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By D. F. Atkins, B. A. Rogers

The constitutional diagram presented herein is relatively simple. Complete mutual solid solubility exists for an interval below the solidus line, a continuous curve with a flat minimum near 22 pct Cb and 1740°C. Upon cooling, the solid solution breaks up, except at the columbium-rich side, from two causes: zirconium-rich alloys transform under the influence of the ß-a transformation in zirconium; alloys of intermediate composition decompose into two solid solutions below 1000°C. The combined effect is the formation of a eutectoid at a temperature of 610°C and a composition of 17.5 pct Cb. The eutectoid horizontal extends from 6.5 to 87.0 pct Cb. Some age hardening effects have been observed in the zirconium-rich alloys but the positions of the solvus lines remain uncertain. IN recent years, zirconium has been produced in much larger quantities than were available previously. Correspondingly, the incentive for studying its alloy systems has increased, as the number of recent publications on alloy systems testifies. However, only a partial diagram of the Zr-Cb system has been published and relatively few references have been made to alloys of the two metals. Hodge' investigated the Zr-Cb system up to about 25 pct Cb. His data on melting points were not sufficiently numerous to distinguish with certainty between the alternatives of a narrow eutec-tic horizontal and a wide flat minimum in the solidus curve. Although Hodge considered his results on transformations in the solid state to be only tentative, he suggested that the eutectoid in the zirconium-rich alloys lay at about 625 °C and 10 pct Cb and estimated that the solubility of colum-bium in zirconium at 625 °C was near 6 pct. According to Simcoe and Mudge,2 less than 0.5 pct Cb is soluble in zirconium at 800°C. These authors observed an increased strength in both the 0.5 and I pct Cb alloys made with hafnium-containing zirconium. According to Keeler,3 the strength of zirconium is increased by addition of columbium to a content of at least 3 pct. Keeler' also observed a maximum in hardness at about 10 atomic pct Cb and commented on the brittleness of alloys of this composition. Anderson, Hayes, Rober-son, and Kroll5 investigated the tensile properties of Zr-Cb alloys containing 5.1 and 12.9 pct Cb at room temperature and at 343°C. The 12.9 pct alloy had a high tensile strength at room temperature but also a low percentage of elongation. All alloys had high elongation at 343 °C. Littona measured strength and elongation values of annealed alloys containing up to 27.5 pct Cb and found low elongation values for all of the alloys of high columbium content. Some observations on the resistance of Zr-Cb alloys to corrosion in water at high temperature have been published by Lustman, De Paul, Glatter, and Thomas' who found that additions of columbium up to 1 pct had only a minor effect on the corrosion resistance of zirconium. Preparation of the Alloys Raw Material: Zirconium of a relatively good grade was available for making the alloys. It was obtained as scrap pieces that had been left over from an operation that included production by the iodide process, melting under a protecting atmosphere, and fabrication to plates. The individual pieces had hardness values of 24 to 32 Ra and a typical analysis is shown in Table I. The columbium also was scrap trimmed from sheets. It was furnished by the Fansteel Metallurgical Corp. and had a high ductility but its analysis was known only approximately. The metal probably contained about 0.5 pct Ta, perhaps 0.25 pct C, and a few hundredths percent each of iron, silicon, and titanium. Melting: The alloys were melted in a tungsten-electrode copper-crucible arc furnace similar to units that have been described recently in the metallurgical journals.'.' The crucible of this furnace is provided with a cavity in which a getter charge can be melted before the melting of the alloy charges. Hardness measurements on the ingots indicate that the getter charge takes up a considerable fraction of the oxygen and nitrogen from the helium atmosphere of the furnace. The alloys used in the investigation are given with their intended compositions, hardness, and melting points in Table 11. Fabrication: All alloys of the Zr-Cb system appear to be amenable to fabrication. At least, all of the compositions listed in Table II could be reduced to wires in a rotary swaging machine. The starting material was either slabs cut from ingots and ground by hand to rough cylinders or narrow strips trimmed from sheets made by cold rolling slabs. However, not all of the alloys could be fabricated satisfactorily by the same method. From 0 to 4 pct Cb and from 20 to 30 pct Cb or more, the alloys could be swaged cold from ¼ in. cylinders to 0.80 mm wires with only one intermediate annealing, sometimes with none. From 40 to 90 pct Cb, the alloys were difficult to swage either hot or cold but could

Jan 1, 1956

By O. R. Wagner, R. O. Leach

Immiscible displacement tests were performed in a consolidated sandstone core over the interfacial tension range from less thdn 0.01 to 5 dynes/cm to better define how interfacial tension (IFTJ reduction can lead to increased oil recovery. Data obtained were displacement efficiency at breakthbrough vs IFT for both drainage and imbibition conditions. These tests simulate water flooding under oil-wet and water-wet conditions, respectively. Results of the study have shown that displacement efficiency under both oil-wet and water-wet conditions can be markedly improved by a sufficient reduction in IFT. In the particular porous media used and for the low pressure gradients employed, the IFT must be reduced to a value less than about 0.07 dynes/cm to achieve increased recovery at the time of breakthrough of the injected phase. Below 0.07 dynes /cm, further small reductions in IFT result in large increases in displacement efficiency. Observed increases in recovery were obtained at pressure gradients which are well below those which can exist in the interwell area of a reservoir under water flood. The effect of pressure gradient on recovery is discussed. INTRODUCTION A residual oil saturation remains in rock which has been water flooded because, under usual reservoir conditions, the driving force which can be generated is inadequate to expel oil trapped by capillary forces. Since these capillary forces can be reduced by reducing the IFT a frequently studied method of increasing oil recovery has been the use of surfactants to reduce the water-oil interfacial tension. Mungan l observed improved recovery in both water-wet and oil-wet systems at 1.1 dyne /cm IFT, finding that the amount of improvement was greater in oil-wet systems. Moore and Blum,2 working with visual flow cell micro-models, con- cluded that recovery cannot be improved in water-wet systems by injecting surfactant solutions. They calculated that, for a pressure gadient of 1 psi/ft in their model, the IFT must be reduced to 0.03 dynes/cm to release oil trapped under water-wet conditions. Berkeley et al.3 indicated that, at representative field flooding rates, the IFT must be reduced to 0.001 dyne/cm to improve recovery, Thus, there is a wide variation of opinion about the IFT levels needed to improve recovery under field conditions. These previous investigators all have used as their experimental method the addition of surfactants to the injected water. The use of surfactant solutions to reduce IFT creates two experimental problems: (1) the loss of surfactant through adsorption on reservoir rock can obscure the true IFT value which exists at the displacement front, and (2) at very low values of IFT emulsifica-tion of oil and water commonly occurs. It is difficult, therefore, to determine whether the increased recovery is caused by IFT reduction as such, or is instead caused by emulsification. Also the properties of the available surfactants limit the IFT range which can be studied. In the present study the purpose is to better define how interfacial tension reduction can lead to increased oil recovery. A matter of great interest is the amount of recovery improvement potentially achievable in this way. The study was made using very low pressure gradients which was well within the range achievable by water flooding in the interwell region of petroleum reservoirs. A unique experimental approach was chosen to avoid adsorption and emulsification problems, and to allow convenient control of IFT. The fluid phases used were the equilibrium vapor and liquid phases of the methane-n-pentane system. The interfacial tension level was varied by changing the equilibrium pressure of the methane-pentane system over the range from 1,200 psia to near the critical pressure (2,420 psia). All tests were performed at a controlled temperature of 100F. The IFT-vs-pressure relationship for the methane-pentane system was based on the data of Stegemeier and Hough,6 and on new data obtained in this study. With this experimental approach it has been possible to study displacement at lower values of IFT than have been previously investigated.

