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By Arch J. Alexander

COAL is produced, in commercial quantities, in thirty-five of the sty-five counties of West Virginia. Oil and gas are produced, commercially, in forty-two counties. So, you may readily see that coal, oil and gas are closely related as to production areas. Many of the West Virginia coal mines are studded with oil and gas wells, as drilling has been done in thirty-two of the coal bearing counties. When the drilling of oil and gas wells was placed under the regulatory control of the Department of Mines on June I, 1929, it was estimated, by the State Geological Survey, that 64,000 wells had been drilled in West Virginia and that 34,mo wells were then being operated as oil and gas producers. No records of many of these remaining 30,000 abandoned wells exist and some of them remain a standing menace to safety as our coal extraction continues. Of a total of 13,100 new wells drilled since June 1929, approximately 5,200 have been drilled through coal measures. Approximately 7,000 wells, which were drilled through coal measures, have been abandoned in the same period of time. Many of these wells were drilled prior to the enactment of the oil and gas laws. Prior to the enactment of the Oil and Gas Law, which established the Oil and Gas Division of the Department of Mines in 1929, there had been several mine explosions attributable to cutting into un- charted wells and the improper plugging of other wells. The most serious explosion was that of Mines No. 47 and No. 49 of the Consolidation Coal Co. in Marion Co., when one of the so-called plugged wells leaked or seeped through some 80 ft of strata to the coal bed elevation, filling the mine with gas, the gas being ignited, killing a good many men and wrecking two coal mines. Legislation, to combat well hazards to coal mines, was slow in coming. In 1928, R. M. Lambie, then Chief of the Dept. of Mines, got sufficient support from coal, oil and gas interests to get the legislature to pass our present oil and gas laws. These statutes not only protected the coal industry but went a long way toward conserving the oil and gas resources of our state. Before drilling for oil or gas on any tract of land, known to be underlaid with one or more workable seams of coal, the well operator is required to submit a map of the area showing the location of the proposed well, and to send a copy to the Dept. of Mines and a copy to the coal operator. If no objections to the location of the proposed well are made by the coal operator within ten days, a drilling permit and a number for the well are then issued and work may proceed. If, however, the location of the proposed well is objected to by the coal operator, on the grounds that the location of the well will interfere with present mine operations, projected workings, or other- wise Cause a dangerous condition, the operator may file a written objection with the Dept. of Mines.

Jan 1, 1948

By C. W. Allen, B. D. Cullity, H. S. Choi

The torsional deformation of aluminum and magnesium crystals is investigated, with particular reference to the dependence of proportional limit on crystal orientation. The proportional limit is found to be governed by the average value of the resolved shear stress on the most highly stressed slip systems, but the proportional limit does not strictly obey a critical-resolved-shear-stress law. The behavior of a cylindrical single crystal stressed in tension is well known: plastic flow begins when the resolved shear stress on the most highly stressed slip system reaches a critical value. There is much less understanding of the effect of torsion on such a crystal and on the way in which the critical-resolved-shear-stress law should be applied to torsional deformation. In the present paper particular attention is paid to the dependence of plastic yielding on crystal orientation and lesser attention to the mechanism of flow after yielding has occurred. New work on aluminum and magnesium crystals is presented, and previous results obtained in this laboratory on magnesium1 are re-examined. STRESS DISTRIBUTION The problems involved in torsional deformation of single crystals are due entirely to the complexity of the stress distribution. In tension, if loading conditions are perfect, the shear stress on any particular slip plane is completely uniform over the entire area of that plane. In torsion, on the other hand, the stress on any selected plane in a particular direction varies not only from center to edge of the specimen but also around its perimeter. It is convenient to express the stress at any point in terms of t0, which is the shear stress acting at the surface of a cylindrical specimen on a plane normal to the axis and in a direction tangential to the cylinder. At point P of Fig. 1 this stress acts in the direction of axis 2 and is given by To = 2T/pr3 [1] where T is the applied torque and r the specimen radius. This stress can be resolved on any chosen slip system, and details are given in the Appendix. Let P be the point on the specimen surface where the stress is to be evaluated; P is defined by its angular distance A from an arbitrary reference line through 0 normal to the axis. his line is usually taken as the direction of incidence of the X-ray beam used to determine the crystal orientation.) Then the shear stress t, acting at P in direction Dona plane whose normal is N is given by Ts/TO = sin ? 0, cos ?d sin (?0, - ?) + cos ?, sin ?d sin (?d - ?) [2] where 0, and Od are the angles between N and D, respectively, and the axis, ?0 and ?d are the angles between the projections of N and D, respectively, on the transverse plane and the reference line through 0. By means of Eq. [2], the stress 7, acting in any given slip direction can be computed. In the previous work on magnesium1 only gross slip tangential to the specimen surface was considered, and this

Jan 1, 1963

By John B. Campbell, George G. Binder, Loren H. Jenks

Conventional methods of producing crude oil generally leave in the depleted reservoir 1 to 3 bbl of oil for every barrel brought to the surface. This paper describes a field test which explores the possibility of using gas-driven liquid propane to improve oil recovery efficiency. Laboratory theoretical and experimental studies leading to the field test indicated that low residual oil values could be obtained using limited amounts of propane driven by gas. The field test involved (I) repressuring the reservoir to the vapor pressure of liquid propane, (2) injecting the liquid propane, and (3) injecting dry natural gas to drive the propane and oil to the producing wells. Considerable preliminary work, including new drilling, work-overs, and a pressure survey was necessary. During the test, oil production rates have averaged about nine times the final primary rates. The field average GOR is still below the pre-test value. Oil recovery to date is 112,000 STB. About one-third of the 143,-000 bbl of propane injected has been produced to date. Results of the C-2 block test are encouraging and larger, more definitive field projects ore indicated. INTRODUCTION The cost of finding new crude oil reservoirs continues to increase. Today the oil industry is drilling more and deeper wells and making fewer big discoveries. Nevertheless, the demand for oil and oil products increases each year. It is natural that oil companies, faced with this situation, concentrate on recovering more of the oil existing in our known crude oil reservoirs. There is room for much improvement. For every barrel of oil brought to the surface by present day methods of producing crude oil, generally 1 to 3 bbl are left behind in the depleted reservoirs. The "unrecoverable" oil in petroleum reservoirs is largely "trapped" by capillarity. Since flushing with a solvent is exceedingly effective in combatting oil loss due to capillarity, much effort in this direction has been made in recent years1,2,3,4,5. Liquefied petroleum gas (LPG) has been suggested as a relatively inexpensive. abundant, easily recoverable solvent for crude. Some operators have observed striking responses in oil recovery at production wells offsetting input wells in LPG storage reservoirs6,7,8. In spite of the low unit cost of LPG, however, it is uneconomic in general to inject a volume of LPG into a reservoir to remove a like volume of oil. A modification of solvent flushing in which a limited quantity of liquid propane is gas driven through a reservoir appears capable of recovering much more than 1 bbl of oil per barrel of propane injected. Also, most of the propane injected should be recoverable for sale or re-use. Since such a process could well have widespread and profitable application, The Carter Oil Co. is making an extensive evaluation of the technique's possibilities. Laboratory development of the gas-driven propane recovery technique was sufficiently encouraging to justify testing in the field. Since 1952, the Production and Research Departments of The Carter Oil Co. have cooperated in a field test in the C-2 Block leases of the

