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By Orville R. Lyons

DISCUSSION Judson S. Hubbard (The Humphreys Investment Co., Denver)—In this very interesting paper several brief references are made to the Humphreys spiral, a device used for cleaning fine coal. In Table I, Plants 76 and 77, data are given on spiral performance treating Raton and Trinidad coal. The fine coal, as fed to the spiral in these instances, is actually a table middling, hence the more easily treated material was previously removed and a large number of particles were present which were difficult to clean. Mr. W. M. Bertholf of the Colorado Fuel and Iron Co. presented a paper in February, 1946, Cleaning Table Middlings from a Coal Washery with the Humphreys Spiral Concentrator, from which I quote: "In considering the results of our tests it should be noted that the feed was our table middling, and that any real separation is a 'moral victory' as there is little material that could properly be called coal and practically no heavy rock, the consequences being that previous attempts to clean the middling have not at all been successful." Referring again to Table I, Plants 72, 73, 74, and 75, these data were obtained by Yancey and Geer and others and presented at the February 1950 Meeting, AIME, in a paper entitled Laboratory Performance Tests of the Humphreys Spiral as a Cleaner of Fine Coal. Results shown for those tests involve all particles from 8 mesh through the colloids, which admittedly is not an ideal situation for spiral feed if much refuse is contained in the —80 mesh or —100 mesh size range. As an illustration of the effect of treating too broad a size range, let us consider Plant No. 75, Kentucky No. 9 seam. Spiral feed was 8 mesh x 0. Now had this been 8x100 mesh the percentage of misplaced material would have been 8.0 pct instead of the reported 15.26 pct. Similar comparisons can be made on the other data presented with respect to the spiral. Other types of equipment show a similar trend in that whenever too fine a size is treated in a given unit process the percentage of misplaced material increases. Since the spiral is working near the finer end of the size range, it will sometimes be advantageous to treat the entire range of —8 mesh material rather than to deslime and make a fair showing on, say, the +80 or + I00 mesh. Desliming is subsequently done in any case in the dewatering or thickening operation. Results obtained by spiraling any given coal depend on factors too numerous and complex to discuss here, but there are strong indications that proper preparation of feed to the spiral can improve results obtained on some of the raw coals tested. This is clearly pointed out at the end of the aforementioned paper by Yancey and Geer. "The spiral is an extremely simple device which involves no moving parts and is constructed almost entirely of unmachined castings. Since it is such an uncomplicated mechanism, operation is simple and virtually foolproof. These characteristics, which go far toward insuring low cost operation, are attractive attributes in any coal cleaning unit." Certain equipment used in conjunction with the spiral has resulted in a decrease in the percentage of misplaced material, notably in actual practice the launder screen which is used to remove objectionable high ash fines from a spiral-washed coal product. Private correspondence with the U. S. Bureau of Mines has intimated that an additional yield of coal is possible by flotation of the spiral middling. Possible future improvements and developments may result from other methods now under consideration. Finally, some compromise must be made between the best metallurgical performance and the best practical or economical results. Mr. Lyons emphasizes in his summary this objective of overall economy in selection of equipment. G. B. Walker (American Cyanamid Co., Stamford, Conn.)—I had the pleasure of reviewing the draft of this paper and my curiosity was aroused by the data given for Tromp plants, in that all of the examples shown appeared to be 2-product separations, whereas all the Tromp plants with which I am familiar have been 3-product units. The data given for plants No. 101 and 102 appear to be taken from Tromp's brochure on his process and represent the results obtained at the Dominale plant in Holland which was operated for many years by Mr. Tromp. The plant, which was designed to treat 58 tons per hr, was sampled while treating 35 tons per hr of 3Y4x-in. coal. Example 101 appears to conform to what would result if the middling product were calculated into the refuse product, while Example 102 represents the calculation of the middling into the coal product. It is believed that Examples 103 and 104 represent the operation of the Willem-Sophie Mine in Holland recalculated on the same basis. In checking the English examples given by numbers 14, 15, 16, and 17, the same procedure seems to have been followed. These results have, apparently, been taken from an article in Colliery Engineering in August 1941, describing the initial operation of the Williamthorpe Colliery of the Hardwick Colliery Co. Two vessels are employed in this plant, one to treat soft coal and one to treat hard coal. Example No. 14 presents the results that could be obtained from the soft coal bath if the middling were calculated into the refuse, and Example 15 the results when the middling is calculated into the coal. Examples 16 and 17 represent the same expedient in the case of the hard coal bath. Of interest to this discussion is the fact that during the past year the Simon-Carves Engineering Co. in England has installed in the Williamthorpe plant their new "Sim-Car" medium cleaning system which is based on magnetic extraction and control and which is licensed under the Heavy-Media Separation Processes patents by the American Zinc, Lead and Smelting Co. This system has been described in the December 1951, issue of Colliery Engineering. It is reported that since the Williamthorpe Colliery was changed from the Tromp system of medium cleaning to the Magneto-Motive method of medium control the opera-

