run was made with a solid Lucite cylinder substituted for the core. The change in volume of the lines was about 10 per cent of the change in pore volume of the core. No correction was needed for the permeability measurements because there was no measurable pressure drop in the lines at the maximum overburden pressure. Relative gas permeabilities were measured by the stationary liquid method described by Osoba, et al.' Gas saturations were obtained by allowing the kerosene from a kerosene saturated core to evaporate out. This procedure was followed

Jan 1, 1953

Launching Platform - Drift Indicator- Stratascope-are components of Carbide and Carbon Chemicals new Mining Machine No. 3.

Jan 1, 1953

By O. A. Carson

"IntroductionTHE ZINC-BASE die casting alloys in common usage contain approximately 4 per cent aluminum as the major alloy element. In addition, they contain about 0.05 per cent Mg .and may• have a small amount .of copper. These are usually the only •elements intentionally present.Small amounts of some impurities have been shown to have a deleterious effect on the properties of these alloys and therefore the impurities are kept low by starting with '99.99%' zinc.The reasons for holding the aluminum content at 4 per cent are not clear. Some statements appear in the literature that higher aluminum increases the brittleness, but probably the chief reason was the relative price of zinc and of aluminum when 4% alloys became firmly established. At that time, aluminum was three to four times the price •of zinc on a weight •basis. Recent prices, roughly equivalent per lb., make aluminum considerably cheaper than zinc on a volume basis and suggest that increased aluminum content would result in a decrease in the cost per piece due to the lower density of the alloy.Little information could be found in the literature and, therefore, it was decided to determine some physical properties of the higher aluminum zinc-base alloys made from high-purity zinc."

Jan 1, 1953

By Joseph J. Wallace

1. The investigation shows that there are 2 coal beds of major importance in Letcher County from the standpoint of present production - Upper Elkhorn No, 3 and Fire Clay - and 5 beds of minor importance - Whitesburg, Flag, Haddix, Elkhorn Leader, and Amburgy, The Upper Elkhorn No. 3 and Fire Clay beds contain the largest remaining known reserves. 2. Known measured and indicated reserves in all beds, based on a minimum thickness of 14 inches and on 1,600 tons per acre-foot of coal in place, are estimated at 1,353 million short tons as of January 1, 1952. Of this total, 1,056 million short tons ere in beds 28 inches and more thick. Areas in each bed were omitted from the estimate because available data relative to the bad characteristics are too meager to make an estimate that conforms with the definitions of measured and indicated coal adopted for this study. Should future drilling or development prove reserves in these areas, such reserves should be added to the total estimated reserves.

Jan 1, 1953

In this paper is given a general description of the Black Star copper orebody, its relation to the lead orebodies and the controlling factors in the mineralisation.Copper ore, in the form of chalcopyrite, was first noted at Mount Isa in 1930 during the surface drilling campaign to prove the downward continuation of the silver-Iead-zinc orebodies.Details of the occurrence are set out in table 1.Other sub-commercial widths were also disclosed and examination of these occurrences showed that commercial mineralisation could not be expected within 800 ft. of the surface. It was therefore decided that further exploration was not warranted until underground workings had advanced to this horizon.Detailed surface mapping showed two small outcrops of the host rock of the copper orebody. One occurrence, 50 ft. x 75 ft., was of quartz, with leaching suggesting former dolomite. Another outcrop, further north and west of silicified shale, with low grade oxidised copper, has recently been found. Both occurrences were above the hangingwall of the main copper orebody.When the workings in the silver-Iead-zinc orebody reached No. 7 level (875 ft. below the surface) further...

Jan 1, 1953

By Cyril Stanley Smith

METALLURGISTS - or at least metals - have been of central importance in most of the inventions that have shaped the course of man's history. From the first Bronze Age tools to the iron armor of the Roman soldier, the cannon, cast type for printing, the steam engine, the electric motor and modern electronic devices, technological progress has revolved around some particular property or comb nation of properties selected from the metallurgist's repertory. The recent utilization of the energy of the atomic nucleus (currently for military purposes alone but with great constructive implications for the future) is no exception to this, although the use of uranium and plutonium in metallic form is of secondary importance, since the significant properties are those of the nucleus and not of the electrons responsible for metallic behavior. THE METALLURGIST AND ATOMIC ENERGY The metallurgist has a role of central importance to play in the future development of atomic energy. Not only must he make and shape the fissionable materials themselves, but he must also develop auxiliary materials to withstand the extreme conditions imposed on nuclear reactor components by the high heat-transfer rates needed for efficient utilization of the fuel and by the perplexing but interesting effects of radiation on the structure and properties of materials. It is doubtful if there is currently any other field potentially more rewarding to a young metallurgist. Quite apart from the all important but relatively short-range considerations of national security is the vision of the effect on civiliza-