Jan 1, 1958

By C. F. Knutson, Martin Felsenthal, J. D. Lung, J. D. Sudbury

This paper has been written to summarize the laboratory and field studies leading to injection of Pacific Ocean water into the Third Grubb formation. Laboratory tests for studying the permeabilities of cores to Pacific Ocean water are described. Resu1ts of these tests showed that the water could be successfully injected if it is chertzically stable, sterile, and properly filtered. Clay swelling was shown to be a comparatively minor factor in permeability reduction. Studies leading to development of an economical system for properly conditioning the ocean water are discussed. It was necessary to control pH, calcium carbonate deposition, bacterial growth, iron solubility. oxygen, and suspended .solids. A relatively simple system combining the use of sulifur dioxide, a quaternary rlmmonium chloride, and filtration was shown to adeqrrately control all these factors. This combination has not previozrsly been used as a water treating technique. Evaluation tests of the water conditioning system prior to injection are described, and results of such tests are presented. Control measures needed to insure a continusously adequate water treatment are reviewed. INTRODUCTION The utilization of sea water for waterflooding has only recently been attempted. Knowledge of treating requirements has been limited, and in most cases no water treating has been done. Prior to the initiation of the Third Grubb zone pilot water flood at Ventura, Calif.,1,2 extensive laboratory research was done in an effort to define the treatment necessary to provide a suitable injection fluid. Close coordination and cooperation between field and research personnel were found to be the foremost requisites in developing the most economical and practical method for treating ocean water. LABORATORY STUDIES Plugging Tendencies of Untreated Ocean Water A program of laboratory studies was initiated for the purpose of evaluating whether ocean water could be injected into the formation for prolonged periods of time without causing plugging of the pore spaces of the formation. Because of the fairly low permeability of the formation (averaging about 40 md), it was realized from the outset that a water of exceptionally high quality was needed. Ocean water used in the laboratory studies was carefully filtered through ultrafine fritted glass filters, having nominal maximum pore sizes of 1.4 microns. Permeability tests were then performed on representative core material from the formation. It soon became apparent in these tests that filtration alone was not a sufficient treatment for the ocean water. Prolonged injection of the filtered water caused rapid plugging of the core samples. The permeability decline of a typical sample is illustrated by Curve A in Fig. 1. The several factors which can contribute to this plugging tendency are briefly reviewed below: Interaction with Formation Clays An evaluation of clay swelling effects on liquid permeability was made using core samples from the Grubb formation. An oil was chosen for determining the reference liquid permeability because it would not tend to react with any clays that might be present in the formation. The samples were then extracted, dried, and resat-urated with either treated ocean water, formation water, or fresh water. Permeabilities to the various waters were then determined. Results of this test series are summarized in Fig. 7. The difference between the oil permeability and water

Jan 1, 1957

By J. P. Hammond, C. J. McHargue

THERE have been no publications on the wire texture, on the cold-rolled sheet texture, nor on the recrystallized sheet texture of vanadium. Since it has a body-centered cubic structure, it would be expected to show strongly preferred orientations such as are found in iron' and molybdenum.' The wire textures of body-centered cubic iron,3 tungsten," molybdenum,5 antalum,6 iobium,6 and brass6 have been found to have [110] directions lying parallel to the wire axis. Wires of iron,' containing 1.95 pct V or 1.95 pct Si,7 and steel8 retain their texture upon recrystallization. Molybdenum9 and tungsttln' wires retain their texture after recrystallization at low temperatures. A [loo] recrystallization texture has been reported for mo1ybdenum9 and for a Fe-Ni alloy (53 atomic pct Ni).10 The cold-rolled sheet texture for iron,' mild steel," and molybdenum chiefly one in which the [110] directions lie parallel to the rolling direction and the (100) planes lie parallel to the rolling plane with a deviation from this position chiefly about the rolling direction as an axis. This paper presents the cold-rolled and the re-crystallized wire textures, and the cold-rolled and the recrystallized sheet textures for vanadium. The results show that the textures in vanadium are not significantly different from those reported for other body-centered cubic metals. The vanadium used in this investigation was the so-called "ductile" vanadium which has a nominal composition within the following limits:12 0, 0.05 to 0.12 pct; H, 0.001 to 0.004; N, 0.02 to 0.04; C, 0.03 to 0.07; and V, 99.8 to 99.9. The wires were formed by rolling annealed rods of 0.280 in. diam to 0.028 in., a reduction in diameter of 90 pct. The wires were then electrolytically etched to 0.005 in. diam and used as such for specimens. Annealed sheet was reduced 95 pct in thickness from 0.100 to 0.005 in. with a two-high, 4-in. diam mill using reductions no greater than 10 pct per pass. In order to avoid temperature effects, the sheet was allowed to cool between passes. X-ray specimens were made in the form of posts from the sheet. The sheet was mounted in a fixture and the edges were polished using metallographic technique. Each edge was alternately polished and etched during the last stages in order that all worked material would be removed. These post specimens were approximately square in cross-section. The specimens to be recrystallized were wrapped in tantalum foil, sealed in evacuated quartz tubes, and annealed at 1600°F. The X-ray data were obtained from transmission shots made with a 0.030 in. pinhole camera, and molybdenum radiation with a zirconium filter inserted between the specimen and film. The grain size was sufficiently small in both the cold-worked and recrystallized material to give satisfactory results with the specimens stationary. In order for the wire texture to be determined, transmission X-ray patterns were taken with the