Jan 1, 1953

By Orville R. Lyons

DISCUSSION Judson S. Hubbard (The Humphreys Investment Co., Denver)—In this very interesting paper several brief references are made to the Humphreys spiral, a device used for cleaning fine coal. In Table I, Plants 76 and 77, data are given on spiral performance treating Raton and Trinidad coal. The fine coal, as fed to the spiral in these instances, is actually a table middling, hence the more easily treated material was previously removed and a large number of particles were present which were difficult to clean. Mr. W. M. Bertholf of the Colorado Fuel and Iron Co. presented a paper in February, 1946, Cleaning Table Middlings from a Coal Washery with the Humphreys Spiral Concentrator, from which I quote: "In considering the results of our tests it should be noted that the feed was our table middling, and that any real separation is a 'moral victory' as there is little material that could properly be called coal and practically no heavy rock, the consequences being that previous attempts to clean the middling have not at all been successful." Referring again to Table I, Plants 72, 73, 74, and 75, these data were obtained by Yancey and Geer and others and presented at the February 1950 Meeting, AIME, in a paper entitled Laboratory Performance Tests of the Humphreys Spiral as a Cleaner of Fine Coal. Results shown for those tests involve all particles from 8 mesh through the colloids, which admittedly is not an ideal situation for spiral feed if much refuse is contained in the —80 mesh or —100 mesh size range. As an illustration of the effect of treating too broad a size range, let us consider Plant No. 75, Kentucky No. 9 seam. Spiral feed was 8 mesh x 0. Now had this been 8x100 mesh the percentage of misplaced material would have been 8.0 pct instead of the reported 15.26 pct. Similar comparisons can be made on the other data presented with respect to the spiral. Other types of equipment show a similar trend in that whenever too fine a size is treated in a given unit process the percentage of misplaced material increases. Since the spiral is working near the finer end of the size range, it will sometimes be advantageous to treat the entire range of —8 mesh material rather than to deslime and make a fair showing on, say, the +80 or + I00 mesh. Desliming is subsequently done in any case in the dewatering or thickening operation. Results obtained by spiraling any given coal depend on factors too numerous and complex to discuss here, but there are strong indications that proper preparation of feed to the spiral can improve results obtained on some of the raw coals tested. This is clearly pointed out at the end of the aforementioned paper by Yancey and Geer. "The spiral is an extremely simple device which involves no moving parts and is constructed almost entirely of unmachined castings. Since it is such an uncomplicated mechanism, operation is simple and virtually foolproof. These characteristics, which go far toward insuring low cost operation, are attractive attributes in any coal cleaning unit." Certain equipment used in conjunction with the spiral has resulted in a decrease in the percentage of misplaced material, notably in actual practice the launder screen which is used to remove objectionable high ash fines from a spiral-washed coal product. Private correspondence with the U. S. Bureau of Mines has intimated that an additional yield of coal is possible by flotation of the spiral middling. Possible future improvements and developments may result from other methods now under consideration. Finally, some compromise must be made between the best metallurgical performance and the best practical or economical results. Mr. Lyons emphasizes in his summary this objective of overall economy in selection of equipment. G. B. Walker (American Cyanamid Co., Stamford, Conn.)—I had the pleasure of reviewing the draft of this paper and my curiosity was aroused by the data given for Tromp plants, in that all of the examples shown appeared to be 2-product separations, whereas all the Tromp plants with which I am familiar have been 3-product units. The data given for plants No. 101 and 102 appear to be taken from Tromp's brochure on his process and represent the results obtained at the Dominale plant in Holland which was operated for many years by Mr. Tromp. The plant, which was designed to treat 58 tons per hr, was sampled while treating 35 tons per hr of 3Y4x-in. coal. Example 101 appears to conform to what would result if the middling product were calculated into the refuse product, while Example 102 represents the calculation of the middling into the coal product. It is believed that Examples 103 and 104 represent the operation of the Willem-Sophie Mine in Holland recalculated on the same basis. In checking the English examples given by numbers 14, 15, 16, and 17, the same procedure seems to have been followed. These results have, apparently, been taken from an article in Colliery Engineering in August 1941, describing the initial operation of the Williamthorpe Colliery of the Hardwick Colliery Co. Two vessels are employed in this plant, one to treat soft coal and one to treat hard coal. Example No. 14 presents the results that could be obtained from the soft coal bath if the middling were calculated into the refuse, and Example 15 the results when the middling is calculated into the coal. Examples 16 and 17 represent the same expedient in the case of the hard coal bath. Of interest to this discussion is the fact that during the past year the Simon-Carves Engineering Co. in England has installed in the Williamthorpe plant their new "Sim-Car" medium cleaning system which is based on magnetic extraction and control and which is licensed under the Heavy-Media Separation Processes patents by the American Zinc, Lead and Smelting Co. This system has been described in the December 1951, issue of Colliery Engineering. It is reported that since the Williamthorpe Colliery was changed from the Tromp system of medium cleaning to the Magneto-Motive method of medium control the opera-

