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By Howland Bancroft

AMERICAN investment in foreign mining interests today faces its greatest task. U. S. dollars must make possible the. steady procurement of the minerals our defense effort consumes in huge quantities. The two most vital factors involved in foreign procurement are time and the continued good will of the nations from which minerals are purchased. The Point IV program was formulated to care for the second item, but it has failed to do the job. Its lack of success has not been from intent or from basic failure in formula. Foreign Investment, Four Eras Foreign mineral development, in so far as participation by private capital from the United States is concerned, may be divided into four main chronological categories: First: The period prior to the first World War when people, capital and products moved with relative freedom across international boundaries, and London was the recognized mining seat of the world. By the end of 1919 the United States direct investments abroad amounted to $3.9 billion of which some $900 million were in mining and smelting and $600 million in petroleum. Investment climate throughout most of the world was excellent. Second: The period between the end of World War I, when the international economy had been shaken from its foundations, and the beginning of the great depression of the 1930's, which still further disrupted the world economy. By that time the world mining center had moved across the sea and the United States direct investments abroad had increased to $7.7 billion of which mining and smelting accounted for $1.2 billion and petroleum for $1.1 billion. Investment climate was good in most parts of the world. Third: The period of the depression of the 1930's and the beginning of World War II during which foreign trade was still further disorganized and the international economy collapsed. Nazi barter agreements were initiated in many parts of the world, and Soviet propaganda commenced to make its, influence felt in many countries. During this period United States direct investments abroad decreased to $7.3 billion. Mining and smelting investments during the same period decreased some $200 million, though direct investments in foreign petroleum areas increased an equal amount. Investment climate became less and less hospitable in all parts of the world affected by economic nationalism. Fourth: The period since the beginning of World War II during which total direct investments abroad increased from $7.3 to $13.7 billion. Of this sum, at the beginning of 1950 investment in foreign mining and smelting is reported to have been $1.2 billion-back to where it was in 1929, and in petroleum to have reached $3.7 billion. Investment climate remained favorable in the countries respecting contractual obligations and fair in their treatment of invested capital. [ ] As noted above, the relative freedom of passage across international boundaries by people, capital and products ended with World War I and the situation remains unchanged in a greater part of the world. While this same war upset international economy, the depression of the 1930's caused the collapse of world trade, and exports from all countries fell to an alarmingly low figure. Some countries almost ceased to export. Chile, for example, reported a drop of 88 pct in exports. Countries with

Jan 1, 1952

By M. P. E. Desvaux, P. Charsley

OLIP-line observations on copper alloys, using the electron microscope, have been made by a number of workers,13 but this work has been confined to a brass. In a CuAl alloys Koppenaal4 and Koppenaal and Fine5 have made observations with the optical microscope and by the use of interferometry. They found that the observed slip step heights inside the Liiders bands accounted for only 42 pet of the total macroscopic strain. The suggestion was put forward that optically unresolvable slip in other parts of the specimen accounted for a major part of the macroscopic strain. This is surprising since it is known from other workers that slip in a brass is inhomogeneous; i.e., large amounts of slip occur on individual {lll) closelys paced than being shared by a large number of closely spaced planes. Furthermore, a brass and a CuAl alloys with high concentration of aluminum exhibit similar deformation characteristics and slip-line patterns. Prior to investigations into the behavior of copper and a CuAl alloys under reversed stresses in tension and compression, some preliminary experiments have yielded results which the authors think resolve this discrepancy, and throw some further light on the behavior of a CuAl in tension. An experiment was carried out on a 10 at. pet CuAl single crystal, of gage length 7.5 cm, diameter 3.1 mm, and orientation shown in Fig. 3 (inset), for the purpose of resolving the above discrepancy. The specimen gage length was electropolished for 10 min in a 50:50 orthophosphoric acid (SG=1.75)-distilled water system, with 2 v across the cell and a current density of 0.5 amp per sq cm. The cathode was made of copper. After a tensile strain of 0.067 ± 0.001, intense slip was observed over a length 2 cm of the gage length whilst the rest of the specimen was relatively undeformed. In the lightly deformed region, slip bands of mean width 20 /x were spaced about 1 mm apart on average. The transition from the heavily slipped region (usually called a Liiders band) to the lightly deformed region was gradual, the slip-band density increasing as the "Liiders band" was approached. In the latter, the slip bands became so close together that, to the naked eye, the specimen appeared to be continously slipped, and the typical microtopography of this region is shown in Fig. 1. Twelve electron micrographs were taken at random from replicas of the Liiders-band region, and the widths of the slip lines were measured. The slip lines account for an over-all tensile deformation of 7.0 ± 0.7 pet, after allowing for the lengths of the un-slipped regions, which is in good agreement with the macroscopic strain. The distribution of slip-line widths was also measured and is shown in Fig. 3. Since Koppenaal could not resolve slip lines with height less than 540A (limit of resolution represented by dashed line), then it was deduced that he could have measured only about 50 pet of the deformation within the 'Liiders Band'. It is concluded, contrary to the suggestion of Koppenaal,5 that virtually all the macroscopic strain is accommodated within the "Luders band" and that there is no need to invoke fine slip distributed uniformly over the gage length.