Jan 1, 1953

By H. F. Silliman, Daniel R. Hull, John R. Freeman

IN the normal operation of a brass-rolling mill, sheet and strip has, for the most part, been finished in comparatively thin gauges, involving a substantial amount of coldwork and a considerable number of anneals. This condition has been disturbed by the prep0nderance of cartridge brass, which is not rolled to thin gauges, and particularly by brass for artillery cartridge cases, on which the mill may finish its work at a thickness between 0.400 and 0.900 in. Obviously, the amount of rolling and the number of anneals to which such a product can be subjected are small compared with strip that is carried to a thickness of a few hundredths of an inch. As a result, critical examination into the internal condition of metal has been made on an extensive scale at a stage of manufacture that would not, in normal times, have been chosen for complete inspection. Under these conditions, a type of defect has been recognized that is not seen at thinner gauges. It might be more accurate to call it the appearance of a defect, since it refers to an apparently laminated, discontinuous structure, which, in fact, does not exist as such, and disappears after suitable treatment. For this reason it has been called a phantom lamination, which the authors consider an appropriate term. It is the purpose of this paper to describe the phenomenon and the conditions of its occurrence and, at least tentatively, to discuss its nature and cause. Great numbers of phantoms may be found in 2: 1 brass, either hot-rolled or cold-rolled. They are also found in 70-30 brass, sometimes when hot-rolled and generally when cold-rolled. It is not believed that phantoms are confined to these alloys but this paper is limited to them for the purpose of description. HOT-ROLLED 2:I BRASS For illustration, therefore, a typical cake of hot-rolled 2: 1 brass has been chosen. This was rolled to a slab 7/8 in. thick, from a casting 5 in. thick by 24 in. wide by 18 in. high, which was believed to have been sound. After hot-rolling and cooling, the slab was sheared and a portion of such a shear cut is shown in Fig. 1. It would be difficult to convince anyone viewing this specimen that the metal was not unsound. The impression would be confirmed by the appearance of a tensile break, as shown in Fig. 2. This is an ordinary tensile-test piece from metal just described. Although there was nothing in its tensile strength or elongation that suggested unsoundness, it appeared run through with pipes and laminations. To question the reality of such a condition would imply questioning the obvious. But, considering the history of the metal, it w0uld be difficult to believe that it could be so bad as it appeared. It seemed reasonable, though, that if the defects were what they appeared to be, they could be traced back from the sheared or broken face.

Jan 1, 1945

By Lawrence B. Wright

The Republic district, Washington, is of new interest because of the discovery of new gold-silver ore within a unique structural pattern. The camp was revived in 1937 fol1owing installation of a plant to treat low-grade disseminated ore at Knob Hill and further stimulation followed discovery of "cross vein" breccia ores in 1939. Previous writers 1-2 ascribed the quartz veins to a latite porphyry stock, but are in disagreement as to its precise location and extent. This study leads to the conclusion that the ores have a more profound parentage linked to a broad system of thrust faults and folds, the mechanical origin of which is related to a southward trending (Sanpoil) syncline connecting with the Lewis and Clark zone of shift described by Billingsley and Locke3 in 1939. The Republic anticliue and a cross anticline recumbent against Cretaceous granodiorite. and involving some 4000 ft of Eocene andesite flows and early Miocene lake beds, localize the ores, mainly along the east flank, in a series of openings simulating drag folds and steeper than the folded flows. These broad structural features no doubt reach deeply into the basement rocks, where at appropriate crossings and junctions it is suggested that heat effects gave rise to ore-making materials, including, in this instance, intrusive breccias that later were mineralized, and comprising the broader bodies of new ores. The breccia ore is seen crosscutting the earlier narrow quartz veins with a welding of the two at junction areas by a second surge of ore minerals. The ore mined and developed since 1937 equals district production from 1896 to 1937 The ores are typified by cherty quartz, adularia and some barite, with fine pyrite and marcasite, polybasite, pyrargyrite, tetrahedrite and gold. Selenium is present, possibly with gold, as a normal selenide. The disseminated ores, as well as the vein and breccia ores, are localized principally in one 500-ft flow (Knob Hill andesite), which has been traced around the crest of the low northward-plunging Republic anticline. The gold-silver ratio in the earlier narrow veins is about I to 4 and in the disseminated and breccia ores, I to 7. The latter higher silver ratio is deemed to reflect the character of the second surge of mineralization. Sills and dikes of the Columbia River (Miocene) basalt cut the folded structure and ore, thus placing the mineralization in the middle Miocene. Introduction The Republic district of north central Washington is of new interest because of the discovery, development and extraction of new gold-silver ore; also, because of a unique local structural pattern believed to be integral with the broader tectonic mechanism of the continental framework. This district had 40 years of modest rating following its discovery in 1896. Its narrow ore bodies, complex mineralogy. and early inadequate metallurgy, together with the apparent bottoming of ore near 1000 ft, limited production to 300,000 oz of gold and 1,000,000 oz silver between 1897 and 1914. The camp was then reduced to lease Life until 1937, when the gold price increase of 1933 to $35 per ounce

Jan 1, 1949

By Lawrence B. Wright

The Republic district, Washington, is of new interest because of the discovery of new gold-silver ore within a unique structural pattern. The camp was revived in 1937 fol1owing installation of a plant to treat low-grade disseminated ore at Knob Hill and further stimulation followed discovery of "cross vein" breccia ores in 1939. Previous writers 1-2 ascribed the quartz veins to a latite porphyry stock, but are in disagreement as to its precise location and extent. This study leads to the conclusion that the ores have a more profound parentage linked to a broad system of thrust faults and folds, the mechanical origin of which is related to a southward trending (Sanpoil) syncline connecting with the Lewis and Clark zone of shift described by Billingsley and Locke3 in 1939. The Republic anticliue and a cross anticline recumbent against Cretaceous granodiorite. and involving some 4000 ft of Eocene andesite flows and early Miocene lake beds, localize the ores, mainly along the east flank, in a series of openings simulating drag folds and steeper than the folded flows. These broad structural features no doubt reach deeply into the basement rocks, where at appropriate crossings and junctions it is suggested that heat effects gave rise to ore-making materials, including, in this instance, intrusive breccias that later were mineralized, and comprising the broader bodies of new ores. The breccia ore is seen crosscutting the earlier narrow quartz veins with a welding of the two at junction areas by a second surge of ore minerals. The ore mined and developed since 1937 equals district production from 1896 to 1937 The ores are typified by cherty quartz, adularia and some barite, with fine pyrite and marcasite, polybasite, pyrargyrite, tetrahedrite and gold. Selenium is present, possibly with gold, as a normal selenide. The disseminated ores, as well as the vein and breccia ores, are localized principally in one 500-ft flow (Knob Hill andesite), which has been traced around the crest of the low northward-plunging Republic anticline. The gold-silver ratio in the earlier narrow veins is about I to 4 and in the disseminated and breccia ores, I to 7. The latter higher silver ratio is deemed to reflect the character of the second surge of mineralization. Sills and dikes of the Columbia River (Miocene) basalt cut the folded structure and ore, thus placing the mineralization in the middle Miocene. Introduction The Republic district of north central Washington is of new interest because of the discovery, development and extraction of new gold-silver ore; also, because of a unique local structural pattern believed to be integral with the broader tectonic mechanism of the continental framework. This district had 40 years of modest rating following its discovery in 1896. Its narrow ore bodies, complex mineralogy. and early inadequate metallurgy, together with the apparent bottoming of ore near 1000 ft, limited production to 300,000 oz of gold and 1,000,000 oz silver between 1897 and 1914. The camp was then reduced to lease Life until 1937, when the gold price increase of 1933 to $35 per ounce