Jan 1, 1967

By J. R. Long, A. H. Roberson, T. R. Graham, R. S. Dean

Experimental work on the properties of high-purity alloys of the copper-man-ganese-zinc system has necessarily required extensive metallographic work to determine the equilibrium conditions in this system. Previous work on these alloys is fragmentary and, unfortunately, based on alloys made with impure grades of manganese, thus introducing significant amounts of iron, silicon, aluminum and carbon. Since these elements are known to affect equilibrium conditions, it became desirable to re-examine these alloys made from the pure metals. The alpha solid solution field was of particular interest and, therefore, was chosen for the initial work, which was outlined to determine the composition limits of this field. Previous Work Heuslerl conducted an extensive survey of the liquid-solid regions of this system and also made an estimate of the solid-phase boundaries at 340°C. The pertinent part of his diagram is given in Fig. I, but it is of limited usefulness, since it applied to a single temperature only and is based on impure alloys under admittedly nonequilib- rium conditions. Bauer and Hansen,2 likewise working with impure alloys, have determined the phase boundaries for alpha-beta brasses containing small amounts of manganese and indicate an increase in the extent of the alpha field with increasing manganese. This is not in accordance with Heusler or with data obtained on pure alloys.3 They also described a third constituent precipitating in the alpha plus beta field below 350' to 400°C. but did not identify this constituent. Guillet4 and Heike and Ledibur6 have also noted this precipitate. Each of these investigators recognized that impurities present in the manganese could and did have an effect on the structure and properties of their alloys. Corson6 in particular pointed out the hardening effects of silicon, aluminum, and carbon in copper-manganese alloys and Heusler reported that his alloys containing more than 25 per cent manganese were extremely brittle. In all probability this brittleness was due to the impurities present. This early work, therefore, should be taken as a general guide for preliminary studies only, and high-purity alloys may be expected to produce different results. The work of the Bureau of Mines laboratories with electrolytic manganese has been briefly summarized by Dean7 but includes only a short section on this system. Later work3 outlined a limited portion of the alpha field in the neighborhood of 65 per cent copper, 10 per cent manganese, and 25 per cent zinc. The present work was under-

Jan 1, 1945

By A. S. Odeh

This paper analyzes the effect of limited entry to flow at the wellbore on the steady-state productivity of a well. Wells that have been opened to flow along a fraction of their productive interval are termed wells with limited entry. Previous work treated the cases of a partially penetrating well, a well producing from the central portion of the productive interval and a well in which several intervals equally spaced were open to flow. In this paper the open interval can be located anywhere within the productive interval. Thus, in a sense, it generalizes previous work. The finite cosine transform was used to arrive at a solution for steady-state flow of a slightly compressible fluid. The solution was programmed for a CDC 1604 computer. Numerical vaIues for rd = 660 ft, r, = 1/4 ft, and range of sand thickness of 20 to 200 ft are presented in graphical form. The effect of rd and r, values on the result is shown in a table. The correct calculation of skin and damage ratio in the presence of limited entry to flow is explained and illustrated by examples. Moreover, the paper shows how to calculate the net decrease in productivity due to the combined effect of limited entry and perforations. INTRODUCTION In some wells only a fraction of the productive interval is open to flow. Location of this fraction is usually dictated by formation characteristics and reservoir behavior. For instance, if a gas cap exists, the open interval is located away from the gas-oil contact to prevent any possible gas coning. Wells that intentionally have been opened to flow along a fraction of their productive formation are tened wells with limited entry. Obviously, unintentional completions of this type also exist. Limited entry to flow decreases well productivity. Magnitude of the loss depends on the fraction of the formation open to flow, on the thickness of the sand, on the location of the open interval and on the ratio of rd /r, where r , is well radius and rd is the drainage radius of the well. The use of pressure buildup data on producing wells to calculate the condition of the formation around the wellbore is an accepted practice. van Everdingenl and Hurst2 introduced the concept of she skin factor s considered to be due to a thin layer of different permeability immediately around the wellbore. These authors dealt with the case of a well of complete radial geometry, i.e., a well with open-hole completion that completely penetrates the formation. The presence of a low-permeability skin results in a loss of productivity, as does limited entry. Therefore, if pressure buildup data obtained on a well with limited entry are used to establish the presence or absence of skin (i.e., formation damage), and a correction is not made for this loss of productivity, the calculations would result in an erroneous skin value. They might indicate the presence of formation damage when in reality there is none, or they might indicate a value larger than the true value. This could lead to an incorrect basis for planning remedial measures. Muskat3 studied the problem of partially penetrating wells for the case of incompressible flow. He presented equations and figures which allow estimation of loss in productivity. Brons and Marting,4 using equations based on Nisle's work,5 studied the loss of productivity for three cases. The first was for a partially penetrating well; the second was for a well producing from only the central portion of a productive interval; and the third was for a well in which several intervals equally spaced were open to flow. Their work was for steady-state depletion-type reservoirs wherein the well radius of drainage is established and the fluid is considered to be slightly compressible. Considered in this paper is the problem of wells with limited entry in which the open intervals are located anywhere within the productive sand. The finite cosine transform is used to arrive at a