Jan 1, 1953

By T. F. Mueller, P. A. Witherspoon

For the case of an infinite radial system operating at constant terminal rate, the reservoir engineer often uses the "point source" solution of the diffiusivity equation to study pressure interference effects. At early times and at short distances from the inner boundary these solutions are invalid. The amount of error is often not precisely defined because of mathematical difficulties. Work presented here shows that, if dimensionless time is defined appropriately, previous solutions of the pressure equation can be displayed .as a family of curves on one chart. These solutions include the point source solution (referred to in the field of hydrology as the Theis solution) and other solutions obtained with digital computer methods. With these curves, an exact evaluation of the pressure drop within a reservoir or an aquifer can be made by the engineer. Examples of field problem solutions are presented. In most reservoirs the error involved when the Theis solution is employed is often negligible; whereas, in the calculation of interference effects in an aquifer, a substantial error can occur through such an approach. INTRODUCTION Flow equations are used in petroleum engineering to study the behavior of individual wells and reservoirs. In the case of wells, the pressure response at the wellbore face is the major point of interest; whereas, in the case of reservoirs, the pressure response at the interface of the aquifer boundary is sought. To aid in such studies, the flow equations have been solved in terms of the behavior at these two inner boundaries. Only limited work has been published in regard to the pressure conditions away from these points, i.e., within the reservoir or aquifer. Theis and Mortada are among the few who have reported on this problem. The Theis approach employs the exponential integral and is valid for pressure conditions that occur some distance away from the flow disturbance. It is derived from the concept of a point source, as opposed to a flow across some finite area. The Mortada results, on the other hand, are valid at all points within the reservoir or aquifer. They are presented in terms of dimension less ratios of the radius where the pressure is desired to the radius where the flow rate is measured. Their main use, in the past, has been in aquifer studies. The published results are presented in the form of graphs that are limited to a maximum radius ratio of 64. These graphical results are cumbersome to interpolate at non-integral radius ratios, so that one may be forced to utilize a rather involved analytical expression presented by Mortada. BASIC EQUATIONS The solutions of Mortada and Theis are both based on the diffusivity equation as applied to the case of an infinite radial system subject to a constant terminal rate. The equation is obtained by combining the material balance equation with Darcy's flow equation. The assumptions implicit in the use of this equation are as follows: (1) a single fluid is present that occupies the entire pore volume; (2) the reservoir is horizontal, homogeneous, uniform in thickness, and of infinite radial extent; (3) compressibility and viscosity of the fluid remain constant at all pressures; and (4) fluid density obeys the equation Using the diffusivity equation in situations where the above conditions do not hold will result in errors. These errors (not discussed here) but only the errors which arise in the solution of the equation itself. The diffusivity equation for the homogeneous reservoir conditions cited above can be written in cylindrical coordinates, as To obtain a dimensionless equation, so a single solution can be used for applications of different porosity, permeability and fluid properties, the following transformations are usually made: After these transformations are made, Eq. 3 .can be written in dimensionless form, as MORTADA SOLUTION One solution of Eq. 6 has been given by Mortada.