Jan 1, 1949

By J. P. Heller, H. B. Bradley, A. S. Odeh

It is an accepted procedure to represent oil field displacement problems in which the pressure is relatively constant by a potentiometric model. Variations in reservoir permeability thickness product are represented in the model by proportional variations in electrolyte depth. It is shown that significant errors are present wherever these variations are of such magnitude that the consequent differences in the electrolyte depth in the model or any regions therein are appreciable in comparison with their respective horizontal dimensions. To demonstrate the order of magnitude of this error, a hypothetical linear oil field in which permeability varies linearly with distance was treated both analytic.ally and by potentiometric model. The results obtained from the model are compared with the exact solution for various configurations of linear geometry. Deviations in flow times up to 11 per cent were observed. It is confirmed that these discrepancies can be reduced by increasing the areal scale and/or decreasing the vertical scale of the model. It is the purpose of this work to assist in the design of potentiometric models by indicating the relationship between this error and the chosen scale factors. INTRODUCTION The fundamental geometrical criterion which determines whether the pressure distribution in an oil or gas reservoir may be simulated in a conventional potentiometric model is the requirement that all reservoir parameters be constant along any vertical line between its upper and lower boundaries. This situation never obtains exactly; nevertheless, it is usually assumed that there is no permeability stratification within the section of interest, that all wells completely penetrate the sand, that there are no gravitational effects, and that variations in thickness of the sand are small compared to the horizontal extent of the field. In these ways the reservoir problem is reduced to two dimensions in which there is no variation of pressure in the vertical direction within the limits of the sand. Variations in sand thickness and/or horizontal pesmeability may be taken into account as described by Muskat, by considering the fluid conductivity of the reservoir in its horizontal plane to be proportional to the product of permeability and sand thickness. If the variations in sand thickness are small compared to the horizontal dimensions of the reservoir, then it is a good approximation to consider the reservoir problem to be essentially two dimensional. The same approximation, however, is made in the simulation of the assumed two-dimensional reservoir by the electrolytic model. The model, if it is to take into account variations of permeability-thickness product, must of necessity be made in three dimensions, that is, with variable depth. Most potentiometric model studies and theoretical treatments reported in the literature to date2,3,4,5,6,7,8 are those in which either an average permeability was used or a constant permeability was assumed. This is understandable since detailed permeability data are not usually available for the majority of reservoirs. Many investigators have recognized that the failure to incorporate permeability variations within a reservoir in model studies leads to serious error in predictions made

Jan 1, 1957

By John C. Calhoun, J. E. Warren

A study of waterflood efficiency, given in terms of oil recovery at water breakthrough and u1timate recovery, has been made on short, consolidated Pyrex glass cores rendered oil-wet by chemical treatment. Contact angle. interfacial tension, permeability and porosity were the variables considered. Oil and water viscosities, core length and velocity of flooding were held constant. The data permit interfacial tension, contact angle, porosity, and permeability to be grouped into a scaling coefficient along with viscosity, velocity of flooding and length of core. Correlation of the .scaling coefficient with recovery at water breeakthrough is found to follow prediction; correlations of ultimate recovery demand a scaling coefficient different from that which correlates breakthrough recovery. The work indicates that, with proper control, a group of similar natural cores, of permeability plug size, call he correlated 10 indicate basic flooding performance. INTRODUCTION The fraction of oil recovered from a porous medium is related to both reservoir conditions and production techniques. An investigation of all factors that enter into this relationship is necessary in order to arrive at the optimum method of exploitation for oil reservoirs. To define this relationship, laboratory studies have been made by a great many investigators. However. an important obstacle arises if the results of these experiments on water flooding are to be applied to practice. Ditferences in behavior are to be expected between reservoirs of the dimensions encountered underground and those used in laboratory work. Factors which play an important role under laboratory conditions may be of no consequence in reservoirs. Laboratory operating practices generally differ from field operating practices. Thus. a mere understanding of the mechanism of the displacement of oil by water is not enough. It is just as necessary that the process be analyzed dimensionally to give continuity and validity to the conversion from laboratory to field. The theory of oil displacement that has come to be accepted by the majority of those who are associated with reservoir mechanics had its beginning in the work of Leverett¹ and Buckley and Leverett2. The banking of oil, observed by many previous workers, was described by the "fractional flow" and the "frontal advance'' equations. The validity of the Buckley-Leverett theory was substantiated by the experimental and theoretical work of Terwilliger et al³; moroever, the theory was extended by the introduction of the idea of a "stabilized zone" to describe the banking of oil. Levine5 showed that the Buckley-Leverett equations gave reasonable agreement between calculated and experimental breakthrough recoveries only if the capillary pressure and gravity terms were included. Rapoport and Leas1 investigated the properties of linear floods and showed that both breakthrough and maximum recovery are related to a "scaling coefficient'' derived from the Buckley-Leverctt equations. Jones-Par-ra and Calhoun6 presented another scaling coefficient which included both viscous and capillary variables. Such scaling coefficients should suffice to predicl waterflood efficiency. However, some experimenters report data which does not appear consistent with the healing coefficient approach. For example, Engelberts and Klinkenberg7 conducted an extensive series of experiments on a dimensional model which contained a