Jan 1, 1969

RUSSIA was the United States Number One source of manganese ore in 1948 when 34 pet of imports were received from that source, stated Norwood B. Melcher, assistant chief, ferrous metals and alloys branch, Bureau of Mines. In 1949, this country received only 20 pet of 1948 shipments from Russia, and only token amounts are now being received. Aggressive programming by industry and government resulted in prompt increases in shipments from major, producing sources; India, Gold Coast, and the Union of South Africa all increased exports to fill the vacuum left by Russia and provided an excess adequate to increase total imports approximately 290,000 short tons in 1949. Again in 1950, and with, even less ore from Russia, imports increased another 290,000 short tons. Since the shift from Russia as a source of manganese, the United States has received in total about 85 pet of its imports from India, Union of South Africa, Gold Coast, and Brazil in that order of importance. Producers of both home consumed and merchant ferromanganese have been able to adjust downward the manganese content of the home-consumed product and so obtain partial relief. Millions of tons of steel were produced in 1951 with a relatively low grade ferromanganese. This adjustment has been made without decreasing the quality of the steel, although with some increase in cost through introduction of new problems, including increased hand- . ding of material and additional removal of carbon. Forced into a pattern of price and grade structure such as exists today, the producer of ferromanganese must adopt one of three possible courses as a short-range program: 1-He may continue to deplete his stocks by producing standard (78 pet) ferromanganese and hope that the future will bring some form of relief; 2-he may attempt to produce 78 pet ferromanganese by paying higher prices for premium ores; or 3-he may drop the grade of ferromanganese and stretch stocks and future supplies of ore as far as possible. The present rundown condition of Indian railroads is attributed to the fact that the service has had no opportunity to recuperate since the beginning of World War II, while the demand for the movement of commodities has probably increased. The Union of South Africa has expanded its exports to the United States greatly since 1948, but, the showing of that country in 1951 was disappointing. Efforts have been made for some time by firms in the United States, at the urging of the manganese miners in the Union, to prevail on the railroad authority to grant and make available larger allocations of cars for manganese ore movement. As a whole, such efforts have been unsuccessful. Although the allocation of rail shipping has been the obvious factor in the decreased movement of ore, many other less determinate factors appear to be involved. Brazil, long an important supplier of manganese to the United States, has important manganese deposits in three areas, all of which are significant to this country. The Gold Coast is an important source of supply. Its metallurgical ore is particularly of significance because of its unusually high grade which permits considerable latitude in blending with the lower grade materials of South Africa and India. The Belgian Congo should have an output of 100,000 tons or more annually beginning this year. R. S. Dean presented two papers. One with K. M. Leute on hydrometallurgical methods for recovery of manganese from domestic ores and one as sole author on the so-called carbamate or Dean process. The two papers tied into each other. In the first mentioned he reviewed the various processes applicable to oxidized, and nonoxidized and reduced ores. The advantages of each .were pointed out. So far the only process tried on a substantial scale on oxidized ores was the SO2 process used at Las Vegas, Nev., on Three Kids ore during World War II. Many problems were encountered. Some of them were whipped while some of those remaining perhaps would have been whipped had time permitted. Since then work has been done elsewhere to avoid the formation of the troublesome thionates encountered at the Three Kids plant. Dean discussed the thionate and NO, processes as applied to oxidized ores. The only commercially used process on reduced ores is that of making electrolytic manganese. Among others that have been considered are the nitric acid process, the Bradley-Fitch ammonium sulphate process, and Dean's ammonium carbamate process. Dean's thesis was that extremely large tonnages of so-called low grade manganese ores are available, and that these should not be depleted in attempting to simulate a foreign metallurgical grade ore. He pointed out that the grade of the domestic manganese ores would be considered high if the same grade were found in copper ores. The selling price of electrolytic manganese and electrolytic copper are roughly the same. In addition to electrolytic manganese, he believes that domestic ores should be used to make exceptionally high grade products. These might be battery grade oxide or substantially pure oxide sinter, which might be used for high manganese alloys or for upgrading metallurgical grade manganese to produce a high manganese ferroalloy. The carbamate process is based on the fact that manganous oxide is readily soluble in concentrated ammonia solutions containing ammonium salts. In solutions of sufficiently high concentration the manganese exists as an anion. Lixiviants of ammonia and ammonium carbonate permit extraction of the manganese from reduced ores and the manganese can be recovered as carbonate by heating or by driving off ammonia. R. V. Lundquist presented a paper on upgrading high-silica ores or concentrates with sodium hydroxide to extract silica and to yield a product with a more favorable manganese: silica ratio. The NaOH is, regenerated in part by CaO.

Jan 1, 1952

By M. Metzger, T. A. Read

The strengthening effects of hydroxide and synthetic plastic films in the creep of cadmium crystals were studied. The results were broadly consistent with the naive mechanical model. The dislocation-film reactions and the significance of the macroscopic stresses associated with certain films are discussed in the paper. ALTHOUGH a number of studies have been made of the strengthening of metal single crystals produced by surface films usually less than Ir in thickness, the mechanisms underlying this phenomenon are still not well established. Roscoe' first noted the critical shear stress and the stress-strain curve of cadmium-crystal wires to be raised markedly by the presence of oxide films. Subsequent investigators2-' have confirmed the effect for several metals and films including a number of plated poly-crystalline metal films. Harper and Cottrel1" with a thin film on zinc presumed to have formed as a result of etching and washing treatments) did not detect a strengthening at a rate of extension of 10 ' sec-' although at lo-' sec-' the film raised the flow stress by 7 pct at 0.0005 extension and by 22 pct at 0.01. The marked strengthening at moderate strains thus appeared to be the result of a dynamical effect dependent on the rate and amount of plastic flow. Other observations'. " are consistent with this view. The large effects of films on the tensile creep rate of single crystals were demonstrated when the observation of Andrade and Randall," that the creep rate of cadmium crystals increased on immersion in aaueous solutions of certain cadmium salts. was shown' * to hold only when a film was present initially and was explained by the attack of the solution on the film and the removal of its strengthening effect. Changes in the creep rate interpretable in terms of the removal or formation of various films have been observed by other investigators.3,8,10,31 Certain other experiments have been reported in which surface films or liquid environments have affected the plastic behavior of metals, but these are not within the scope of the present work which deals with the effect of solid films on single-crystal slip. Possible Mechanisms—The film does not significantly reduce the load on the crystal in the elastic range (the elastic moduli of film and crystal are not too greatly different and the area of the film is so small that its share of the load is negligible) so that the initial operation of internal Frank-Read sources is not affected. However, as Fisher" has pointed out, a source terminating on the crystal surface requires only half the critical stress for activation as an internal source of the same length and a relatively strong film (even a very thin one) would pin the free ends of the surface sources so that, if surface sources are responsible for plastic flow in a clean crystal. such a film would increase by roughly a factor of 2 the stress necessary for generation of dislocation loops at a given rate. The other general possibility is that the film resists the passage to the crystal surface of internally generated dislocations. If the film is adherent and if the specimen is to exhibit slip of the same general character as a film-free specimen, the film must deform or fail in shear at the active slip planes. The naive mechanical model, where shear-stress relaxation across the active slip plane in the metal transfers load to the film until it deforms and slip can

Jan 1, 1959

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky's approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky's paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By E. DeGolyer

WAR has wrought sharp and sudden changes in the pattern of the oil industry. The most obvious and most striking of such changes have been in the fields of transportation and refining. A third of the world's total oil production formerly started to market, tanker-borne, over the waters of the Gulf and Caribbean. Most of this oil went to our North Atlantic ports, supply points for the world's greatest consuming center. This tremendous traffic, disrupted by the loss of tankers as a result of requisition for military purposes and by the activity of enemy submarines, has had to be substituted largely by such lines of supply as could be improvised without loss of too much time. No single solution for this gigantic problem has been found nor is it likely to be entirely solved for some time to come. It has been solved in part, however, by rearrangement, reversals, and patching up of existing pipe-line systems; by overland transport of crude and products in tank cars on a scale never before attempted; by barging over inland waterways; and through the construction at long last of the "big-inch" line, the first leg of which is just being put into operation as far as Norris City, III. The tank-car traffic alone, reaching a peak of deliveries of 856,710 barrels per day into District 1 during the week ending Sept. 19, 1942, and accomplished at an expense of millions of dollars in extraordinary transportation costs, defrayed by the Defense Supply Corp. and by the mobilization of tank cars from all over the nation, is a story worth the telling but by some of those who directed it.