Jan 1, 1966

By J. Weertman

It is shown that conditions suitable for the conversion of straight dislocations into helices are common in crystals hardened either through long-range dislocation interaction or by jog formation on dislocation lines. For dislocations other than screw dislocations or dislocations nearly screw in orientation, helices can be formed with the aid of core difhsion at temperatures low relative to the melting point of the material. It is assumed that, once formed, helices will degenerate into dislocation tangles. THE dislocation tangle is one major dislocation arrangement observed by the transmission electron microscope which had not been predicted previously from dislocation theory. Since first being observed, the tangle itself has become important in applied dislocation theory. The Cambridge school (P. Hirsch) bases part of its theory of work hardening upon this phenomenon.' In spite of the fact that the tangle obviously is a structure of prime importance to a cold-worked crystal, until recently relatively little attention has been paid to the question of exactly why or how tangles arise. It was generally assumed at first that cross slip and perhaps jog formation will lead to tangles. However Wilsdorf and schmitz2 concluded that cross slip cannot markedly contribute to the tangles. The Wilsdorfs and Maddin3'* have proposed that tangles arise by means of prismatic dislocation loops and superjogs which are produced by a precipitation of point defects. Dislocations with superjogs or which have joined with prismatic loops are themselves dislocation sources and they can produce new dislocations, a process they call "mushrooming", which then tangle with each other. There is no question that the Wilsdorfs et al. mechanism as well as the cross slip one can pro- duce tangles. However these may not be the only paths leading to tangle formation. In this paper we wish to consider another way tangles can form. Our work will be based on the theory of dislocation screw We wish to show that whenever a crystal is cold-worked there always is present a "driving force" leading to helix formation and thus to tangle formation. We do not expect to observe well-developed, regular helices in cold-worked metals. Rather we would expect that after a helix is formed random interactions with nearby dislocations will cause a well-developed helical dislocation to go over into an irregular form. A dislocation tangle is, of course, a grouping of dislocations with irregular forms. Therefore we feel that, in accounting for the formation of dislocation tangles, it is sufficient to show that many dislocations in a cold-worked crystal will take on helical form. The crucial step is helix formation. In order to have a straight dislocation assume a helical form, diffusion of vacancies, or interstitials, must occur. Our discussion of tangle formation therefore will be limited to crystals which have been deformed at temperatures ranging from about one fifth to half their absolute melting point. In this tem per a ture range appreciable core diffusion is possible. (There is no problem in explaining tangle formation at temperatures greater than half the melting point. At such temperatures dislocation climb through a bulk diffusion of point defects gives an extra degree of freedom to dislocation motion. This extra freedom of motion makes tangle formation easy.) At temperatures much below one fifth the absolute melting temperature diffusion processes are sufficiently slow that helix formation does not occur. Of course helix or tangle formation could occur in material deformed at very low tempera-tures which was subsequently warmed in order to make the thin specimen necessary for electron-microscope examination. Since within the temperature range of approximately one fifth to half the melting temperature the diffusion of point defects in the core of the dislocation is rapid, we can reasonably assume that within