Jan 1, 1953

By D. B. Smith, John Chipman

THIS investigation was undertaken as a prerequisite to the study of sulphur activities in the liquid system Fe-Cu-Ni, a continuation of the work of Sherman, Elvander, and Chipman,¹ using the same equipment and the same experimental technique. Temperature measurements are made with a disappearing filament optical pyrometer, sighting through a prism onto the surface of the melt which is heated by induction. To obtain true temperatures by this means, a calibration is necessary, since, in the absence of true black-body conditions, the observed temperature is always lower than the true temperature. This calibration is actually an emissivity correction, since the emissivity is a function of both temperature and melt composition. The original furnace was used with a deeper metal bath to provide sufficient depth of immersion for the thermocouple which was inserted through the sampling hole. The atmosphere was a 50-50 mixture or argon and hydrogen passing through the furnace at a rate of 1000 ml per min, and preheated by means of a molybdenum resistance coil. It was assumed that the rapid gas flow effectively eliminated any error which might have resulted from the presence of metallic vapor. The charge in each case consisted of about 300 g of metal, contained in a high purity, dense alumina crucible. At each melt composition, readings of the optical pyrometer and of a thermocouple immersed in the molten metal were taken simultaneously. Calibration curves of optical vs. true temperature were then made for each melt composition investigated. Thermocouples were made of 0.010 in. platinum and platinum-10 pct rhodium. They were checked against the melting point of chemically pure copper. Silica protection tubes with an outer diameter of approximately 1/8 in. were used. The depth of immersion of the tip in the molten metal was approximately 1 14 in. The life of these small thermocouples was relatively short, varying from approximately 1 min at 1550°C to 10 min or longer at 1300°C. Melts containing iron corroded the protection tubes more than those without iron present. Measurements taken while heating checked those taken while cooling, indicating the absence of a temperature gradient between the molten metal and the thermocouple. Results The temperature range of the. measurements on copper-free metals extended from the melting point to 1600°C. For copper the upper limit was 1380°C, and the data were extrapolated linearly for comparison with observations on the other metals and alloys at 1535°C. Examples of typical calibration curves for various melt compositions are shown in Fig. 1. These curves, besides providing a calibration system for the given experimental conditions, also give a basis for the calculation of true emissivities at the effective wavelength of the pyrometer, 0.65 micron. The starting point of the calculations is the value of the emissivity of iron at its melting point. Taking the melting point of electrolytic iron under hydrogen as 1535°C, and using the corresponding emissivity value of 0.43, as determined by Dastur and Gokcen,² the emissivities can be determined as functions of composition (and temperature, if desired). The relationship used is the Wien equation: ln(Ea)=C2/?(1/T1-1/Ta where E is the emissivity; a, the transmissivity of the optical system; C,, the fundamental constant, 14,380 micron-degrees; A, the wave length of light used (0.65 micron); Tt, the true temperature, OK; and T., the apparent temperature, OK. At the melting point of iron the observed temperature was 1358"; this gives 0.62 for the transmissivity, which compares with 0.65 in the similar system used by Dastur and Gokcen. The emissivities of all the compositions investigated were determined at 1535°C, after obtaining from each calibration curve the corresponding temperature. These results

Jan 1, 1953

By George C. Lipsey

FOR many years the mining of coal and other minerals occurring in sedimentary formation has been planned according to information obtained by diamond drilling. Placer mines have used churn drills for sampling and estimating deposits, and some metal mines have used the method either wholly or in part. The diamond drill method, therefore, although not entirely new, has come into more prominence in the last few years. Several large-scale developments now being planned or in the production stage have used this method in varying degree. This paper will describe the operations of the Howe Sound Exploration Co., Ltd. at Snow Lake, Manitoba, where a gold mine was developed and equipped for mining and milling wholly on the basis of diamond drilling results. The property has been in operation nearly 3 years, so that results can be compared with the estimates and assumptions made from the diamond drilling. In developing the subject it is necessary to outline as briefly as possible the normal method of mining, from discovery to production stage. Table I sets forth these various stages, the methods of financing, the percentage of total cost, and the relative time interval required for each section of the work. The plan presented in this table cannot be applied to all mining developments, but it gives a basis on which to work. In Stages 2 and 3 the investment is moderate, and if the property does not respond favorably the options or interests can be terminated. Stage 4 represents a sizeable investment, and it is more difficult to drop the property after this part of the operation is completed. Stages 2, 3, and 4 may be repeated several times by diflerent groups or companies before Stage 5 is reached, but when Stage 5 has been started the total capital investment must be provided and there can be no turning back. It will be noted that there is a total of 116 units of investment in the overall cost if one company proceeds with Stages 2, 3, 4, and 5 in order. Stage 4, however, consumes time which is important when markets are being considered. Bringing a property into production when metal prices are low is much more difficult than when the prices are high, and if this stage can be set aside production is attained more quickly. When Stage 4 is eliminated the total becomes 86 units of cost for Stages 2, 3, and 5, but an adjustment of 14 units must be added to Stage 5. These 14 units represent the useable value of Stage 4. Thus Stage 4 represents an investment of 30 units if carried on before Stage 5, but 14 units if included with Stage 5. This is accounted for by the fact that development work can be accomplished more cheaply under Stage 5, since everything that is done is planned on a production basis with permanent services. Stage 4 must of necessity be governed by expenditures, and a great many temporary services, including housing and power plants, must be provided. The prospect shaft is a small one, and drifts,