Jan 1, 1967

By Howard Martens

HARDNESS behavior of commercial titanium alloys following various heat treating processes has been studied for some time. However, the hardness of such alloys following a definite measured cooling rate from the single phase region has not been reported. Therefore, a series of experiments was conducted on the three alloys: 150A, 130A, and 130B. The manufacturers gave the following compositions for these alloys: Ti 150A: 0.045 pct C, 0.069 pctN, 1.32 pct Fe, and 2.68 pct Cr; RC 130A: 0.13 pct C, and 7.9 pct Mn: RC 130B: 0.11 pct C, 3.5 pct Mn, and 3.2 pct Al. A method similar to that described by Greninger was used, and the cooling rate varied from 6" to 9200°F per sec. The cooling curves were recorded on a Speedomax or a recording oscillograph, and the hardness was measured on a Tukon hardness tester using a Knoop indentor with a 500 g load. The curves of Fig. 1 show the variation of the Knoop hardness with the cooling rate for these three alloys. The alloys 150A and 130B behave in a similar manner, as shown by the curves. In neither of these alloys was it; possible to retain the high temperature ß phases, even by the most rapid cooling rate. The slow cooling rates produced a typical ß structure in these two alloys. As the cooling was increased, these phalses became more finely dispersed and the hardness increased. This increase in hardness with cooling rate continued for the 150A alloy until a rate of approximately 1000°F per sec was reached. At this cooling rate, the structure showed the result of the dif-fusionless transformation of the ß solid solution to the supersaturated a solid solution which is referred as a'. At higher cooling rates, the structure showed no change and the hardness showed no great change, as indicated by the dotted portion of the curve in Fig. 1. The increase in hardness with cooling rate for the 130B alloy continued until a rate of approximately 300°F per sec was reached. At this rate the structure was produced and the maximum hardness was reached. Higher cooling rates caused no marked changes in hardness or structure. The alloy 130A behaved in a different manner, as shown by the curve of Fig. 1. The structure produced by the slow cooling rates was a typical a+ß structure, which became finely dispersed as the cooling rate increased. The hardness increased with cooling rate and reached a maximum at approximately 120°F per sec. At this maximum hardness, the structure showed the result of the decomposition of the ß phase into the ß + phase structure. As the cooling rate was increased, smaller amounts of the at phase were formed and the alloy became softer. For cooling rates of 3000°F per sec and above, the high temperature ß phase was retained and the hardness of the alloy did not change markedly. Acknowledgment This paper presents the results of one phase of research carried out at the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. DA-04-495-0rd 18, sponsored by the Dept. of the Army, Ordnance Corps.

Jan 1, 1957

By J. P. Martin, A. H. Geisler, J. H. Crede, E. Both

The investigation of a 50 pct Co alloy was undertaken to determine whether there was any direct correlation between the structure and properties of Co-Fe alloys which were given various magnetic heat treatments. The magnetic anisotropy and texture of the 0.002-in. cold-reduced 98 pct material tend to decrease and change in nature with increasing temperature of the recrystallization anneal. Annealing samples in a magnetic field had little effect on either the magnetic properties or texture. However, cooling them in a magnetic field greatly improved their magnetic properties. THE beneficial influence of a magnetic field applied during the heat treatment of certain soft magnetic materials has been known for a long time. Early work showed that the presence of a magnetic field of a few oersteds during the heat treatment of Fe-Ni alloys will cause a large increase in maximum permeability. A pronounced increase in the residual induction which is produced by the magnetic anneal causes the hysteresis loop to approach the shape of a rectangle. Such results are beneficial since the desired properties are high permeability, high induction at maximum permeability, high residual induction, and low coercive force. More recently Libsch and coworkers1 studied the effect of magnetic annealing on the hysteresis properties of a series of Co-Fe alloys prepared from powders. They observed good response for the 35 and 50 pct Co alloys but little response for the 42 pct Co alloy. They pointed out that this was somewhat surprising since the 42 pct alloy has a high linear magnetostriction and zero crystal anisotropy and similar conditions in Fe-Ni alloys give excellent response to magnetic annealing. They found optimum properties to be at the 50 pct composition with residual induction, Br = 19,000 gauss and coercive force, Hc = 0.68 oersteds after the magnetic anneal. Before the magnetic anneal these values were B, = 12,600 gauss and Hc = 1.15 oersteds. The optimum treatment consisted of cooling from above the y-a transformation temperature to 900°C in a field of 20 oersteds, holding 11/2 hr at 900°C, then cooling at a rate of 20° to 25°C per min in the field to below 230°C. Cooling rate mainly affected coercive force with the value decreasing from 1.09 to 0.88 oersteds as the rate was increased from 3° to 48°C per min. Cooling from 1020" to 900°C in a field followed by further cooling to 230°C without the field gave properties decidedly inferior to those for samples annealed with the field applied throughout the cooling. They concluded that to get the best properties the samples must be cooled in a field to a threshold temperature above which the alloy is plastic enough to be affected by magnetostriction. In this respect the holding temperature must be high enough so that the alloy exhibits good plasticity to permit the optimum orienting of magnetic domains by relaxation of magnetostriction. In contrast, the holding time was of less significance for there was little improvement when the time exceeded 1/2 hr. The improvement in properties effected by magnetic annealing has usually been attributed to the establishment of a domain texture caused by the "freezing in" of magnetic strains. On the other hand, Smoluchowski and Turner2,3 apparently found that a magnetic field applied during recrystallization could alter the crystal texture. If this effect is real, improved properties would also be expected when