Jan 1, 1963

By Paul D. Conatore

INTRODUCTION There are important reasons for a discussion of tungsten resources, reserves, and production in the Circum-Pacific area. First, the world's chief tungsten deposits, as well as most of the world's tungsten reserves and production, occur in this region. It is well known that the world's largest tungsten reserves are located in southeastern China and that for many years, the largest individual mine in the world was there. Although China still has the world's greatest tungsten production, the very high-grade scheelite mine of Canada Tungsten Mining Corporation in the Northwest Territories is the largest producer of tungsten today. There is certainly a great quantity of tungsten in Asia, but the strategic importance of this fact is now offset by the wide distribution of mines and production facilities throughout the world, especially in other parts of the Circum-Pacific area such as Australia, Canada, and the United States. In addition, much of the Circum-Pacific area is comprised of Mesozoic-Cenozoic orogenic belts. These global tectonic units are regarded as very favorable for additional tungsten deposits, particularly scheelite-bearing tactites, and consequently, prospecting and exploration will most likely be concentrated in the Circum-Pacific area. Second, tungsten must be regarded as one of the, most important metals of modern industry because of its very special properties. It has the highest melting point, the highest tensile strength at elevated temperatures, and the smallest compressibility of any metal. The metal also possesses a very high density, excellent corrosion resistance, good thermal and electrical conductivity, and a low coefficient of expansion. As a result, tungsten has found increasing importance in a wide range of industries. From the filament in an electric lamp, to cutting tools and drilling bits, to the exotic radiation shields that protect supersonic aircraft and spacecraft, tungsten plays an indispensable role in our daily lives. The primary objective of this paper is to present an overview of important facets of known and suspected tungsten in the Circum-Pacific area. Resources, reserves, current production, planned capacity expansions, and new operations, as well as an assessment of the probability for development of deposits in the Circum-Pacific area, are discussed. RESOURCES The average crustal abundance of tungsten has been estimated at 0.0015 kilograms per tonne. A comparison of the abundance of various metals in crustal rocks to that of tungsten is presented in Table 1, which shows that tungsten abundance is similar to that of its commonly associated metals, tin and molybdenum. Table 1. AVERAGE CRUSTAL ABUNDANCE OF VARIOUS METALS (Grams per Tonne) [ ] With careful thought, it can be realized that tungsten ore deposits result from the concentration of the metal, through normal geologic processes, to levels substantially greater than its average crustal abundance. The minimum technologically and economically workable tungsten concentration, or cutoff grade, is a function of (1) deposit tonnage, (2) mining and milling methods, (3) production tonnage, (4) capital and operating costs, (5) tungsten market conditions, and (6) value of associated recoverable metals. The tungsten cutoff grade that is currently exploitable at a profit varies from 0.09% W03 to 1.55% W03, reflecting concentration factors from 470 to 8200, as shown in Table 2. Table 2. CURRENT TUNGSTEN CUTOFF GRADES [ ]

Jan 1, 1982

By R. G. Grieves, G. Thodos

A method is presented for the accurate calculation of the cricondentherm and cricondenbar pressures of multicomponent hydrocarbon mixtures of known composition. The mixtures may contain six and quite possibly any number of components including paraffins, isoparaffins, olefins, acetylenes, naphthenes and aromatics. The approach is similur to that used for calculating critical pressures and cricondentherm and cricondenbar temperatures. The critical pressure, the normal boiling point and the approximate vapor pressure behavior of each component are all that art required. A stepwise culculation procedure is necessary for mixtures containing more than two components. From an analysis of 22 binary systems and 118 mixtures, the average deviation of calculated cricondentherm pressures from reported values is 2.4 per cent. For nine multicomponent mixtures the average deviation is 1 per cent. Considering 19 binary systems and 108 mixtures, the average deviation of calculated cricondenbar pressures from reported values is 1.7 per cent. For 15 multi-component mixtures, the average deviation is 2.2 per cent. INTRODUCTION A knowledge of the phase behavior in the critical region of multicomponent hydrocarbon mixtures is of value both in industrial processing operations and for the optimum operation of gas condensate reservoirs. Accurate methods of calculating the critical temperatures and critical pressures4,6,7,8,9,23 and cricondentherm and cricondenbar temperatures6p10 of multicomponent hydrocarbon mixtures are available in the literature. If the cricondentherm and cricondenbar pressures could be calculated with equal accuracy, the entire phase diagram of a multicomponent hydrocarbon mixture could be well approximated. The work of Etter and Kay6 is limited to systems containing the normal paraffins and has not been tested on systems containing a heavier component than heptane. In addition, the development of their multicomponent equations is based upon a limited number of mixtures containing from three to six components. Silverman and Thodos have considered systems containing both paraffinic and non-paraffinic hydrocarbons, but their correlation is limited to binary systems and is highly inaccurate for methane systems. Eilerts has done extensive work on the cricondenbar pressure; he has produced an excellent correlation for binary systems. However, his procedure for multicomponent mixtures is chiefly useful for highly complex mixtures requiring a knowledge of the vapor-liquid equilibrium behavior of the mixtures; he has not considered the cricondentherm pressure. The objective of this study was the development of an accurate and rapid method for the calculation of the cricondentherm and cricondenbar pressures of multicomponent mixtures containing all types of hydrocarbons and having a wide volatility range. The approach that was adopted is similar to that used by Grieves and Thodos for cricondentherm and cricondenbar temperaturesl0 and for critical pressures.9 However, methane systems had to be considered separately and a modified stepwise calculation procedure was utilized for the cricondertherm pressure. The correlations were developed in a manner similar to those for critical pressures and cricondentherm and cricondenbar temperatures. Based upon binary data reported in the literature it was observed that the ratios of cricondentherm and cricondenbar pressure to the pseudocritical pressure (molar average), pt/ppc and pp/ppc, respectively, in two-component systems depended upon the mole fraction of the low-boiling component and upon the diversity in properties of the two components. A dimensionless boiling-point parameter Tb,/Tb was chosen to represent the diversity in properties of the components. For a binary system, Ti,'is the molar average of the normal boiling points of the two components involved. For a multicomponent system it is either the molar average of the normal boiling points of all of the components involved or the molar average of the normal boiling point of the pure low-boiling component and of the atmospheric boiling point of the low-boiling-free mixture of