Jan 1, 1943

By M. C. Flemings, F. R. Mollard

Two-phase Pb-Sn alloys, ranging in compositiotz from 12 to 26 at. pct Pb, were unidirectionally solidified in a convection-fvee system, with thermal gradients in the liquid of up to 480°C per cm. Plane front solidification Loas achieved in all alloys at sufficiently steep gradient and slow growth rate. Conditions causing breakdown of the interface to a cellular or dendritic structure were roughly as predicted by a sinlple constitutional supercooling criterion. Structures of alloys of near-eutectic composition, solidified with plane front, exhibited a lamellar structure; the alloys furthest from the eutectic exhibited a rod-like morphology. Assumptions used in a previous paper for calculations of solute redistribution in two-phase plane front growth are shown to be reasonable for Pb-Sn alloys. Results of calculations are in good agveement with experiment. These show that variations in growth rate during solidification of the composite produce marked changes in average composition of the solid. IN a previous paper, Part I,' conditions necessary for plane front solidification of two-phase alloys were discussed and calculations given on solute redistribution in this type of solidification. This paper, Part 11, describes experiments on Pb-Sn alloys, designed to check the assumptions of the analyses presented, and to demonstrate their applicability to a given alloy system (Pb-Sn). APPARATUS AND PROCEDURE General. A vertical crystal growing unit was built for the study as described below, and "normal solidification" employed throughout (i.e., the ingot was completely melted except for a portion near the bottom end and then solidification initiated). The furnace was designed to permit achieving very low interface velocities, and steep gradients, in essential absence of convection; it is sketched in Figs. 1 and 2. Simple heat flow considerations indicated choice of a small-diameter specimen (ingot) to achieve high thermal gradients; ingot size chosen was 0.3 cm in diam. The ingots were held inside silica tubes 0.06 cm wall thickness. The requirement for an essentially convection-free system was met by use of the vertical furnace with the heat source over the heat sink, as well as by use of the small diameter ingots. In addition, by selection of tin-rich Pb-Sn alloys, the diffusion boundary layer (lead-rich) was denser than the bulk liquid and would not cause convection. The only apparent driving force for convection in this system was the small transverse temperature gradient resulting from heat flow into the samples from the furnace. Such convection must have been small, however, since 1) no temperature fluctuations in the melt were noted in the recordings, which would have indicated turbulent convection, and 2) experimental results obtained and described below could not have been achieved in presence of significant convection. Ingot Preparation. Pb-Sn alloys ranging from 12 to 26 at. pct Pb were prepared from high-purity lead and tin (99.9999 pct pure metal). Each alloy was prepared by first melting the pure metals in the proper ratio in air, in a Pyrex container. The melt was then stirred thoroughly with a graphite rod and cast into a preheated graphite mold. Ingots were then prepared from these castings for use in the actual experiments; each ingot consisted of a rod of alloy, 15 cm long in a 25-cm-long transparent fused-silica tube, 0.3 cm ID and 0.06 cm wall thickness. One chromel-alumel thermocouple, made with 0.004-in.-diam wire and protected by a two-hole alumina tube, was inserted into each ingot. The 1.5 cm of the thermocouple nearest the bead were protruding from the alumina tube and were coated with a very thin layer of boron nitride paste which provided electrical insulation while allowing good heat conduction. The electrically welded junction size was about that of each wire and the cross section of the two wires represented about 0.3 pct of the sample cross section. Including the coating, the thermocouple cross section still represented less than 0.5 pct of the ingot cross

Jan 1, 1968

By M. Semchyshen, A. P. Coldren, W. G. Scholz

A survey of the Fe-Mo-B system was made to determine the extent to which boron might affect the microstructure and strength properties of iron-rich Fe-Mo alloys. Seventeen vacuum-induc tion melted ingots were prepared with approximate mo-lybednum contents 01 2, 4, 9, and 19 wt pct and approximate boron contents of 5, 14,50, and 630 ppm by weight. Phases extracted from annealed specimens and identified by X-ray diffraction analysis included E Fe3MO2, Mo2FeB2, and an oxide hazling a diffraction pattern practically identical to that of MnFez04. Three types of alloy strengthening were observed: a) Fe-2 pct Mo-B alloys were hardenable by a bainitic-type transformtion of austenite to ferrile; b) Fe-4 pct Mo-B alloys were hardened by the solid-solution mechanism; and C) Fe-9 pct Mo-B and Fe-19 pct Mo-B alloys were hardened by precipitation of the E Fe3Moz phase. Boron was observed to have a very strong hardening effect in the Fe-2 pct Mo alloys and a mild strengthening effect on the 1200°F properties of the Fe-4 pct Mo alloys. In the Fe-9 pct Mo alloys there was no consistent effect of boron on strength at either room temperature or 1200° F. The Fe-19 pct Mo alloys were so brittle that meaningful tensile or creep-rupture data could not he obtained. No dispersion hardening from borides was recognized in any of the alloys. THE high-temperature properties of iron-rich Fe-Mo alloys were studied by Reiter and Hibbard.' They found that the strength of the alloys increased markedly as the molybdenum content was raised from 0 to 15.9 pct by weight. The authors explained the various degrees of strengthening in terms of a) solid-solution strengthening, b) strengthening from a martensitic-type transformation, and C) precipitation strengthening. The objective of the present investigation was to conduct a survey of the iron-rich portion of the Fe-Mo-B system to determine whether the beneficial effects of molybdenum on the strength of iron can be enhanced by the presence of boron. It was thought that perhaps fine dispersions of molybdenum- rich borides would be found which could improve the high-temperature strength of ferritic alloys beyond the strengths attainable by molybdenum additions alone. Also, it was considered worthwhile to study the effects of boron in alloys which are essentially free of carbon. Most, if not all, of our present knowledge about boron in high-temperature alloys pertains to alloys containing carbon and carbides. EXPERIMENTAL PROCEDURES Alloy Preparation. Seventeen 8-lb ingots were prepared from electrolytic Plastiron, unalloyed molybdenum chips, and boron powder by a vacuum-induction melting procedure employing hydrogen as the main deoxidizer. The alloys were melted in alumina crucibles using 35-lb melts, with each melt being split four ways to achieve varying boron contents within four Fe-Mo base compositions. The results of chemical analyses conducted on chips machined from the chilled ends of the ingots are presented in Table I. The boron analyses were performed by a spectrographic method utilizing primary standards prepared from boric acid. They indicated that in ingots to which no boron was