Jan 1, 1954

By F. D. Rosi, C. A. Dube, B. H. Alexander

WHEN a deformed polpcrystalline metal is heated to a sufficiently high temperature, a recrystallized structure develops which consists of small, essentially stress-free grains. This transformation is referred to as primary recrystallization. Under certain conditions, on prolonged annealing of the specimens, a type of grain coarsening occurs in which a small number of grains commence to grow at various points by devouring the neighboring finegrained primary structure, which, in itself, exhibits a marked stability toward normal grain growth. This grain coarsening process has been referred to by Burgers' as "secondary recrystallization" or "exaggerated grain growth." Although much work has been done on recrystallization and growth processes, present knowledge of the factors which determine the occurrence and growth of secondary grains is inadequate for the advancement of a theory which accounts for the observed characteristics of this recrystallization phenomenon. In this respect, it would be important to make measurements of the velocity of growth of these large secondary grains. The early work of Feitnecht2 on aluminum showed that the size of secondary grains increased with temperature and time, suggesting that such measurements would be possible. More recently, Burgers1 found that the growth velocity of these grains in aluminum was constant over a large time interval, as is generally found for the growth velocity of primary grains in a uniformly deformed test piece.3-5 It is reasonable to expect that the determination of the activation energy of the secondary growth process might lead to a better understanding of the underlying atomic mechanism. This investigation, therefore, is one of a series primarily designed to measure the growth velocity of secondary grains at various temperatures for silver, copper, and aluminum. It is hoped that these studies along with those of orientation relationships, will establish a sound basis for theorizing as to the origin and nature of the secondary transformation. Experimental Procedure The metal used in the present investigation was high-purity silver (999.9 fine), which was supplied in the form of cold-rolled plates 0.250 in. thick. These plates were annealed at 500°C for 1 hr and then straight-rolled to a thickness of 0.04 in. in three reductions of approximately 45 pct, followed in each case by an anneal at 450°C for 1/2 hr. The 0.04 in. sheets were given a final reduction of approximately 50 pct, which resulted in a thickness of 0.02 in., thereby insuring two-dimensional crystal growth. Individual specimens of this material about 1x3 cm were used for all heat treatments, unless otherwise noted. The annealing was carried out under an atmosphere of argon in an Inconel tube furnace whose temperature was controlled to within -+2°C. Metallographic examination of the secondary transformation was accomplished by mechanically polishing the specimens on one side to approximately one half their thickness through 2/0 metallographic emery paper, and then electrolytically polishing in a solution of potassium ferrocyanide and sodium cyanide. With a current density of approximately 20 amp per sq dm, the time required to obtain a satisfactory surface varied from 3 to 5 min. Standard potassium bichromate was used to etch the electrolytically polished surfaces. A heavy etch with this solution produced a sharp contrast between the secondary grains and the fine-grained primary structure, darkening the latter while leaving the large secondary grains bright. All area measurements of the secondary crystals were made with a planimeter on enlarged tracings of the grains.

Jan 1, 1953

By Paul A. Beck, John Towers, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350' to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.' Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.' Walker's specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By John Towers, Paul A. Beck, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350' to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.' Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.' Walker's specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By T. K. Perkins, L. E. Bartlett

Values of rock surface energy (i. e. energy required to form a unit area of new surface) are useful for interpretation of drilling and fracturing phenonema This paper describes the adaptation of a cleavage technique (splitting of large rocks under controlled conditions) for measuring surface energies. Values of surface energy obtained at room temperature and at low crack extension rates are reported for a variety of sandstones and limestones. Elastic moduli, tensile strengths and compressive strengths of the samples are also reported. The values of Young's moduli (measured in bending) are relatively low, probably because of the low stress levels imposed. Measured values of surface energy me generally higher than anticipated and probably reflect inelastic yielding near the extending tip of the crack. INTRODUCTION The technology of petroleum production includes many operations such as drilling and fracturing, which involve rock breakage. One of the fundamental properties of a rock needed to fully explain breaking and fracturing phenomena is the surface energy (i. e. the energy required to form a unit area of new surface). In this paper we describe an adaptation of the cleavage method (splitting of the rock under controlled conditions) to utilize large rock samples. Application of the theory of elastic cantilever beams and the Griffith concept of mechanical stability permits the calculation of surface energies from simple measurements. Values of surface energies obtained at room temperature on dry samples and at low crack extension rates are reported for a variety of sandstones and limestones. Measured values of Young's Moduli, compressive strengths and tensile strengths are also reported for the rocks. THE EXPERIMENTAL METHOD Equipment designed to cleave large rock samples is shown on Fig. 1. This equipment consists essentially of two steel blocks cemented to a rock sample and forced apart with a steel rod. A ball joint and a pivot prevent bending stresses in the rod. A differential thread arrangement permits the rod to advance only 0.012 in./revolution of the driving nut. The axial force in the rod is measured with type FA-50-12 Baldwin Lima Hamilton strain gauges and a BLH type 20 strain gauge reader. Separation of the blocks is measured with a Starrett 656617 dial gauge. The massive nature and design of the equipment minimize the amount of elastic energy stored in the steel parts as the stress in the rod is increased. This will permit the rock to split under controlled conditions as will become clear later. Fig. 2 shows a sketch of the rock sample during cleavage. Guide slots are cut longitudinally along the rock sample as suggested by Berry.1 An initiating slot is also cut across the top of the block to a depth of 1 to 2 in. During cleavage, elastic energy is stored in the flexed beams of rock of length C. If the length of steel rod L is held constant and the crack extends in length, then the elastic potential energy stored in the rock decreases. However, surface energy must be supplied as the crack extends in length. Griffith6 has proposed the following criteria for mechanical stability. The crack will extend as long as the potential energy available is greater than the surface energy required. However, the crack will stop extending when the change in potential energy with change in crack length is just equal to the change in surface energy with change in crack length. See Eq. 1.

By F. C. Schora, H. P. Meissner

Both a graphical and an analytical technique are presented for calculating stream compositions and temperatures in adiabatic staged systems in which solids travel countercurrently to a gas stream. Such a system might be a tower containing several plates, on each of which the descending solid is fluidized by the rising gas stream. Examples are presented in which chemical reactions occur, including the oxidation of SO, by a solid catalyst and the gaseous reduction of iron oxides. COUNTERCURRENT staged processes involving reactions between solid and gas streams are becoming more common. These operations are generally carried out in a series of beds of fluidized solids, with each bed or "plate" acting as a stage. Fig. 1 is a schematic diagram of such a series of stages located in a column, down through which a solids stream moves from stage to stage counter to a rising gas stream. Typical reactions carried out in such systems are the dehydration of aluminum trihydrate, the calcining of limestone, and the gaseous reduction of iron oxides. Calculation of the performance of these counter-current systems rapidly becomes more complex with increases in the number of stages and in the number of chemical reactions occurring. Calcula-tional procedures for isothermal operations of such systems have been described.4 Actual tower operations, however, are generally adiabatic, and in consequence far from isothermal. The object here is to present both graphical and analytical techniques applicable to such adiabatic towers operating continuously and in steady state. In this introductory discussion, the graphical techniques presented are of the McCabe-Thiele type, rather than of the Pon-chon type. In all the examples presented, it will be assumed that both thermal and chemical equilibrium are attained in each bed. The assumption that the gas and solid streams leaving each bed are at the same temperature as the bed is in accordance with the familiar behavior of actual fluidized solid systems. Chemical equilibrium, on the other hand, is not necessarily attained in any given stage between these two streams, even with deep beds, since reaction rates may be slow. In the last section of this paper, discussion is presented of methods suitable for use when chemical equilibrium is not attained. The adiabatic tower in Fig. 1 has "n" stages numbered from 1 to n, starting with the bottom stage as number 1. In analyzing this tower's performance, it is important to express gas flow rates in terms of a key component or element which remains completely within the gas stream throughout the tower. Similarly, solid flow is best expressed in terms of a key compound or element which remains within the solid phase throughout the tower. Thus, in burning limestone with a hot flue gas, the gas flow might be expressed as G, the pound mols of nitrogen flowing through the tower per unit time, while solid flow might be expressed as S, the pound atoms of calcium in all forms in the solid stream per unit of time. Defined in this way, both G and S are constant throughout the tower. The enthalpy of the gas and solid streams are now best expressed in terms of these key components. That is, the gas stream enthalpy H is expressed as Btu in the total gas per mol of the key component in the gas. Similarly, the solids stream enthalpy h is expressed as Btu in the total solid stream per pound mol (or pound atom) of the key component in this stream.