Jan 1, 1965

By D. B. Smith, John Chipman

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

Jan 1, 1953

By Paul Gordon

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

Jan 1, 1965

By C. S. Smith, Chih-Chung Wang

TURNBULL and his collaborators1,2 have developed the theory of homogeneous nucleation as applied, inter alia, to solidification of liquid metals. Vonnegut³ and Turnbull4 have shown that if a liquid metal is subdivided into small droplets a vast majority of them will undercool very considerably before solidification, generally to as low as about 0.8 of the freezing temperature on the absolute scale. The nuclei effective at small degrees of supercooling in bulk metal seem to be internal or surface heterogeneities, relatively small in number. If the metal is subdivided, those droplets that happen to contain such nuclei will solidify at a temperature not greatly below the true freezing point, but only a small part of the whole volume will be affected and the majority of the drops will under-cool to the much lower temperature at which homo- geneous nucleation occurs as a result of fluctuations. It occurred to one of the authors that an appropriate subdivision to give effective freedom from random nuclei is produced during the solidification of many alloys that contain a minor amount of a phase of low melting point, and that one might then expect marked undercooling of the distributed phase. Experimental: The alloys selected for initial study were copper with minor amounts of lead and bismuth, and aluminum with tin. In all these alloys, the major component freezes at a temperature not much below that of the pure metal, and there is little further change in constitution on cooling until the lower melting point constituent freezes in an almost pure state. Cooling curves were taken using the controlled heat flow method permitting approximate specific heats to be obtained. Chromel-alumel thermocouples were used, with the standard emf tables, since extreme precision was not needed. The crucible (3/4 in. id, 5/16 in. wall) was made of B & W K-20 insulating brick. It held about 10 cc of the alloy being investigated. The cooling rate was 2.5" to 2.9°C per min under a controlled temperature difference of 20°. Approximate specific heats were computed from the inverse rate curves together with data from a blank run and from a standard run with a copper cylinder of known heat capacity. The alloys for investigation were made from high-purity metals (99.99+pct) and cast into graphite molds. The castings were machined to fit the crucible and to provide a hole for the inner thermocouple. Cooling curves were taken after heating to a temperature about 50" above the melting point of the minor, lower melting-point, constituent. Results The lead phase in an alloy of copper with 5 pct lead did not undercool more than 3" below the melting point of lead (327°C) either as cast or after annealing to produce a new dispersion of the liquid phase. A copper-zinc-lead alloy with 23.75 pct zinc and 5 pct lead undercooled more but showed no thermal effect below 319°C. A cast alloy of copper with 5 pct bismuth undercooled to 249°C (M.P. bismuth 27l °C), but once solidification started it was completed at the same temperature. This was anticipated, since the bismuth forms a nearly continuous phase between the grains of copper, and a solid crystal nucleated anywhere would rapidly* con- sume the entire network of liquid, unless the physical continuity of the liquid were broken through volume changes, inadequate fluidity, or gas evolution. Similar arguments apply in the case of copper-lead alloys, where the lead-rich liquid forms a network along grain edges, though not grain faces. In both cases there would be a few isolated particles