Jan 1, 1964

By C. S. Matthews, M. J. F. Rosenbaum

The purpose of thir work wax to lcarn it~lzut infori~lation could he obtained from various typs of pilot water floods and to attempt to find the optunum pilot patter11, for a revervoir which had previously been depleted by a solution gas drive. The study was made in the laboratory with mathemetical methods a dynamic analog and a potentiotnetric analog. Results werp tested against the field llistorics of a nrrnlber of pilot water floods. At a reasonable valrre of currzulative injection, the total production rate for the one-injector five-spot should reach about 6.5 per cent of injection rate, and for a four-injector five-spot, about 9 per cent. Accurate estimates of ultimate recovery cannot be made on the basis of such snzall prorluction rates. However, with a pilot composed of nine ir1jector.s and 16 producers the production rate is approximately 50 pcr cent of injection rate at a reasonable value of camulative injection. Sonle inforn~ation for extended performance predictions might he obtained from such a large pilot. These conclusions were drawn on the basis of results obtained for unit mobility ratio, and a sturly using tlre potentiometric analog was made of the effect of other mobility ratios to determine the range of applicability of these predictions. For the four-injector, five-spot pilot with the ratio of production to injection rate (before water breakthrough) is about twice that for with it is about two-thirds; and with M0= 10, it is about one-third For high mobility ratios, it was found that the production rate increased considerably as water-cut increased. These result can be used to modify, qualitatively, the inter.pretntions based on curves for the unit rnobilit\. ratio CaSeS. It was found that the maximum ratio of production rate to injection rate obseriled in field pilot floods was of rhe scime order as that prerdicted by these methods. The time required to reach thisr maximum did not generally agree with the time predicted for a homogeti~orir reservoir. The differcrlce between predicted and observed time of response gives an indication of the permeability profile and of the condition of the producin,g wells. Pilot water floods of the pattern type are generally carried out in reservoirs which have been depleted by solution gas drive and are at low pressure. Under these conditions, oil and water can be considered incompressible. It is assumed that, as the water is injected, an oil bank forms ahead of it and that there is a distinct interface between the water zone (or bank) and the oil zone (or bank) and between the oil zone and the region ahead of the oil zone. It is further assumed that only gas is mobile in the unflooded (gas) region, only oil is mobile in the oil bank and only water is mobile in the water bank. The saturations and the mobilities associated with each zone are assumed uniform. We idealize our reservoir to be homogeneous, horizontal and of constant thickness. Effects of gravity within the producing layer are assumed negligible. If the actual time-dcpendent flow problem is approximated by a acries of steady-state problems. the potential and stream function in the oil bank and water hank satisfy Laplace&apos;s equation in two dimensions. We can therefore use a poteiitiometric analog of this system. Potentiometric models have yielded uscful results in this laboratory&apos; and clsewhere in the study of a variety of secondary recovery problems. For the case where M = I, we generally prefer to use theoretical mcthods as well as a simpler dynamic analog. Except where otherwise noted, the ratio, side of five-spot/wellbore radius. is taken to be 3,600. a figure which corrcsponds to a normal-size wellbore in a 10-acre well spacing. THEORETICAL EVALUATION OF VARIOUS PILOT PATTERNS, Mw0 = 1 <&apos;he theoretical models which we used to examine the performance of various pilots are shown in Fig. 1. Image theory was used to determine the ratio of production rate to injection rate as a function of the volumc of the flood. The ratio of production rate to injection rate was chosen because this is an easily measurable quantity which is characteristic of a pilot

By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

The effects of aeration on an aqueous suspension of pyrrhotite were studied and their results correlated with flotation tests using xanthates as collectors. The effects of copper activation and of pH variation were determined and possible mechanisms postulated. PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents,3 or by starch.&apos; The object of this work was to study the floatabil-ity of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH. Preparation of the Pyrrhotite Sample: It was desirable that the highest grade of pyrrhotite obtainable be used for this experiment, since the presence of other minerals could affect the surface properties.5 However, no pyrrhotite was available as crystals, and massive deposits of hydrothermal origin commonly contain considerable amounts of chalcopyrite. Pyrrhotite concentrate was, therefore, prepared from a sulphide deposit occurring near Aitkin, Minn. The deposit is of pyrometamorphic nature consistirlg mainly of pyrrhotite and pyrite with graphite, silicates, and carbonates as gangue. The ore, already crushed through 3 mesh when received, was screened at 65 mesh and the undersize discarded. The oversize was crushed through rolls, and then stage-ground dry in an Abbe porcelain mill, the —65 mesh portion being screened out after every 15 min of grinding until all the material passed through this size. The ground product was then concentrated with a drum-type dry magnetic separator. The rougher concentrate was cleaned twice and then demagnetized. The final product was split in a Jones splitter and stored in air-tight bottles. Microscopic examination of the concentrate showed that it was relatively clean and free of pyrite, locked particles, and gangue. By means of the krypton gas adsorption method," the specific surface was determined to be 3000 cm2 per g. The chemical and screen analyses of the final concentrate are given in Tables I and II respectively. It is a well-recognized fact that the oxidation of some sulphide ores during stockpiling, grinding, and conditioning affects their flotation behavior. The problem of oxidation may become serious in the case of pyrrhotite, since this is known to be more easily oxidized than many other sulphides. To ascertain the extent of oxidation, an experiment was carried out by aerating an aqueous suspension of pyrrhotite with air, oxygen, and nitrogen as follows. A 300-g sample of pyrrhotite in 2700 ml of water was agitated and simultaneously aerated in a Fager-gren-type laboratory flotation machine. A Precision wet test meter was connected to the air inlet valve, the flow rate of the gas being kept constant at 0.3 cu ft per min throughout the experiment. Samples of approximately 30 ml each were taken from the cell at 0, 4, 10, 20, 35, 60, and 90 min. After the pH was taken, each sample was filtered and the filtrate was analyzed for total iron and sulphur. The iron was determined colorimetrically by the thioglycolate method using a green filter.&apos; The filtrate was oxidized with bromine to convert all of the soluble sulphur compounds into sulphate and this was determined with a Parr turbidimeter." When aeration tests were made in alkaline circuit, calcium hydroxide or sodium hydroxide was added at regular intervals to maintain a constant pH. A similar procedure was followed in an experiment to determine the abstraction of copper. ion by pyrrhotite. In this case various quantities of cupric chloride were added. The filtrate from each sample taken was analyzed for copper, total iron, and sulphur. The carbamate method with a green filter was used for the copper analysis,&apos; since this method could tolerate a considerable amount of iron in the solution. A pneumatic cell, made from a 350-ml fritted glass Buechner funnel, was used for this experiment. The detail of the assemblage has been described elsewhere." In the present work a stainless steel baffle was inserted in the cell. This baffle overcame the tendency for the coarse pyrrhotite particles to be swirled around the wall of the cell and thus fail to collect in the froth. A 50-g sample of pyrrhotite was added to the cell which contained 260 ml of water. When pretreat-ment of the sample was desired, reagents, such as activator and pH regulator, were then added and the pulp was conditioned for a specified conditioning time. Prior to the addition of the collector approximately 15 ml of the solution were removed for pH measurement and for iron and sulphur analyses. Copper when used as activator was also determined. Collector and frother were then added and the pulp was conditioned for an additional 2 min. Air was admitted to the cell and the froth removed. The separation required from 4 to 6 min, depending on the characteristics of the froth. The float and non-float products were filtered, dried, weighed, and assayed for iron.