Jan 1, 1962

By S. M. Brisbane

THE life of refractory linings in rotary cement kilns can be shortened by uneven or inadequate support of the kiln and its shell and by variations in the conditions of operation. Alteration of these factors may, according to their nature, bring about mechanical deterioration of the lining or promote chemical attack. Chemical attack has been described elsewhere.1-4 The distortion of cement kilns has been discussed in a general manner by Rochow,6 ho indicates the amount of distortion which may occur in an unlined shell, and by Rosenblad: who states that the deformations of the shell are greatest above the trunnions. The present article indicates the extent of the distortion of a kiln to an oval shape in certain selected positions and the deviation from a straight line of the kiln along its length between two supports. The cement kiln is a long, hollow, rotating cylinder consisting of steel plates which may be either welded or riveted together. This shell is supported on tires, frequently 60 ft apart, which roll on trunnions. The large mass of the kiln causes distortion of its cross-section; it becomes slightly oval, i.e., diameters lengthen as they become horizontal and shorten as they become vertical. There is also a tendency for the shell to bow between supporting tires; this bowing may be upwards or downwards depending on the position of the weight forces and the supports. The extent of the deviations from the ideal kiln shape was investigated. Observations described in this paper were made on the shell of the clinkering zone between the first and second tires of two of the kilns at the Geelong works of Australian Portland Cement Pty. Ltd. The kilns were both 400 ft long and 10 ft diam with a welded enlarged burning zone 11 ft 6 in. diam. The shell was fabricated from mild steel and in this section its thickness was 1 in. It was lined with 41/2 in. of chemically bonded magnesite-chrome bricks which were jointed with mild steel plates. The kilns operate on a 4 pct slope and the speed may be varied between 0.75 and 1.68 rpm. The wet process is used; kilns are coal fired and are fitted with integral coolers. Temperatures within the kiln are difficult to determine with any accuracy because of the absence of black body conditions, but surface temperatures are probably in the range 1420° to 1470°C. Average shell .temperatures at the two positions at which the deformation studies were made were 370°C and 355"C respectively. Methods: In determining the ellipticity it was necessary to measure the lengths of the vertical and horizontal diameters while the kiln was in operation; data obtained from a stationary kiln would not have the same practical significance. For this purpose the four points V, W, X, and Y at the ends of two mutually perpendicular diameters were marked on one kiln. The point X is shown in Fig. 1. For the measurement of the length of the vertical diameter a vertical column, to which a horizontally aligned telescope was attached, was placed 10 ft from the kiln. The telescope could be racked up and down in a vertical plane. Two sets of readings were taken, one set when each of the points V, W, X, and Y was at its maximum height above the

Jan 1, 1957

By A. Rosenzweig, M. M. Karnowsky

The generalized binary diagram of the Au-Sn-Pb system is presented. The chief characteristic is the pseudobinary between lead and AuSn. On the high-gold side of the pseudobinary, four reaction isotherms were found at 363°, 274°, 225°, and 204°C. On the low-gold side of the pseudobinary, three reaction isotherms at 277°, 205°, and 176°C were found. A vertical section from the eutectic solder composition to gold was developed from the isothermal sections generated. METALLURGICAL problems arising from the intentional or accidental formation of Au-Sn-Pb alloys in soldering applications have indicated a need for information on the phase equilibria in this ternary system. The literature indicates that a complete diagram presenting this information has not been prepared. Even the recent excellent work by prince' entitled "The Au-Pb-Sn Ternary System" actually extends only to the AuSn or 50 at. pct Au range. There are more events in the 50 to 100 at. pct Au than in the less than 50 at. pct range. This article by Prince furnished much guidance in preparing this report. Initial efforts with the isopleth from the eutectic solder composition 61.9 wt pct Sn-38.1 wt pct Pb and 0 to 90 wt pct Au indicated that extensions of the work to the whole of the diagram (even if in less detail) were necessary to understand this system. In undertaking the construction of such a diagram, this study used differential thermal analyses (DTA) and metallography with verification and identification of phases by electron microprobe analyses. EXPERIMENTAL PROCEDURE The procedure began with the development of a cell which would be unreactive with lead, tin, and gold, retain its strength to 1100°C, exclude oxygen, and also furnish a suitable well for insertion and protection of a thermocouple to monitor temperature changes in the material. Such a cell would make it possible to reuse the sample should a repetition of determination be desired. Fig. 1 is a photograph of two such quartz cells as finally developed. The specimens have been run many times. The cell is made up of an inner sample bucket and an outer capsule with a thermocouple well which the sample surrounds. The DTA unit was an assembly devised from available instrumentation. The sample holder was a 3-in.-long cylinder of nickel, 2 1/2 in. in diam, fitted securely in a vertical tube furnace. Two holes 7/8 in. in diam were symmetrically located to receive the quartz cells. A dummy cell with nickel powder was used as the reference. The absolute temperature was recorded with a Pt/Pt 10-pct Rh thermocouple with an automatic Kaye ice bath compensator. (Calibration indicated the compensator to be accurate to better than ±0.5° over the 100° to 1000°C range.) The absolute temperature was measured in the sample and recorded on an L&N mul-tirange recorder with a full-scale display of 1 mv and automatic ranging of 99 mv. The differential signal between the sample temperature and the reference temperature was amplified with an L&N microvolt amplifier and recorded on an L&N Speedomax G recorder. Since two charts were obtained, the chart speeds were equalized and each event was noted on the differential chart, and the temperature at that time was obtained from the temperature record.