Jan 1, 1956

By E. F. Bradley, R. I. Jaffee, H. R. Ogden, E. S. Bartlett, D. N. Williams

The mechanical properties of solid-solution-strengthened columbium alloys have been assessed as a function of alloying additions. Studies included the effects of tungsten, tantalum, molybdenum, and vanadium. Elevated temperature fabrication was required at alloying levels above about 15 pct W or 10 pct Mo. Tungsten, molybdenum, and vanadium additions increase tensile strength at room temperature and 2200°F, but tantalum additions exert little strengthening. Similarly, tungsten, molybdenum, and probably vanadium additions increase the ductile-to-brittle transition temperature, and tantalum additions decrease this parameter. The 2200°F stress-rupture strength is increased by tungsten and molybdenum additions; with 20 to 25 at. pct additions, 100-hr rupture strengths of 30,000 psi are obtainable. Small vanadium additions exhibit mild stress-rupture strengthening, and tantalum additions are innocuous. At 2500°F, tungsten additions retain stress-rutpure strengthening capability, but molybdenum additions are much less effective. Tantalum additions augment the stress-rupture strengthening of tungsten plus molybdenum additions at 2500°F. Of the refractory metals, columbium possesses specific potential for structural use in the temperature range from 2000" to about 2500°F. Desirable features of columbium are its good low-temperature ductility, ease of fabrication, oxidation mechanics (lack of a volatile oxide at moderate temperatures), good availability and reserves, and relatively low density. However, alloying is required to provide attractive strength at elevated temperatures. Published information concerning alloying be- havior of columbium relative to mechanical properties is sketchy, particularly in consideration for long-time applications at temperatures in excess of 2000°F. Only a few stress-rupture data at temperatures from 2000" to 2500°F have been reported;'-' these are too meager to allow rationalization of the effects of various alloying additions on creep or stress-rupture properties. Additional published data do, however, give some insight toward understanding of systematic alloying behavior for columbium relative to low-temperature strength4-' and ductility,' and elevated temperature tensile behavior.4,6 This paper is intended to augment previous knowledge, and to promote understanding of the alloying behavior of columbium for long-time structural service at elevated temperature. BASIC CONSIDERATIONS Solid-solution strengthening is recognized to be of prime importance in improving strength in columbium-base alloys. Other strengthening mechanisms may be (and are, in current alloys) used to augment solid-solution strengthening. As strengthening results primarily from lattice distortion, the strengthening effectiveness per atom depends upon atomic size mismatch between solvent and solute. Another factor in this regard is conformance to ideal solution behavior in the solid solution. Thus, for example, despite appreciable differences in the degree of mismatch between tungsten (5 pct), molybdenum (5 1/2 pct), and vanadium (7 1/2 pct) in solution in columbium, all are about equally effective in straining the columbium lattice at room temperature.'-' Similarly, tantalum additions do not strain the columbium lattice, and little strengthening is expected. Size effects being equal, maximum solution strengthening at high temperatures is anticipated to result from the addition of elements that increase the melting temperature of columbium. This expectation is based on an increase in the electronic bonding forces exhibited in the transition metal series as electronic structures approach those of the Group Vl metals. Of the metals that exhibit ex-

Jan 1, 1963

By J. W. Freeman, D. N. Frey

Fundamental reasons for the improvement in creep resistance of an austenitic alloy by cold working were investigated mainly by X-ray diffraction. The creep resistance was found to be improved by the internal stresses in the lattice of the alloy induced by the cold work. THIS investigation was concerned with the fundamental reasons for improvement in creep resistance of an austenitic alloy as a result of cold working. Also, the investigation was carried out to elucidate the conditions under which cold working could be expected to improve the creep resistance. To achieve these ends, creep resistance and internal structure were correlated for a variety of cold-worked conditions. Since the aim of the investigation was not to obtain specific and extensive information on any one alloy, creep testing was done with a single stress at 1200°F. Structural studies were carried out primarily with X-ray diffraction characteristics. The alloy used, low carbon N-155, was selected on the basis of being representative of at least some of the alloys used in gas turbines. Low carbon N-155 alloy in the form of %-in. sq bar stock was used in this investigation. The chemical composition, in percent, was: C, 0.13; Mn, 1.43; Si, 0.34; Cr, 20.73; Ni, 18.92; Co, 19.65; Mo, 3.05; W, 1.98; Cb, 0.98; N, 0.14; and Fe, balance. The bar stock was produced from a 13-in. sq billet, finished to 7/s in. round cornered square between 2060" and 1910°F. Prior to use in this particular investigation, the bar stock was solution-treated 1 hr at 2200°F and water quenched. This procedure was used in order to put the stock in a condition where effects of prior processing were minimized. Experimental Procedure The specific approach to the problem was twofold. First, the influence of cold working, under various conditions, on the creep rate under a single stress at 1200°F and on the internal structure was in part determined. Second, the effect of annealing at various times and temperatures on the creep rate and internal structure of the cold-worked samples was in part evaluated. The first step was basic to the investigation—creep resistance and structure were to be correlated. The second step was taken to see if the annealed samples showed some internal changes which could also be correlated with changes in creep resistance. This it was felt would facilitate solution of the basic problem. The creep and structural studies were carried out on samples reduced approximately 5, 15, and 40 pct at room temperature and 15 pct at temperatures up to 2200 °F. Annealing of various of the samples was done at 1200°, 1400°, 1600°, and 1800°F for time periods up to 1000 hr. Studies of the annealed samples were concentrated on materials rolled approximately 5, 15, and 40 pct at room temperature and 15 pct at 1400°F. The creep tests were carried out at 1200°F under 40,000 psi, the latter being approximately the 1000 hr rupture stress of the material

Jan 1, 1952

By J. Trevor Eyton

This paper addresses some of the financial risk hedging mechanisms available to a corporation contemplating entering the mining business at a significant level of investment. The approach which I have adopted is that of a case study relating to the risk hedging aspects of Brascan Limited's acquisition of 46% of Noranda Inc., formerly Noranda Mines Limited, followed by some remarks on options open to mining companies for reducing financial risks. To appreciate the rationale for Brascan committing over (Can.) $800 million to the natural resource sector, some knowledge of Brascan's parent company, Edper Investments Ltd., is required at the outset. Edper Investments, prior to acquiring a 48% interest in Brascan, controlled Trizec Corporation, one of the world's largest property companies. Edper also was involved in the financial services sector through Continental Bank of Canada and Hees International Corporation. For some considerable time prior to Edper's investment in Brascan, Edper felt a need to provide a better balance to its portfolio of property and financial services. Brascan was rich in cash, relatively unleveraged, and with important existing holdings in natural resources and consumer products. The acquisition of a controlling interest in Brascan provided an opportunity to balance Edper's portfolio of property and financial services with world class acquisitions in natural resources, supplemented by consumer products and financial services. The end result of Brascan's activities over the last few years is illustrated by the following analysis of the book value of Brascan's assets at the end of December 1983. [Can.$% Millions _ Natural Resources81748 Consumer Products 654 38 Financial Services 157 9 Other Operations895$1,717100% ] Source: Brascan 1983 Annual Report. The large emphasis on natural resources came about from the fact that for Canadians operating mainly in Canada, natural resources were attractive. We were impressed by Canada's position in the world natural resource industry as illustrated by some of the following statistics: [CommodityCanadian Estimated Production In 1983 As % of World Total Newsprint 30 Potash 21 Uranium 18 Molybdenum 17 Zinc 17 Pulp 16 Nickel 16 Saw Logs 11 Silver 8 Copper 7 Lead 6 Gas 5 Oil3] Source: U.S. Bureau of Mines and Brascan estimates. In addition, the quality of Canada's reserves looked good to us. The polymetallic nature of many of Canada's orebodies offered a hedge against risk relating to any one metal. Put another way, the by-product metal credits offered a net operating cost advantage with respect to many of the metals mined. Our energy costs also appeared to provide Canada's natural resource industries with an advantage. We considered Canadian mining expertise as amongst the world's finest, as were the exploration equipment and technology developed in Canada. In addition, Canada offered a stable political climate and one we knew. Further, we felt the Canadian Government's future role in the industry would, on balance, be benign, partly because the Canadian content of the mining industry was very high in contrast to the petroleum industry. Granted, we could find cheaper sources of copper; however, to do so would involve venturing into regions where country risks were higher.