Jan 1, 1955

By S. Ramachandran, R. G. Woolery

INTRODUCTION Union Carbide is currently operating an in-situ leach project on the Palangana Dome area in Duval county. This deposit meets all the requirements for in-situ leach in that the ore (1) is below the water table, (2) is in a permeable horizon, (3) is amenable to chemical leaching, and (4) is confined by impervious layers. This project has been under commercial production since 1976, and its capacity has been expanded on three occasions since going on-stream. Recently, additional uranium reserves were discovered on the Rogers-Cardenas (R-C) property about 32 km north of the Palangana operation. The ore is located within the Oakville sands and its characteristics are quite similar to those of the ore at Palangana. Both are an unconsolidated Arkosic sand high in clay and calcium carbonate. The R-C ore, however, is somewhat coarser with a mean particle size of 0.15 mm as compared to a mean particle size of 0.07 mm for the Palangana ore. In all respects it would appear that this ore would be a candidate for in-situ leach as a satellite operation to Palangana. Unfortunately, R-C ore is above the water table and, therefore, not amenable to the Palangana practice. Because of the limited known reserves in this deposit, it is readily apparent that conventional mining and milling are out of the question. However, because of its proximity to our Palangana operation, it seemed worthwhile to consider other options. The most viable route based on our past experience was to heap leach the ore. Our recent success at our Gas Hills facility and our Maybell operation, in employing a heap leach practice to our marginal reserves seemed to be a logical approach for processing this ore. Our experiences at both locations are described in "Heap Leaching - A Case History" by R. G. Woolery et al., Mining Engineering, March 1978. In both instances the process is an acid leach circuit and acid consumption averages 20 kg/t H2SO4. A preliminary feasibility study showed that because of the high strip ratio required for the R-C project to be successful, additional ore reserves must be located and that a method of heap leaching with an alkaline circuit would have to be developed. As a result of this paper study, the decision was made to proceed with a program of additional exploration drilling to determine the total ore reserves that could be mined economically. The Mining Department will evaluate each ore zone for cutoff grade, strip ratio, and expected mining cost. At the same time, a laboratory program to evaluate the available core samples for amenability to heap leaching with respect to an estimate of uranium recovery and processing costs was developed. This program is currently in progress, and at this time, we are just completing our process amenability study. BENCH-SCALE EVALUATION OF THE R-C ORE The initial bench-scale slurry leach tests on the R-C ore showed an acid consumption in excess of 200 kg/t H2SO4. These data, of course, discouraged us from considering this process route. Not only would the acid cost be prohibitive, but the gypsum generated by the reaction of the sulfuric acid with the calcium carbonate of the ore would severely effect the percolation of the lixivant. For this reason, the laboratory program was directed toward an alkaline circuit compatible with heap leaching. Because of the proximity of the R-C property to our Palangana operation, it seemed advisable to integrate the processing of this ore into the production at Palangana. Doing so would enable us to bring the R-C property into production by merely enlarging our present facilities at Palangana; otherwise, construction of a grass roots plant would be necessary. Ideally, the simplest method would be to construct the heaps at Palangana and employ an ammonium carbonate/bicarbonate leachant compatible with the in-situ production liquor. The product liquors could then be co-mingled or processed separately as desired. To determine if this goal was practical, samples of the R-C ore were obtained, and a laboratory program initiated. Heap leach amenability testing consisted of preliminary bench-scale evaluation to determine optimum solution strength and ultimate uranium recovery, followed by small column tests to confirm the bench-scale metallurgy and to determine percolation characteristics. These bench-scale tests are being followed by pilot-scale testing approximating field conditions. As expected, the bench-scale tests showed that the dissolution rate is considerably slower for alkaline leach than has been our experience in acid leaching. Because of the slower reaction rates, product liquor grades will be lower than for acid, as greater volumes of solution are required for satisfactory uranium extractions. The greatest influence on reaction times found in the laboratory was the carbonate/bicarbonate strength and oxidant addition. However, the higher salt concentration reduced the efficiency of the IX resin circuit and about 25g/L salt proved to an upper limit compatible with subsequent IX treatment. The oxidant contributed significantly to the early extraction rate but seemed to have only minimal effect on the total practical U308 extracted or the time required to achieve it. This variable will require larger scale testing to determine if the added cost of the oxidant is actually justifiable. Thus, the small-scale laboratory slurry tests, based on the 0.088% U308 sample available, indicate that leaching at 25g/L ammonium carbonate/bicarbonate, with or without oxidant, we might expect an 80-85% U308 extraction on this ore.