Jan 1, 1951

By J. M. Roberts, N. Brown

The stress-strain behavior of zinc single crystals was measured over a strain range of 10-6 to 10-2. The phenomenon of macroyielding was observed in detail and plastic strains were detected at almost zero-stress. Closed hysteresis loops were observed during loading and unloading in the strain region of about 10-5. From the hysteresis a frictional stress on the dislocation of about 6 psi was obtained. A preliminary analysis indicates that impurities are primarily responsible for the friction. Nonelastic Strains as much as 10 -4 were recovered depending on the amount of prior deformation. Part of the recovered strain occurs instantaneously upon unloading and the remainder occurs at zero stress. The time dependence of the recovered strain was measured. THIS investigation is concerned with the details of plastic deformation preceding the ordinary yield point as measured with the usual strain sensitivity of about 10-4. The approach leads to internal friction observations in the hitherto neglected frequency range below 10-1 cycles per sec. It is believed that if the phenomenon of macroscopic yielding is to be understood, then the stress-strain curve in the neighborhood of the macroyield point should be greatly magnified. It may then be possible to determine whether macroscopic yielding is a unique event or whether it is a process which begins gradually at a lower stress. In the case of low-carbon steel a unique event obviously occurs at the macroscopic yield point as indicated by a drop in the load, but copper appears to exhibit a gradual transition from the elastic to the plastic state. In zinc the yield point is rather abrupt although the data indicates that some plastic deformation precedes large scale yielding.' One of the purposes of this investigation is to determine whether there is an abrupt transition from the preyield microstrain region to the region of macroscopic deformation. Such a rapid transition would support the concept that there is a critical stress for yielding. The concept that yielding is a unique event associated with such phenomenon as activating a Frank-Read source, freeing the dislocation from solute atoms, dislocations cutting through dislocations, or dislocations moving freely by one another, has been expounded widely on theoretical grounds. It is hoped that highly sensitive measurements of strain in the neighborhood of the macroscopic yield point will shed some light on the event known as the "Yield Point". EXPERIMENTAL METHOD 1) Specimens—High-purity zinc was cast into spherical graphite moulds in air and grown into spherical single crystals by the Bridgman method under a positive pressure of Argon gas. Spectro-graphic analysis of cleaved sections from four crystals showed a purity of 99.994 pet Zn. The specimens were acid machined with an 1/8 in. gage section in a form similar to those used by Parker and co-workers.2 Bausch type grips were fastened to the specimen by Epon VI adhesive. The specimens were oriented so that only [1120] (0001) slip occurred. Fig. 1 shows two of the specimens in the grips. Prior to each test, the gage section of the specimen was given a concentrated HNO3 chemical polish followed by alcohol rinsing and air blast drying. 2) Test Method- The shear tests were performed on an Instron testing machine and the experimental set-up was made very "hard". Strain could be measured to a sensitivity of 10 -6 by means of a capacitance gage extensometer. The design and calibration of this type of extensometer to measure microstrain, as applied to pure shear and tensile tests of metals, will be the subject of a separate paper—therefore, only a brief account will be presented here. The method essentially consists of attaching a