Jan 1, 1985

By Basil B. Zavoico

Production of crude oil in the U.S.S.R. during 1940 is estimated at 222,600,000 bbl., as compared with the revised figure for the preceding year of 220,866,000 bbl., an increase of 0.79 per cent, and at least 20 per cent under the planned output. Baku district (Transcaucasus) remained the outstanding producing area, accounting for 72.33 per cent of the country's production, and this relative importance of the Apsheron Peninsula oil fields will probably continue lor many years to come. In the North Caucasus the Grozny-Dagestan area further extended its decline and the current production in this district amounts to only 6.06 Per cent Of the total U.S.S.R. output, as compared with 35.76 Per cent in 1931 The production of the Kuban-Maikop district remained virtually ullchanged from the preceding year, amounting to 7.64 per cent of the country's total. The Caucasian Province, therefore, in I940 produced 86.03 Per cent of the total production of the U.S.S.R. The promising new Permian Basin district, called Ural-Volga, and referred to sometimes as the "Second Baku," increased its production appreciably during 1940 and the output of that area amounted to 8.31 per cent of the country's total, as compared with 6.35 per cent during 1939. Production in the secondary districts of Russia continued unchanged though some new discoveries in the Emba salt-dome basin suggest that the output of that district may show some increase during the coming years. The drilling operations in Russia during 1940 reached a stage of virtual breakdown and the original footage plans were fulfilled only to the extent of around 50 per cent, while exploration drilling schedules were fulfilled only to the extent of about 25 to 35 per cent. This condition was due to the obvious lack of modern drilling rigs, of good drill pipe and of strong casing. Extended breakdowns occurred with deeper drilling, particularly because with few good drilling rigs available speed was being attempted with rotation rates that the inferior drill pipe and bits could not stand. Twistoffs and endless fishing jobs resulted. The difficulties became so serious a handicap to the Soviet oil industry that it was found imperative to order American drilling equipment and pipe in quantity, a policy that was never favored in the U.S.S.R because it requires expenditure of gold or exchange in major volume, and such exchange usually is reserved only to less bulky key items or to orders directly connected with armaments; also, oil-field machinery is very bulky and the prevailing lack of bottoms makes the transport of the indicated equipment a major problem. But little progress was similarly made in other branches of the Soviet oil industry. NO new major pipe-line construction work was undertaken, consequently the railroads continued to be overburdened with traffic that could be much more effectively handled by pipe lines. No new refinery construction of any magnitude was initiated, though several plants that had been in course of construction for several years were completed during 1940 and operation 554

Jan 1, 1941

By Basil B. Zavoico

Production of crude oil in the U.S.S.R. during 1940 is estimated at 222,600,000 bbl., as compared with the revised figure for the preceding year of 220,866,000 bbl., an increase of 0.79 per cent, and at least 20 per cent under the planned output. Baku district (Transcaucasus) remained the outstanding producing area, accounting for 72.33 per cent of the country's production, and this relative importance of the Apsheron Peninsula oil fields will probably continue lor many years to come. In the North Caucasus the Grozny-Dagestan area further extended its decline and the current production in this district amounts to only 6.06 Per cent Of the total U.S.S.R. output, as compared with 35.76 Per cent in 1931 The production of the Kuban-Maikop district remained virtually ullchanged from the preceding year, amounting to 7.64 per cent of the country's total. The Caucasian Province, therefore, in I940 produced 86.03 Per cent of the total production of the U.S.S.R. The promising new Permian Basin district, called Ural-Volga, and referred to sometimes as the "Second Baku," increased its production appreciably during 1940 and the output of that area amounted to 8.31 per cent of the country's total, as compared with 6.35 per cent during 1939. Production in the secondary districts of Russia continued unchanged though some new discoveries in the Emba salt-dome basin suggest that the output of that district may show some increase during the coming years. The drilling operations in Russia during 1940 reached a stage of virtual breakdown and the original footage plans were fulfilled only to the extent of around 50 per cent, while exploration drilling schedules were fulfilled only to the extent of about 25 to 35 per cent. This condition was due to the obvious lack of modern drilling rigs, of good drill pipe and of strong casing. Extended breakdowns occurred with deeper drilling, particularly because with few good drilling rigs available speed was being attempted with rotation rates that the inferior drill pipe and bits could not stand. Twistoffs and endless fishing jobs resulted. The difficulties became so serious a handicap to the Soviet oil industry that it was found imperative to order American drilling equipment and pipe in quantity, a policy that was never favored in the U.S.S.R because it requires expenditure of gold or exchange in major volume, and such exchange usually is reserved only to less bulky key items or to orders directly connected with armaments; also, oil-field machinery is very bulky and the prevailing lack of bottoms makes the transport of the indicated equipment a major problem. But little progress was similarly made in other branches of the Soviet oil industry. NO new major pipe-line construction work was undertaken, consequently the railroads continued to be overburdened with traffic that could be much more effectively handled by pipe lines. No new refinery construction of any magnitude was initiated, though several plants that had been in course of construction for several years were completed during 1940 and operation 554