Jan 1, 1969

By Che, C. W. Spencer, C. A. Steidel, Yu Li

Grain boundary grooving as it occurs in a 5.5-deg simple-tilt nickel bicrystal immersed in a saturated Ni-S liquid has been studied. A 1/3 (t= time) dependence for the depth of the groove indicates that the rate -controlling meckanism for groove developvnent is volume diffusion in the liquid. The activation energy for the diffusive process is estimated at 15 kcal per mole. Using an extended form of W. W. Mullins&apos; analysis for grooving reactions, a computer is employed to fit the appropriate diffusion equation by a numerical method. From the analysis a possible method of measuring L.S. the solid-liquid interfacial tension is demonstrated. WHEN a polycrystalline solid is heated in equilibrium with a saturated fluid phase, grooves will form at the intersections of the grain boundaries and surface. The equilibrium root angle of these grooves is determined by the balance between the grain boundary and solid-fluid interfacial tensions. The grooves deepen and widen with time due to a difference in chemical potential between the flat interface and the curved interface of the groove. In this investigation solid-liquid interaction at a grain boundary is studied, with the object to determine the mechanism of grain boundary grooving in the presence of a saturated liquid. Extension of Mullin analysis then permits the estimation of the solid-liquid interfacial tension. Herring has demonstrated by dimensional analysis that the quasi-steady state change of the dimensions of a small particle during sintering is proportional flow, evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, respectively, if geometric similarity of consecutive configurations of the particles holds. Mullins has extended this analysis to grain boundary grooving. In the case of shallow grooves he solves the diffusion equations for evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, and obtains the same time dependence for any linear dimension of a groove as Herring found for the change in dimension of small particles. In Mullins&apos; analysis2&apos;3 grain boundary grooving of a bicrystal by volume diffusion in the presence of a saturated fluid phase was considered. Several assumptions were made prior to the analysis: 1) the solid-fluid interfacial tension is independent of crystallographic orientation; 2) the Gibbs-Thompson equation relating curvature and chemical potential is applicable at the solid-fluid interface; 3) the relaxation time of the diffusion field is small compared with the time for appreciable changes in the curvature of the groove, so that the diffusion is divergence-less; and 4) the groove has a small slope relative to the initial flat interface. Usually this last condition is fulfilled only for solid-gas systems. The solution of the diffusion equation under the above conditions produces a t1/3 dependence for any linear dimension of the groove in the case where volume diffusion is rate-controlling. The t1/3 dependence is valid because geometric similarity of the grooves exists for all time. EXPERIMENT In the experiment a 5.5-deg nickel bicrystal of <100> simple-tilt orientation was used.4 Grooving was studied in the presence of a saturated Ni-S liquid alloy as a function of time at 750°, 800°, 850°, and 900°C. A low-angle bicrystal was chosen for study to insure that 2L.S. > .b., where l.s.

Jan 1, 1964

By N. S. Bornstein, M. A. DeCrescente

ThE nickel and cobalt base superalloys employed in gas turbine engines under some conditions&apos; oxidize at an accelerated rate when exposed at elevated temperatures to atmospheres containing minor quantities of sea salt. It is generally agreed by investigators in the field that the major steps comprising this phenomena of accelerated oxidation, also called hot corrosion or more commonly, sulfidation, are a) a slag composed primarily of Na2S04 is formed on turbine components, b) the protective oxide scale is rendered ineffectual, c) the slag reacts with. the substrate to form metal sulfides, and d) the substrate is rapidly oxidized. Sodium sulfate, a minor constituent of sea salt, is formed within the gas turbine engine from the reactions between NaC1, the major constituent of sea salt, and the oxides of sulfur.&apos; Depending upon concentration, engine compression ratio, and temperature, the Na2S04 will be present in the gaseous or condensed state. It has been determined that in order for sulfi-dation to occur the Na2S04 must be present in the condensed state.&apos; Although a number of sulfidation mechanisms have been postulated, there is no consistent explanation of oxide scale breakdown and subsequent catastrophic oxidation. Some investigators believe that after oxide scale breakdown, the Na2SO4 reacts with the substrate to form lower-valent sulfur compounds. The accelerated rate of oxidation is due to oxidation of a nickel-sulfide phase." Other investigators believe that sulfur from the fused salt reacts with chromium in the alloy to form chromium-rich sulfides; thereby depleting the alloy of an element which imparts oxidation resistance.3,4 This publication will demonstrate that the accelerated rate of oxidation associated with sul-fidation is due to interactions between Na20, a con-stituent of NazSO.,, ancl the substrate. The aim of this study was to separate and determine the effect of compounds of sulfur and sodium on the oxidation kinetics of various nickel-base superalloys, in order to elucidate the sulfidation mechanism. The work reported herein is sponsored in part by the Naval Ship and Development Center-Investigation of EXPERIMENTAL PROCEDURE The nickel base alloys B-1900, U-700, and Waspaloy were chosen for this study. The nominal compositions are presented in Table I. The specimens, approximately 1 in. by 1 in. by 0.060 in. received in the "as cast" condition were polished with 600 grit emery, washed, and rinsed with acetone immediately prior to oxidation experiments. Sulfida-tion attack was duplicated in the laboratory by apply-ing a saturated aqueous solution of Na2S04 onto the al loy substrate and subsequently exposing the specimens in oxygen at elevated temperature. The method of Na2S04 application is described elsewhere in detail.6 In another set of experiments the affected substrate microstructure associated with sulfidation was reproduced free of the normal oxide scale, by reacting and diffusing elemental sulfur into the alloy. The experimental procedure is also described elsewhere in detail. All oxidation studies were performed using an Ainsworth thermobalance type RV-AU-1, which is readable to 0.01 mg and is reproducible to ±0.03 mg. The specimens, introduced into a heated furnace, were exposed in the temperature range 800" to 1000°C