Jan 1, 1979

By H. C. Brassfield, R. E. Fryxell, E. C. Duderstadt, E. A. Aitken, P. K. Conn

Permeation rates of hydrogen through are-cast tungsten were measured at temperatures from 1300" to 2600°C with hydrogen pressure differentials of 1 and 0.1 atm across isothermal membranes. Rates were nearly Proportional to square root of pressure, were inversely ProPortional to membrane thickness, and were temperature-dependent according to the equation: p = permeation coefficient in cu cm (stp)-mm per sq cm-min-atmlr2, R = gas constant in cal per mole-OK, T = absolute temperature in OK. Permeation rates of oxygen through tungsten were deternlined in the range 1965" to 2300°C and at calculated oxygen (02) pressures of 3.3 x 10-4 to 2.2 x at?n using sealed capsules containing Kmown quantities of tungsten oxide. Permeation coefficients obtained in this manner had a temperature dependency in the range of 40 to 45 kcal per mole of permeating species. Permeation coefficients for oxygen were higher than those for hydrogen in the temperature range studied. This is probably the result of oxygen solubility being much greater than hydrogen solubility at these temperatures at a gzven pressure. The purpose of this investigation was to determine experimentally the permeabilities of hydrogen and oxygen through polycrystalline tungsten at temperatures ranging from 1300° to 2600°C. Permeation rates of hydrogen through tungsten have been measured at temperatures up to 925°C,but no previous measurements have been reported for the temperature range covered in this investigation. Some diffusion measurements3&apos;&apos; and solubility measurements3 have been made for hydrogen at temperatures below 2200°C. No previous permeability studies of oxygen through tungsten are known to the authors; however, efforts have been made to determine diffusion rates5-&apos; and solubilities PERMEATION THEQRY Permeation has been defined by ortton" as the overall steady-state flow process from the gas phase on one side of a membrane or wall to the gas phase on the other side and includes the steps of adsorption, solution, diffusion, exsolution, and desorption; in a given temperature range, any of these processes may be rate-controlling. For diatomic gases, which dissociate prior to diffusion, the quantity of gas which permeates through a membrane or wall at a given temperature is directly proportional to the surface area of the membrane, the length of time of permeation, and the difference between the square roots of the pressures on each side of the membrane, and it is inversely proportional to the thickness of the membrane when diffusion-controlled, thus: q = total amount of gas permeating a membrane, p = temperature-de pendent permeation coefficient, A = area of membrane exposed, / = time, p i = gas pressure of high-pressure side, p2 = gas pressure of low-pressure side, d = thickness of membrane. When the surface reactions are not rate-controlling steps and the solution of the gas in the metal follows Henry&apos;s law, the permeation coefficient, P, is equal to the product of diffusivity and solubility. The permeation coefficient is also temperature-dependent according to the equation: Po = permeation constant, Q = activation energy, R = gas constant, T = absolute temperature. MATERIALS The tungsten materials used in this investigation were greater than 99.9 pct pure. The interstitial impurities ranged from < 1 to 50 pprn C, 7 to 35 ppm O, less than 15 pprn N, and undetectable quantities of hydrogen. Previous high-temperature studies of are-cast tungsten have shown that thermal treatment similar to that which the hydrogen permeation cells experienced reduces the carbon content from starting levels of 50 to 60 ppm to about 30 ppm. Metallic impurities were in the low (1 to 50) ppm range. The argon gas used in this investigation contained about 8 ppm N. None of the following gases were

Jan 1, 1968

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.&apos; In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/&apos; in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about &apos;/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By D. Cox, M. J. Duggin, L. Zwell

The carbides of approximate composition and Mn have been studied using X-ray diffraction techniques. Those carbides of the type (Fe,Aln)zC ave isostructural with cementite. The cell pararmeters a and c have minimum values at approximately 10 at. pd substitution of manganese for iron; no satisfactory explanation has yet been found for this phenomenon. The carbide fFeMn4)C has a monoclinic unit cell whose dimensions are close to those of ,11,15Cz A neu-troip-dij~ractiot~ study of (F&apos;eAlrz4)C~ reveals that, like MnsCZ, it is isostructural with Pd5Bz. The iron and manganese atoms occupy the palladium atom sites, while the carbon atoms were found to have the same atomic coordinates as the hovon atoms. A neutrorr-diffraction study of indicates that the carbon-atom positions are very close to those occupied in (Fez.,ll/lr~,.3)C. In both carbides studied, tlre iron and manganese atomzs were found to be essentially randomly distributed, although, in the case of (Fe,.811fn1.2)C, it is possible that there may be a slight preference of manganese atoms for- the general (d) positions and a corresponding slight preference of iron atoms for the special (c) positions. It has been found that a complete range of solid solution exists between Fe3C and Mn3C at 1050°C,I although Mn3C becomes unstable when the temperature is reduced to 95O0C,&apos; and can only be retained by rapid quenching. It is also known that a complete range of solid solution exists from Fe5Cz to M~SC~,~ although the stability range of carbides of the type (Fe,Mn)sCz as a function of the relative proportions of iron and manganese is not known. X-ray examinations of Oh-man&apos;s carbide3 and Spiegeleisenkristall,~ which have the approximate compositions (Fe3.67Mnl.33)C2 and (Fe3-,Mn,)C, where x lies between 0.4 and 1, respectively, have been made. The following carbides have also been studied: ] The lattice parameters determined during these investigations are listed in Table I. It is seen that carbides of the type (Fe,Mn)sCz have a monoclinic unit cell while carbides of the type (Fe,Mn)3C have an orthorhombic unit cell. It is evident that the variation of lattice parameters with manganese content is not linear for carbides of the type (Fe,Mn)3C. The coordinates of the atoms in (Fe2.7Mno.3)C have recently been determined by single-crystal analysis., The fractional atomic coordinates have been shown by Fasiska and jeffrey to be in good agreement withj those deduced from an earlier analysis of Fe3C by Lipson and etch.&apos; However, it was impossible to determine whether iron and manganese atoms occupied ordered positions because of the small difference between the atomic scattering factors of iron and manganese. The atomic positions in Mn5Cz (Refs. 8 and 9) and Fe5C2 (Refs. 7 and 8) have been obtained only by comparisons made with the isostructural compounds P~SB~.&apos; Since X-ray diffraction techniques were used in these investigations, accurate positioning of the carbon atoms, which have a low atomic scattering factor, was difficult. No attempt has been made to determine the atomic positions in the other carbides previously studied. It was felt that an investigation of the lattice parameters of a number of intermediate carbides of the types (Fe,Mn)sCZ and (Fe,Mn)& would be of interest. It seemed likely that a neutron-diffract ion study of such carbides would indicate whether ordering occurred between the iron and manganese atoms because of the large difference between the neutron-scattering cross sections of iron and manganese. It also seemed probable that such an investigation would provide a determination of the atomic coordinates of the carbon atoms. I) EXPERIMENTAL DETAILS Specimens, each weighing approximately 20 g, were carefully prepared according to the following proportions: The components were 500-mesh powders of 99.995 pct purity iron and spectroscopically pure carbon and a 200-mesh powder of 99.995 pct purity manganese. The component powders were intimately mixed by prolonged shaking, then each specimen was inserted into a spot-welded cylindrical container of tantalum foil, whose end was closed but not sealed. Each specimen in its envelope was then sintered at 1050° C for 24 hr in a thin-walled evacuated quartz capsule, such a time having been previously found sufficient for equilibrium to be attained.&apos; Each specimen was then quenched in order to attempt to retain the high-temperature phase, as the literature indicates that transformations may occur on cooling. Debye-Scherrer X-ray photographs were taken of each specimen using a 114.6-mm-diam camera, Fig. 1, patterns 2 to 6. The exposure time was 6 hr using filtered iron radiation at a tube voltage of 40 kv and a tube current of 12 ma.