Jan 1, 1941

By D. W. Fuerstenau

MEASUREMENT of zeta potentials is a useful tool to study the surface chemistry of minerals under flotation conditions.1,2 Because there is continued interest in this approach, the apparatus for obtaining zeta potentials of nonconducting solids by the streaming potential method is outlined here. Fig. 1 illustrates the streaming potential apparatus." The streaming potential cell or plug consists of two 24/40 standard ground joints (4) joined with a piece of pyrex tubing 60 mm long and 12 mm in diam (5). The electrodes are made of bright platinum disks 19 mm in diam and 1 mm thick through which 0.5-mm holes have been drilled (6). To the surface of each is welded a piece of 80-mesh platinum gauze. Each electrode is permanently mounted on the ends of the inner parts of the two standard joints by means of a platinum wire (7) which connects it to the tungsten seal at the end of the cell (8). For ease in cleaning and handling the apparatus, the streaming cell is fastened to the 500-ml reservoir flasks (1) by means of two 18/9 ball and socket joints (2). This particular arrangement permits passage of the solution in either direction through the plug of particles. Flow of solution can be stopped by a stopcock (3). One of the reservoir flasks has a large opening to permit insertion of either a thermometer or a pair of electrodes for measuring pH of solutions within the system. In making the experiments, the plug is filled with 48 to 65-mesh particles, but a layer of 28 to 35-mesh particles is placed at each electrode to prevent any of the finer particles from passing through holes in the electrodes. The assembled apparatus is shown schematically in Fig. 2. To eliminate CO2 from the solutions, all experiments are conducted in a nitrogen atmosphere. Nitrogen, used to drive solutions through the plug, is passed through a bottle of concentrated KOH solution to remove CO2 (9). A 9-liter ballast reservoir (10) is used to maintain a more nearly uniform pressure. A series of stopcocks controls the direction of flow nitrogen to the flasks (11). Tubes of as-carite prevent backflow of CO2 into the system (12). Driving pressure, which can be set at any desired value, is measured with either a water manometer (13) or a mercury manometer (14). Reservoir flasks have side arms for making pressure corrections for the difference in water levels in the flasks. Streaming potentials are measured by the circuit illustrated in Fig. 2. The electrodes from the plug are connected through mercury wells (15) to a reversing switch (16), which reverses the polarity of the electrodes depending on the direction of flow of solution through the plug. The streaming potential is measured with a Leeds and Northrup type K2 potentiometer (17). Proper choice of null instrument is important because Eq. 1 assumes that the current which escapes through the measuring instruments is negligible. An ordinary galvanometer cannot be used to determine the null point because

Jan 1, 1957

By Harvey Cline, Donald P. Ferriss

THE violent outgassing of commercial tungsten and other refractory metals when melted in an electron beam zone refining apparatus1"3 is dealt with experimentally by one or both of two approaches. One is to provide a suitable emission current control1,2 the other is to purify the metal in the solid state before melting.4 The first of these is usually sufficient, but the authors chose also to investigate the source of the troublesome gases and to devise means of solid-state purification. Some further insights into the use of tungsten as a structural material at temperatures near its melting point were also revealed in the course of the work. One may speculate on the causes of gas formation in tungsten at high temperature by inferences from the literature and an examination of the impurities in commercial wire. Davenport5 observed microporosity in both tungsten and molybdenum filaments heated to several hundred degrees below their melting points. Studying the function of oxygen in molybdenum welds, Perry, Spacil, and wulff8 attributed similar porosity to the disproportionation of Moo2 to molybdenum metal and Moo3. Tungsten dioxide also disproportionates7 above 2000oC to yield WO3 vapor at considerable pressure. Commercial tungsten contains some 5 to 20 wt ppm O and a similar concentration of carbon depending on the details and precautions of processing. Therefore, evolution of CO is also a strong possibility as a source of gas at high temperatures. Furthermore, even for activities in the order of 0.01, it may be calculated that the pressure of CO at 3000°C would be over 4000 psi, which is in excess of the tensile strength of tungsten at this temperature.9,10 Powder metallurgy tungsten contains some 0.02 pet Fe and 0.002 to 0.005 pet of the elements Ni, Si, Al, Ca, Mn, Mg, and Mo; at temperatures over 2800°c, therefore, these elements will exhibit appreciable vapor pressure, though small compared to that of WO3 and CO. Some of these impurities may react to form high-pressure monoxides such as SiO and A10. Finally, dissolved and occluded nitrogen is an ever-present source of high-pressure gas. Commercial Type 218, General Electric filament wires, 0.025 in. diam, were heated by resistance in 10 -4 mm of Hg and in argon or hydrogen at pressures from 50 µ to atmospheric. For temperature determinations in vacuo, the Jones - Langmuir8 current-temperature relationship was employed. For gaseous atmospheres, the burn-out temperature was assumed to be the same as in vacuo so that a small, constant correction could be made for temperatures below burn-out conditions (i.e., local heating to failure). Several dozen experiments may be summarized by pointing out some structural observations. At 3050oC in 1 atm of A, porosity is very evident after 30 min, as shown in Fig. 1. For the section in Fig. 2, failure occurred 200°C below the melting point and many voids have grown in the grain bound-

Jan 1, 1962

By R. R. Webster, H. T. Clark

The side-blown converter has been investigated as a possible commercial process for the production of low nitrogen steel. During this work, two converters of 3-ton and 22-ton capacity were operated on a pilot plant basis for a total of 214 heats. The steel made in these converters was low in nitrogen and possessed good cold working properties. Some problems of converter operation remain to be solved. IN plants operating with a high iron capacity, sev-eral different refining methods are used in the conversion of the molten pig iron to steel. These include various ore practices in stationary and tilting open-hearths, the duplex process employing the Bessemer converter and open-hearth, and the Bessemer process. At J&L, a considerable part of the iron produced is handled by the Bessemer process, either alone or in conjunction with duplexing, and therefore an appreciable portion of the steelmaking research effort has centered about the method. This paper covers research work on the development of the side-blow converter for the commercial production of low nitrogen ingots and includes descriptions of the operation of a 3-ton and a 22-ton experimental converter at the Aliquippa Works. The refining of iron to produce steel requires the removal of a large portion of the carbon and silicon and the control of manganese, phosphorus and sulphur which are present in the iron in varying amounts. The first large-scale means of refining iron was the acid Bessemer process which was brought into use almost 100 yr ago. This method, using compressed air as the refining medium, accomplishes substantially complete removal of carbon, manganese and silicon. Phosphorus and sulphur are not affected but, by choice of an iron composition sufficiently low in these elements, a commercial product can be produced. Since the process will handle large tonnages rapidly, operates without external fuel and with a minimum of additional equipment, it quickly became the major tool in the early expansion of the steel industry. Later, the basic open-hearth process, by affording control of phosphorus and sulphur and by consuming the large quantities of steel scrap that were becoming available, forced the acid Bessemer process into a secondary position in the industry. During the past two decades the demand for steel to be used in cold forming and drawing operations has gradually increased. Bessemer steel, because of its work hardening and aging characteristics, is not as suitable for these applications as basic open-hearth steel, consequently the decline of the process was accelerated. More recently, because of changing economic conditions, this long range trend appears to have been arrested or perhaps reversed. Ingot production data for recent years furnishes only an incomplete picture of the importance of the converter in the American steel industry; open-hearth furnaces utilize large tonnages of blown metal for which no published statistics are available. Metallurgical Aspects The fundamental difference between Bessemer and open-hearth steels apparently lies not in the method of manufacture but, rather, in the differences in chemical composition of the two steels. It is further believed that the principal features distinguishing Bessemer from open-hearth steel are the higher nitrogen and phosphorus contents of the former. Evidence supporting this position is supplied by tests on laboratory induction furnace heats that were made to contain varying amounts of phosphorus and nitrogen but were otherwise similar to normal low carbon silicon-killed steels. Fig. 1, 2 and 3, summarizing the test results, are taken from G. H. Enzian's paper titled, "Some Effects of Phosphorus and Nitrogen on the Properties of Low Carbon Steels."' Fig. l indicates that phosphorus has a marked effect on the cold work embrittlement of steel as shown by the work brittleness test of Graham and Work.' In the low nitrogen steels, which as a group have the better cold working properties, the effect of phosphorus variations is the more pronounced.