Jan 1, 1970

By R. E. Maringer, B. A. Wilcox, A. H. Clauer, J. H. Sovik

Internal friction measurements from 25° to 1100°C have been made on specimens machined from TD nickel bar. The use of miniature torsional pendulum specimens alloived damping measurements to be made on specimens whose axes were parallel to the original bar axis, at 45 deg to the bar axis, and at 90 deg to the bar axis. There was a marked difference in damping with varying specimen orientation, and this was related to the pronounced micro structural anisotropy of this material. Varying the microstructure by cold working plus re crystallization annealing also greatly affected the damping behavior. Recrystallization essentially removed the broad peak found at 400° to 650°C in as-received TD nickel, and in addition greatly lowered the background damping. DlSPERSION hardened metals such as SAP-type alloys (Al + AI2O3) and TD nickel (Ni + 2 pet ThO2) have been developed primarily to improve high temperature strength properties. There have been numerous damping studies on SAP-type alloys,1"9 and one of these6 showed that the damping capacity was greater than that of 99.5 pet pure Al from 25° to 600°C. Several preliminary observations on TD nickel10 and an experimental Ni-ThO2 alloy11 indicated that here, too, the damping capacity was quite high. A high damping capacity in TD nickel, combined with its relatively good high temperature creep strength, could provide an additional benefit for some high temperature structural applications. This work was undertaken to study the internal friction behavior of TD nickel bar over the temperature range 25° to 1100°C. In Ni-ThO2 and Ni-Cr-ThOz alloys, other properties such as steady-state creep rate,12 creep rupture life,12&apos;13 modulus of elasticity,14 and ultimate tensile strength,14 are sensitive to orientation with respect to the primary working direction. Thus, in order to examine anisotropy effects in damping, studies were made on specimens machined with their axes parallel, at 45 deg, and transverse to the original bar axis. MATERIAL DESCRIPTION AND EXPERIMENTAL PROCEDURES The material used in this investigation was from the same £ in. diam TD nickel bar that has been studied previously.13&apos;15 The structure typical of the as-received TD nickel is shown in Fig. 1, and additional details of the structure can be found in Refs. 13 and 15. Elongated grains are parallel to the bar axis and are about 10 to 15 u long and about 1 u in diam. This structure is very stable, since no recrys-tallization or grain growth occurred after annealing for 3 hr at 1300°C.13 The total ThO2 content was 2.3 vol pct and the particles ranged in diameter from 100 to 1000. The average particle diameter was 370Å and the mean planar center-to-center particle spacing was 2340Å. To examine the influence of grain and subgrain structure on damping, a section of TD nickel bar was swaged and drawn at room temperature from 1/2 in. diam bar to 0.040 in. diam wire (99.3 pct re-duction in area). The structure in Fig. 2 resulted after the wire was annealed for 3 hr at 1250°C. The recrystallized grains were much larger than the grains in as-received bar, but still showed considerable elongation in the direction of working. A high

Jan 1, 1970

By L. H. Sjodahl, J. B. Conway

of each particle on grain boundary movement is proportional to the area it occupies on the grain boundary and this increases with the square of the particle radius. In contrast to the impression gained by Tiwari the effectiveness of a particle, as a grain boundary obstacle, increases rapidly as the particle size increases. The counterbalancing factor in a dispersion of constant volume (e.g., those considered by Zener) is of course the rapidly diminishing number of particles, a situation which does not exist in thoria dispersed materials where the volume fraction of thoria remains constant. Although it has been assumed that the Zener approach is valid for the sake of the above argument, it is open to the following objections: 1) It assumes that the effect of many small particles along a grain boundary is cumulative and does not take into account the possibility of each small particle being overcome separately. In this case the boundary will not be able to move forward until the largest particle on the boundary has been overcome. This means that the rate controlling factor will be the rate at which a few relatively large particles are overcome with the remaining small particles playing a negligible role. 2) When the dispersion consists of very small particles the interparticle spacing is usually small compared to the grain size and most particles are located away from grain boundaries where they can play no part. The most efficient dispersion, from a purely geometrical viewpoint, is one where the particle spacing is equal to the grain size so that all the particles are on grain boundaries. Tiwari&apos;s second point that voids cannot prevent re-crystallization seems to be unfounded as several workes20-23 have shown that voids alone can retard grain boundary movement and recrystallization. To further convince Tiwari, Fig. 17 shows a void in deformed TD Nichrome holding back a recrystallization interface. Tiwari&apos;s explanation for the effect of voids on recrystallization, i.e., they reduce local strain energy and hence lower the driving force for recrystallization may be valid in itself but is irrelevant to the present case where even complete recrystallization after ONE of the more recently proposed expressions for describing stress-strain behavior is that due to Voce.1,2 This equation is usually written: s =s8 ?(s8?so)e??/?c [l] where s is the true stress, ? is true strain, cC is a constant called the characteristic strain, s8 is the asymptotic stress approached at high strain values, and so is the threshold stress at which the plastic deformation begins. While this expression has not been universally accepted as yet it does contain certain features which are consistent with experimental stress-strain behavior. In a more recent publication Hsu, Davies, and Royles3 employed the concept of generalized strain proposed by seth4 and identified a method for linearizing the stress-strain plot. In this approach the generalized strain was given by: where 7 is the generalized strain, 1 is the instantaneous length, 1, the datum length, and n is a constant called the "coefficient of strain measure". A value of n was said to exist which would yield the linearity: s —s+ S[.-(tf] [3] In recent studies of both these approaches, it has been found that while the Voce equation and the gen-