Jan 1, 1967

By Herbert Clark Hoover, Lou Henry Hoover

PREVIOUSLY I have dealt with the methods of separating silver from copper. There now remains the portion which treats of solidified juices ; and whereas they might be considered as alien to things metallic, nevertheless, the reasons why they should not be separated from it I have explained in the second book. Solidified juices are either prepared from waters in which nature or art has infused them, or they are produced from the liquid juices themselves, or from stony minerals. Sagacious people, at first observing the waters of some lakes to be naturally full of juices which thickened on being dried up by the heat of the sun and thus became solidified juices, drew such waters into other places, or diverted them into low-lying places adjoining hills, so that the heat of the sun should likewise cause them to condense. Subsequently, because they observed that in this wise the solidified juices could be made only in summer, and then not in all countries, but only in hot and temperate regions in which it seldom rains in summer, they boiled them in vessels over a fire until they began to thicken. In this manner, at all times of the year, in all regions, even the coldest, solidified juices could be obtained from solutions of such juices, whether made by nature or by art. Afterward, when they saw juices drip from some roasted stones, they cooked these in pots in order to obtain solidified juices in this wise also. It is worth the trouble to learn the pro- portions and the methods by which these are made. I will therefore began with salt, which is made from water either salty by nature, or by the labour of man, or else from a solution of salt, or from lye, likewise salty. Water which is salty by nature, is condensed and converted into salt in salt-pits by the heat of the sun, or else by the heat of a fire in pans or pts or trenches. That which is made salty by art, is also condensed by fire and changed into salt. There should be as many salt-pits dug as the circumstance of the place permits, but there should not be more made than can be used, although we ought to make as much salt as we can sell. The depth of salt-pits should be moderate, and the bottom should be level, so that all the water is evaporated from the salt by the heat of the sun. The salt-pits should first be encrusted with salt, so that they may not suck up the water. The method of pouring or leading sea-water into salt-pits is very old, and is still in use in many places. The method is not less old, but less common, to pour well-water into salt-pits, as was done in Babylon, for which Pliny is the authority, and in Cappadocia, where they used not only well-water, but also spring-water. In all hot countries salt-water and lake-water are conducted, poured or carried into salt-pits, and, being dried by the heat of the sun, are converted into

Jan 1, 1950

By F. D. Rosenthal, F. J. Dunkerley, G. J. Mills

Activities, free energies, and heats and entropies of mixing of liquid Pb-Zn alloys have been obtained by the electrode-potential method between 400° and 650°C. The large positive deviations observed from Raoult&apos;s law are in agreement with the phase diagram, which indicates a wide immiscibility field. A vapor-pressure method was used to extend the activity measurements to 900°C, allowing the maximum of the immiscibility gap to be estimated by thermodynamic calculation. Data on the mono-tectic and eutectic points compare favorably with previously existing work. SEVERAL long-standing methods have been in use for the study of phase diagrams from measurement of the activities of the component metals.&apos; The use of thermodynamic analysis for interpreting equilibria data is comparatively recent, however. Such analysis is usually undertaken by first evaluating the principal thermodynamic functions as, for example, the enthalpy, entropy, and free energy of the alloy constituents. These, in turn, quite often can be correlated with the interatomic potential energies and atomistics of the system, from which a clearer understanding of the causes leading to deviations from ideal behavior is gained. The present study of liquid Pb-Zn alloys is concerned with a determination of these quantities by electrode-potential and vapor-pressure measurements, using these values in calculations involving phase equilibria and to obtain a theoretical insight into an alloy system exhibiting strong positive deviations from ideal metallic solution. A considerable portion of the previously reported work is based on thermal analysis. Supplemented by optical studies of solid alloys, these techniques have revealed the essential nature of the immiscible mixtures that are formed. It is difficult, however, using the phase-

Jan 1, 1959

By B. S. Butler

A. D. Mutch (Falconbridge Nickel Mines Ltd., Ona-ping, Ontario)—This contribution is prompted by the fact that the writer has recently published an article&apos;!&apos; which has in part the same general conclusions as B. S. Butler&apos;s, namely, the form of the standard mineral paragenesis in hypogene deposits and the parallel transition from early high temperature acid to late low temperature alkaline or neutral solutions. Since the writer also recognizes that he is not fully qualified to discuss the formation of ore deposits as a chemical problem, this discussion will be limited to summarizing other observations and will suggest how Butler&apos;s Table II might be made more effective. The form of Butler&apos;s table is not unlike that widely used by European geologists&apos;" in which the various minerals are related to the types of ore fluids—peg-matitic, pneumatolic and hydrothermal. Thus the decrease in temperature and change in pH of the ore-bearing fluids as recognized by Butler may also be paralleled by perhaps even greater changes in composition, density, and character. W. H. Newhouse&apos;s article:" on the sequence of hypo-gene ore mineral deposition is still one of the most complete analyses of the problem. In it he makes four major observations: 1) The order of O, S, As, Sb is the same as their increasing atomic weights and the same as their melting points. 2) The order of the metallic elements is the same as the Schuermann series. 3) The general mineralogical order is paralleled by decreasing heats of formation. 4) The order is generally in decreasing hardness, higher metal content, and higher specific gravity. The order of 0, S, As, and Bi is also the same as their relative abundance. Another point worth mentioning about this series is that As, Sb, Bi, when abundant, often substitute for sulfur in the early pyrite-like minerals, whereas later in the sequence these elements appear to act more like metals. This behavior may be a further indication of the acid character of the early fluids. C. J. Sullivan"&apos; has attempted to show that the sequence of the metallic elements is related to the order of their melting points and has discussed the interrelationship of the different types of bonding of sulfo-phile and oxiphile elements in minerals. Items 3 and 4 might best be summarized by saying that bonding of the minerals in the series appears to be from ionic to covalent to metallic, the early minerals being light in weight, hard, and near-transparent; the intermediate minerals of intermediate weight, semi-transparent, and semi-conducting; and the end minerals heavy, soft, and malleable, opaque and good conductors. A rapid fall in temperature has been assumed to be the cause of ore deposition in many deposits. Perhaps this in turn is the effect of a rapid release of energy in the form of pressure release and change of volume, the first minerals to form being those with the highest heats of formation which absorb the released energy the most rapidly. Butler&apos;s Table II could probably be streamlined and made more effective if the listed compounds were assembled as mineralogical groups as in Dana. Thus the sulfides, arsenides, antimonides, bismuthides, and sulfa salts could be arranged in AX,, AX, A2X2, etc. groups. Since these are continuous substitution series, in which the fields of stability and the heats of formation of the various individual minerals can be fairly regarded as similar, this should be accomplished with no loss of clarity. The occurrence of the individual minerals and the precise sequence of the mineral deposition in any one deposit is probably more dependent on the concentration and relative abundance of the component elements. The assembling of geological data in tabular form such as Butler&apos;s Table II will continue to be a very effective method of studying geological phenomena. The importance of this particular problem has been pointed out by C. F. Park,% who concludes that understanding of mechanisms of the standard paragenesis and interrelated problems of mineral zoning in space and time is one of the major keys to classification of ore deposits.

Jan 1, 1959

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.&apos; Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-&apos;3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968