Jan 1, 1951

By M. T. Hepworth, A. K. Stewart

Iron containing 0.1 pct A1 and -0.9 pct P by weight was internally oxidized in the temperature range 900° to 1300° C, where the bcc structure is stabilized by phosphorous. By measuring the depth of penetration of oxygen with time in an internally oxidized zone for an imposed surface oxygen potential, oxygen permeability was determined. The dgfusion coefficient of oxygen in iron was then calculated using known solubility data, yielding the expression: where Do is the diffusion coefficient of oxygen in bcc iron in sq cm per sec and T is temperature in OK. RECENTLY Hepworth, Smith, and Turkdoganl measured the diffusivity of oxygen in bcc iron and reported the temperature dependence of diffusivity from data determined in the a, and 6 temperature ranges. Subsequently Swisher and Turkdogan' have measured the diffusivity of oxygen in fcc iron. Internal oxidation techniques were employed by these investigators and in this current study. The analysis of this technique is developed by wagner3 (presented in English by Hauffe4 and Rapp 5). In this present study bcc iron stabilized by phosphorous was used to determine oxygen diffusivity in the temperature range 900° to 1300°C. Meijerin 6 has studied oxygen permeability in this temperature range using bcc iron stabilized with 5 pct Sn. Other inves- tigators who have studied oxygen permeability in bcc iron at other temperatures are Schenck et al., 7 Bohen-kamp and Engell, 8 and Bradford. EXPERIMENTAL Electrolytic iron of 99.99 pct purity was alloyed to contain 0.897 pct P and 0.093 pct Al. The maximum weight percent phosphorous required to stabilize bcc iron between 910" and 1392°C is 0.51 pct as determined by Haughton,10 0.42 pct by Roquet and jegaden," and 0.58 pct by vogel,12 with the latter value preferred by Hansen.13 Microprobe analysis indicated that there was no segregation of the phosphorous either before or after permeability studies; therefore, the quantity of phosphorous added was assumed to be sufficient to stabilize the bcc structure. Furthermore, the permeability results of studies on this alloy agreed substantially with interpolated values from previous data on bcc iron.' An ingot of the Fe-P-A1 alloy was hot-rolled to a l-in.-thick slab. Specimens were machined to dimensions: 13/8 by $ by 1/4 in. The experimental apparatus and procedure used have been described before.' A constant oxygen potential was established by passing argon and hydrogen through a column of oxalic acid dihydrate, which has a water vapor pressure which is well-known as a function of temperature. Slab specimens were exposed to a gas mixture sufficiently lean in oxygen to prevent the formation of a surface oxide for predetermined temperature for selected times. The specimens were then quenched, sectioned, and examined metallo-graphically. All quenched specimens were iron-plated to provide protection from the outside sample edge during polishing. Fig. 1 shows a typical microstruc-ture for a specimen oxidized at 953°C for 48.00 hr at a water vapor-to-hydrogen pressure ratio of 0.20. DISCUSSION AND RESULTS The following equation was derived by Hepworth et al.' from Wagner's kinetic expressions for internal oxidation:

Jan 1, 1969

By Paul Gordon

The distribution coefficient, k, of interest in zone refining is generally defined as the ratio of the solid to the liquid solubilities of one element in another at the normal melting point of the solvent. In practice, distribution coefficients are frequently calculated from solubilities at temperatures well below the melting point of the solvent, e.g., at a eutectic temperature. This is done because of the general lack of accurate data on the liquidus and solidus curves in most phase diagrams. The practice is equivalent to assuming that the liquidus and solidus curves are straight lines in the temperature range between the melting point of the solvent and the temperature at which data for the solubilities are known. It is recognized that the k values so derived may be in serious error; we have found evidence in recent zone-refining operations that a case in point is silicon in aluminum. The phase diagram found in the literature for silicon in aluminum indicates a eutectic on the aluminum-rich side at 12.5 at. pct Si and at 577°C,1 and a solid solubility of silicon in aluminum at this temperature of 1.59 pct.2 It also shows the liquidus and solidus as nearly straight lines from 577°C to the melting point of aluminum (660°C)1,2 The k value obtained from this data is 0.13. This is almost exactly the same as the k value (about 0.14)' obtained in a similar way for copper in aluminum. Yet we have found by mass-spectrograph analyses* of three bars of zone-refined aluminum that copper is efficiently removed from aluminum by zone refining but silicon is not. Two of the three bars of aluminum were zone-refined in our laboratories, the other in the laboratories of AIAG Metals, Inc. The former two bars, designated bars PG2 and PG3, were 30 in. long by 1 in. in diameter during refining; each was processed in a high-purity graphite boat* and kept under refining stage of the process consisted of thirty unidirectional zone traverses at rates of about 1 to 2 in. per hr, with a zone length of 1 to 2 in. At approximately the middle of the refining period a 6-in. piece of the impurity-laden finishing end of the bar* was cut off and replaced with new start- ing material. Following refining, the purest 20-in. section of the bar (obtained by discarding approximately 2 in. of the starting end and 8 in. of the finishing end of the bar) was leveled and then analyzed. The AIAG bar was 16 in. long and about 1.2 in. in diameter; it was purified by eight passes of a 2-in. zone at a rate of 1.6 in. per hr, the bar being contained in a sintered alumina boat lined with loose alumina powder of the highest purity. Data for the silicon and copper contents of the three refined bars are given in Table I. Derived data for the efficiencies of the zone-refining operations are listed in Table 11. It is clear from these two tables that the copper is removed much more efficiently—by a factor of 10 to 50 times—from aluminum during zone refining than is silicon. For example, in bar PG3 the thirty zone passes reduced the copper content from 10 to 0.02 ppm, i.e., by 500 times, whereas the same treatment lowered the silicon content by only a factor of about 16. It seem virtually certain, therefore, that the distribution co efficient, k, for silicon in aluminum is well above that for copper and is very likely not much below unity. This also implies that the solidus line on the aluminum-rich side of the A1-Si phase diagram is very probably appreciably curved near the aluminum melting point since the phase-diagram data indicate such curvature is unlikely in the liquidus.

Jan 1, 1965