Jan 1, 1953

By J. T. Norton, Pekka Rautala

The phases and equilibria in the W-Co-C system have been studied by X-ray diffraction methods, metallographic technique, and thermal analysis. In addition to the 7 phase, two double carbides, called 8 and have been revealed. The compositions correspond to CO3 W6C2 and Co3-W10C4. The reactions leading to these phases have been explained and tentative diagrams of stable and metastable equilibria proposed. The basic reactions in sintering cobalt cemented tungsten carbides are discussed. THE W-Co-C system is of fundamental importance in practical carbide manufacturing as well as for the understanding of the sintering mechanism. Surprisingly little is known about this system, for the probable reason that all the important alloys are of two-phase structure and that the diagram Co-WC has been treated as a quasi-binary. This obviously is incorrect, because WC decomposes before melting. One ternary phase, 7, of composition Co3W3C has long been known. It was first studied by Adelskold, Sundelin, and Westgren,1 although the isomorphous iron-tungsten carbide was known earlier. There have been in the literature several reports of two 7 phases.' " Also the 7 phase has been considered unstable by Takeda4 and Westgren.1 The Co-WC diagram has been studied by Wyman and Kelley5 and a quasi-binary diagram has been published by Sandford and Trent.2 Takeda has published a tentative Co-W-C diagram, considering both metastable and stable equilibria. However, the lines of two-fold saturation are shown only partially and it seems impossible to complete the diagram without violating the phase theory. Therefore it seemed desirable to examine the system in more detail. Experimental Procedure The alloys used in the present investigation were made of powders of tungsten, tungsten monocarbide, cobalt, and carbon and were of the grade used in manufacture of commercial cemented carbides. The powders were ground and mixed in small stainless steel ball mills, using balls of the same material. Benzene was used as a dispersing agent. The mixing period was 1 hr, since this was shown to give suffi- ciently good mixing of the powders without too great a contamination from the mill. After ball milling, the specimens were pressed in cylindrical or rectangular dies. No paraffin or other lubricant was used and the small compacts had sufficient green strength to be handled without difficulty. Several sintering furnaces were employed. The most satisfactory arrangement was a vacuum furnace based on the Arsem principle which employed a graphite helix as the resistance heating element. Specimens were placed on graphite stands and there was generally a slight carburization or decarburiza-tion of the specimen surface, depending on the carbon content of the alloy. The evaporation of the cobalt at a sintering temperature of 1400°C was not significant, but became severe at 1500°C and higher. The sintering time was 1 hr at 2000°C and 2 to 4 hr at lower temperatures. It was not possible to quench the specimens, but the cooling rates were rather fast, greater than 300°C in the first minute. In the system under investigation, the reactions are sluggish, and it is believed that the high temperature structures are satisfactorily retained. The principal method of investigating the sintered specimens was X-ray diffraction by the Norelco recording spectrometer. Approximate determinations of the phase boundaries were made by the disappearing phase method. Ternary Phases To study the phase formation in W-Co-C system, a series of specimens was sintered at 1400°C. In this experiment two ternary phases, called here ? and k were formed in addition to the well-known 7 phase. The 7 phase, which has been completely described by Westgren: showed a range of homogeneity from 7 to 20 pct C and from 38 to 48 pct Co. At 1400°C the 7 phase was found to be in equilibrium with monotungsten carbide, 8, tungsten, 8, #?, and liquid. The boundaries toward #? and liquid were difficult to determine and appeared to be very temperature sensitive. The other boundaries are believed to be well fixed. The homogeneity range of 7, as measured in this work, is considerably smaller than the one

Jan 1, 1953

By Fred C. Bond

DISCUSSION Milton C. Shaw and Donald R. Walker (Massachusetts Institute of Technology)—For many years the two empirical rules of comminution bearing the names of Rittinger and Kick have been applied to grinding processes to account for the energy required to crush brittle materials. The basis for Rittinger's rule was the thought that the energy to grind a substance went largely into supplying the additional energy associated with the new free surface, while Kick's law was prompted by the concept of dimensional similarity and is a special statement of the concept of constancy of strain energy to cause rupture. According to Rittinger the energy to grind a given volume varies as the change in the square of the mean particle size, v - A (D2), while according to Kick this energy varies