Jan 1, 1970

By J. L. Thompson

There are two basic forms of the LPG-slug process: the gas driven and the water driven. The pressure required for miscibility between gas and LPG prohibits the use of the gas-driven LPG process in shallow reservoirs. The water-driven LPG slug process normally exhibits good sweep efficiency. However, displacement of the LPG by water is poor. An improvement in this process appears possible by injecting a slug of carbon dioxide between the LPG slug and the water drive. Laboratory experiments were conducted in homogeneous linear systems to determine the effect of pressure on the various displacement zones. In the carbon dioxide-LPG displacement zone, the effect of pressure on the displacement efficiency is negligible above the miscibility pressure. However, the displacement efficiency decreases linearly with decreasing pressure below the miscibility pressure. With water displacing carbon dioxide, it was found that the recovery of carbon dioxide after water breakthrough can be predicted from its solubility in water. A displacement test was conducted with LPG and carbon dioxide slugs large enough to avoid interference between the oil-LPG, LPG - carbon dioxide and carbon dioxide - water displacement zones. Under these conditions, essentially complete oil and LPG recovery was obtained. However, a substantial amount of carbon dioxide was left in the core at water breakthrough. INTRODUCTION It has been shown in homogeneous linear systems that essentially complete oil recovery can be obtained by displacement with a miscible fluid such as LPG. Economic considerations dictate that the valuable LPG also be recovered. Methods proposed for recovering the LPG include (1) displacement with natural gas at a pressure high enough to make the two fluids miscible1 (the disadvantage of this method is that the required pressure of about 1,500 psi is too high for shallow reservoirs) and (2) displacement of the LPG with water2 (principal disadvantage is that a large amount of LPG remains in the formation because of poor displacement efficiency). This paper treats an improvement in the water-driven LPG slug process3,4 where carbon dioxide is injected between the LPG and water. Carbon dioxide is completely or at least partially miscible with propane and soluble in water; thus, displacement efficiency is improved at both ends of the carbon dioxide slug. To minimize effects of other variables, all experiments were conducted in linear core systems. GENERAL PROCESS DESCRIPTION The displacements of propane by carbon dioxide and carbon dioxide by water are considered separately, assuming enough of each is injected to prevent mutual interference. Displacement descriptions are confined only to the part of the pore volume containing mobile fluids unless otherwise specified. The schematic representation is given in Fig. 1. Starting at the producing well, a zone containing only oil is followed by a zone containing a single-phase mixture of propane and oil. The concentration of propane increases in the direction of the injection well and ultimately grades to pure propane. Then follows a zone containing a mixture of propane and carbon dioxide in continuously varying proportions until 100 percent carbon dioxide is reached. In this zone, the concentration of carbon dioxide in the immobile water phase also varies from zero to full saturation. Whether the displacement of propane by carbon dioxide is of complete or partial miscibility depends on pressure and temperature (Fig. 2). If the horizontal line representing the prevailing pressure intercepts the boundary curves of the phase envelopes for the prevailing temperature (i.e., if the pressure is lower than the critical

By W. A. Stickney, J. W. Town

Tests demonstrated that aqueous solutions of sodiu~n sulfide would dissolve over 95 pct of the cinnabal- in 5 pct Hg flrotation concentrates and 60 to 90 pct of the cinnabav in low-grade ol-es. Double-leach tests showed that potassiutn sulfide would dissolve 90 pct of the avsenic sulfide in Hg-As satnples and only 1 to 10 pct of the Hg; the sodium sulfide would then dissolve 80 to 90 pct of the rernaining Hg and 30 to 70 pct of the vemaining As. 1 HIS paper describes the extraction, by alkaline sulfide solutions, of mercury from cinnabar-bear ing ores and flotation concentrates. Leaching time and solution temperature had minor effects on mercury extraction when compared to the effects of reagent quantity and ore type and grade. Cinnabar, although readily soluble in sodium sulfide, was only partially soluble in potassium sulfide and essentially insoluble in ammonium sulfide. A double leach process was developed to extract selectively the arsenic from Hg-As products with K2S and to treat the residue with sodium sulfide-hydroxide solutions to extract the mercury.&apos; Mercury was then recovered from the pregnant solutions either by precipitation with metallic aluminum or by electrodeposition. The solubility of HgS in alkaline sulfide solutions was first reported by Volhard in 1878.&apos; The first reported commercial application was made in 1915 when Thornhill applied the method to the treatment of an amalgamation tailing.3 Mullhollen, in 1911. described the chemical reaction of HgS with Na,S and alkaline hydrate to be:4 Most investigators have reported using a 4-pct sodium sulfide and a 1-pct sodium hydroxide soluti~n.3-4 An increase in temperature or excessive dilution of the solution causes the reaction to be reversed. Church Holmes described a similar process used for the extraction of antimony from silver concentrates at the Sunshine Mining Company&apos;s mill at Kellogg. Idaho.5 More recently. Erspamer and Wells reported the results of leaching studies on a Hg-Sb ore from Alaska.6 EXPERIMENTAL PROCEDURE Leaching tests were made on samples of mercury ore from eight deposits in Oregon, Washington, and Idaho. In addition. tests were made on flotation concentrates from seven of the samples as well as a flotation concentrate from an operating mill. Since previous investigators reported reagent requirements greatly in excess of that required by the equation HgS + Na2S = HgS . Na2S, initial studies were made on chemically pure HgS. Results showed that the reaction actually required about 1 g of Na,S per g of HgS in an aqueous solution rather than 0.338 g of Na,S as indicated by the equation. To check further the matter of reagent requirements, Na2S and HgS were mixed together in equal mole ratios. Water was then added, a drop at a time, until the components reacted; X-ray diffraction analyses showed no HgS nor Na,S present. The yellow hydrate compound which formed would not redissolve until about three additional mole equivalents of Na,S were added to the solution. This indicated that a stable solution would require at least 4 moles of Na2S for each mole of HgS. While these implications may be valid for pure HgS, the possibility of entirely different results caused by the existence of other elements present in ores and concentrates was recognized. Consequently, experiments of the same order were made on samples of a flotation concentrate from a producing mill. The concentrate, containing about 18 pct