Jan 1, 1953

By J. P. Denny

The constitution of the Ga-In system was determined by thermal methods. An experimentally determined metastable equilibrium line (an extension of the indium-rich liquidus) was obtained. The various alloys were studied metallographically using polished samples obtained by a casting method. These low melting alloys required a special dry-ice assembly to maintain a suitable temperature. RECENT interest in alloys that are liquid at room temperature has led to rather extensive investigation of gallium-base alloys. Widely distributed over the earth, gallium could be produced in substantially larger quantities than at present, if a significant demand existed.' One study' has established its presence in 12 out of 14 zinc blends, in all of 15 aluminum ores, in 4 out of 12 manganese ores, in 35 out of 91 iron ores, and in all of 7 magnetite ores. It occurs as a rule in minute amounts, however, leading to high extraction costs. Recent quotations run from $2.50 to $7.50 per g. During the course of the present investigation, portions of the system Ga-In have been redeter-mined, and the results of this study are presented herein. Thermal and metallographic methods have been employed. Lecoq de Boisbaudran, the discoverer of gallium, conducted the first investigation" on Ga-In alloys in 1885. The temperatures of incipient melting, and of completion of melting, were determined at four alloy compositions. In 1936, Hansen' constructed a eutec-tic-type phase diagram for the system Ga-In, based on . work. The existence of a Ga-In compound was regarded as improbable by Hansen, and subsequent investigations are in agreement. French, Saunders, and Ingle3 conducted a more complete study of the system in 1938, using thermal methods. Their phase diagram is a eutectic type, containing a unique concave-upward liquidus. The solid-solution range of gallium in indium was reported as 9.5 pct by weight, and that of indium as less than 1 pct, at the eutectic temperature. The eutectic composition, determined as being bracketed by the compositions showing a true horizontal at the eutectic temperature (16°C), was reported as 76 5-0.5 pct Ga and 24 i 0.5 pct In. Experimental Procedure The preparation of Ga-In alloys is simplified by the low melting points involved. Various compositions were prepared by melting in pyrex tubes, using a cover of distilled water or parafin to prevent the alloys from wetting the glass wall. In all cases, the melts were homogenized. by stirring. Where possible, both cooling and melting curves were determined. The extensive undercooling of gallium was found to prohibit a satisfactory cooling-curve analysis of gallium-rich alloys, however, and transition points on the gallium side of the eutectic could be determined only by melting curves. The inverse rate method of thermal analysis proved to be most satisfactory and was used to a great extent. Various heating and cooling rates were used, ranging from 0.2" to 5.0°C per min. Low temperature melting analyses were conducted within a constant temperature bath, maintained at about 70 °C. The alloys were solidified (under water or paraffin) within a pyrex tube, using dry ice; the tube was then sealed within a cold Dewar flask, the unit transferred into the constant temperature bath, and periodic temperature readings taken. The high temperature melting-curve determinations and all cooling-curve determinations were made in a vertical tube furnace. At near-eutectic compositions, the furnace was placed within a refrigerated room held at —20°C. Accordingly, the furnace on cooling approached —20°C asymptotically and permitted the determination of those phase transitions occurring below room temperatures. Temperatures were measured with a 30-gage iron-constantan thermocouple, immersed directly in the alloy. To prevent contamination of the melt, the leads and junction were coated with Lucite, applied by painting with a solution of Lucite in ethylene dichloride. Electromotive force measurements were made with a Leeds and Northrup precision potentiometer, type 8662. The couples were calibrated against the boiling point. of water and, at lower temperatures, against a calorimeter thermometer having a Bureau of Standards certificate. The melting points of gallium and indium used in the present investigation were determined as 29.-77° and 156.1°C, in good agreement with previously reported values of 29.78°C° and 156.4"C.' The spec-

Jan 1, 1953

By W. Rostoker

PART of a program of research on the Ti-A1 system1 involved a study of the lattice parameters of the titanium-rich a solid solution, which has a hexagonal close-packed structure. For this work, a 14 cm Debye-Scherrer powder camera and filtered CuK, radiation was used. For each pattern, the parameters were calculated by a least squares solution of the five strongest high angle lines. This provides an accuracy of i0.005A or better. The results are shown graphically in Fig. 1. It will be seen that an unusual change of slope occurs in the curve for the C parameter at high aluminum contents. Such anomalous changes in slope have been recorded by RaynorV or several magnesium-rich solid solutions. The effects were interpreted in terms of a special contribution to the lattice distortion due to factors of electronic origin predicted by Jones." Jones' theory, in substance, suggested that an unusually large expansion of the lattice would begin when the electron per atom concentration in the alloy was increased to a value at which an overlap just began from one Brillouin zone to another. Con-

Jan 1, 1953