Jan 1, 1962

By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952

By Donald Ofte, L. J. Wittenberg

The absolute viscosity coefficients and activation energies for viscous flow of bismuth, lead, and zinc are reported. The viscosities were measured in an oscillating cup viscosimeter from nearly 1000°C to within 1 deg of the melting point of zinc; 2 deg of the melting point of lead; and in the supercooled condition of bismuth, 9 deg below the melting point. Two methods of relating the change in the viscosity coeflicient with temperature were compared. From the plot of the logarithm of viscosity (77) as a function of reciprocal absolute temperature (1/T), the equations of the lines which fit the data are: AS a part of the Reactor Fuels and Materials Research program at Mound Laboratory, precise measurements of the physical properties of liquid metals are of interest because the desirability for a low vapor pressure liquid coolant in high-temperature nuclear power plants has focused attention on the properties of the liquid metals.&apos; Also, a clearer understanding of the liquid metal state can be achieved when better measurements are available. For these reasons, the viscosity values of certain liquid metals have been determined. The viscosities of the liquid metals, bismuth, lead, and zinc are measured in an oscillating cup viscosi-meter. In this apparatus the liquid is sealed in a right-circular cylindrical cup which is attached to a torsion fiber so that the system forms a torsion pendulum. The damping effect of the molten metal upon the normal oscillations of the torsion pendulum is a function of the viscosity of the liquid. This method is advantageous because of the small amount of sample required (8 to 10 cc), the ease of remote operation of the apparatus in a vacuum system, and the containment of the liquid metal in a hermetically sealed, nonreactive, tantalum crucible. With the liquid metal sealed in the crucible, loss of liquid by vaporization and chemical reactions with atmospheric gases are prevented. Additionally, an absolute viscosity determination is obtained which avoids the sources of possible error in a relative measurement. The difficulties in a relative method include the repetitious cup calibrations, and the uncertainty inherent in the practice of calibration of the apparatus at room temperature and extrapolation to the high temperatures necessary for the investigation of most liquid metals. The oscillating cup viscosimeter was first described by Meyer in 1891.2 The first complete mathematical treatment offering an absolute measurement of viscosity with this type of apparatus was proposed by Andrade and chiong3 in 1936 for an oscillating sphere filled with a liquid. This solution was modified to include a right circular cylinder by Hopkins and Toye4 in 1950, and R. Roscoe5 in 1958. Roscoe&apos;s treatment for the calculation of the viscosity of a liquid at a particular temperature from the logarithmic decrement and period of oscillation of the torsion pendulum was used in this investigation. A detailed description of the method of calculating the viscosity from these measurements has been reported earlier.&apos; This calculation has been programmed for the IBM 704 and IBM 1620 computers for expedition of the otherwise laborious calculations. APPARATUS The cutaway view of the apparatus in Fig. 1 shows the suspension system within the high vacuum enclosure. The low residual gas pressure. maintained between 1 x 10-4 and 5 X 10-6 mm Hg during a determination, avoided both air drag on the pendulum and

Jan 1, 1963

By W. L. Falke, A. A. Cochran

A basic problem in connection with manganese is to find economical ways to utilize domestic resources. As a part of its program to conserve domestic mineral resources and to reduce dependence of foreign sources, the Bureau of Mines had conducted extensive research to broaden manganese technology and to find economical, technically-feasible processes for recovering manganese from these low-grade resources. This paper analyzes some of the major difficulties which have been encountered in previously proposed processes for treating low-grade manganese ores and discusses a process which may circumvent many of these difficulties. Vast deposits of low-grade manganese ore exist in the U.S., yet domestic production is insignificant compared to the more than 2 million tons of ore imported yearly into this country.&apos; A basic problem in connection with manganese is to find economical ways to utilize domestic resources.2 As a part of its program to conserve domestic mineral resources and to reduce dependence on foreign sources, the Bureau of Mines has conducted extensive research to broaden manganese technology and to find economical, technically feasible processes for recovering manganese from these low-grade resources. Although a great many processes have been proposed for treating domestic manganese resources, a failing of many of them is that too many steps are involved for economical operation.&apos; Some of the major processes that have been proposed were reviewed by Norman and Kirby.3,4 Chlorination processes have become increasingly useful as a means of recovering valuable metals from raw materials, because the relative cost of chlorine (Cl2) and hydrogen chloride (HC1) has decreased through the years, and because the corrosion resistance of materials of construction has been improved. The objective of these processes is to form metal chlorides that are more volatile or water-soluble than are the corresponding oxides or sulfides; these compounds then can be separated from the gangue or other minerals by volatilization or leaching. Several chlorination processes for the recovery of manganese have been investigated by the Bureau of Mines5-8 and others; the major chlorination processes were reviewed in 1963, and their main features were compared.4 In all these processes, the simultaneous leaching or volatilization of iron chlorides with manganese chloride (MnCl2) is a problem, and the more iron that is present, generally the greater the problem. The leaching step is not highly selective, and the product of this step is, at best, suitable only for the production of ferromanganese or for further processing to remove iron. The product of the volatilization step is, in all cases, a mixture of iron and manganese chlorides that contains too much iron even for ferromanganese production, and must undergo additional processing steps for iron removal. THERMODYNAMIC CONSIDERATIONS The literature indicates that the desired chlorination reactions will proceed at practical rates at temperatures near 1200°K (927°C). Free energy changes at 1200°K for the critical steps of the reduction and chlorination reactions9-11 follow: Most of the research on chlorination processes for manganese recovery has been done with HC1 rather than with C12, for the following three main reasons: 1) Recycling of the chlorinating agent, which is economically vital, appeared to be easier for HC1

Jan 1, 1968