Jan 1, 1961

By M. Cohen, D. J. Blickwede

Quantitative observations concerning the carbide phases in high speed steel are of importance for two general reasons: (1) the carbides, being inevitable constituents of the final structure, exert a direct influence on the properties of the steel; and (2) a substantial proportion of the total alloy content is tied-up in the carbides, and hence the extent of their solution on austenitizing governs the composition of the steel matrix. The latter relationship has a vital bearing on the response of the steel to tempering as well as on its performance in subsequent service. Accordingly, in the course of a long-term study of the behavior of high speed steels, the authors were confronted with the problem of securing quantitative data on the carbide phases. The obvious method for acquiring such information is to isolate the car-bides from the steel and subject them to chemical, X ray diffraction and other measurements. There are well-known extraction techniques which involve the chemical or electrolytic solution of the less noble matrix (ferrite, marten-site or austenite), thus leaving a residue of the carbide phases. However, the results obtained must be scrutinized carefully1,2 since the carbides may be affected by the chemical or electrolytic action. It is the purpose of the present paper to describe the experiments leading to an electrolytic-extraction technique for quantitatively isolating the carbides from both I and hardened high speed steel. Particular attention is paid to the amount, as well as the composition, of the carbides so that the matrix analysis becomes ascertainable by subtraction from the overall steel composition. Illustrative results are given for the M-2 grade of tungsten-molybdenum steel. Review of the Literature The chemical method of dissolving the matrix selectively with respect to the carbides makes use of dilute non- oxidizing reagents such as hydrochloric or sulphuric acid. Although this simple procedure has led to the determination of the cementite composition,3,4 it achieved only limited success because of the interaction between the acid and the carbide residue. Some of the carbides may not only be destroyed in this way, but the hydrogen released is likely to remove part of their carbon as hydrocarbon gases. The electrolytic technique of isolating carbides has the advantage of rapidly dissolving the specimen (anode) in the presence of less reactive solutions than are practicable with the chemical method. This reduces the possibility of chemical attack on the carbides, and furthermore, the hydrogen evolved during the electrolysis is released at the cathode which is not in close proximity to the carbides. The common electrolytes adopted for this purpose are hydrochloric and sulphuric acids.5-l1 Aqueous solutions of ferrous salts have also been used.12,13 A considerable advance in experimental technique was introduced by Treje and Benedicks14 who developed a double-compartment cell for electrolytic extraction, the anode and cathode chambers being separated by a porous diaphragm. A solution of 15 pct sodium citrate, 2 pct potassium bromide and 1 pct potassium iodide was selected for the anolyte, while the catholyte consisted of a 10 pct solution of copper sulphate, with copper serving as the cathode. This type of cell has a number of desirable characteristics: 1. The anolyte has a pH value close to 7, at least at the beginning of the run. 2. The iron that dissolves from the anode-specimen forms a water-soluble complex ion with the citrate, thereby preventing the precipitation of iron hydroxide (which would contaminate the carbide residue) despite the neutrality of the solution. 3. Copper deposition instead of hydrogen evolution occurs at the cathode, and this avoids an increasing concentration of hy-droxyl ions which (in an otherwise neutral solution) might cause the precipitation of insoluble hydroxides. 4. Contamination of the anode chamber by copper sulphate is inhibited by the porous diaphragm. Houdremont and coworkers15 applied the above method (with the further refinement of excluding oxygen during the electrolysis, washing and drying) to the extraction of carbides from a series of plain carbon steels after various heat treatments. They had quantitative success only with specimens in the annealed condition, and concluded that the size and shape of the carbide particles play an important role in the isolation process, with large spheroids exhibiting the least tendency to decompose during the electrolysis. Up to the present time, the citrate double-cell has not been used to any extent for isolating the carbides of high alloy steels, apparently on the grounds that the complex carbides are more resistant than cementite to attack in the simpler acid electrolytes. In particular, Bain and Grossmann7 and Gulyaev10.10a have employed the hydrochloric acid cell for their investigations of the carbides in high speed steel.* It will be demonstrated here that this type of cell is capable of yielding quantitative results in the case of high speed steel, and actually has certain advantages over the more complicated double cell. However, in order to provide a rigorous test of the quanti-tativeness of electrolytic procedures for the problem at hand, both methods were studied in considerable detail.

Jan 1, 1950

By W. L. Prehn, Adele Chambers, R. L. Slobod

The centrifuge has been found to be an extremely useful tool for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. The use of the centrifuge for determining the properties of small core plugs has been discussed in the literature,',' but practically no experimental evidence has been presented justifying the use of this method in preference to other methods (mainly disc method) now in use. Data have been accumulated and are now presented demonstrating the advantages of the centrifugal method, some of which are: (1) rapid establishment of equilibrium, (2) excellent precision yielding very reproducible results, (3) availability of high pressure differences between phases, (4) simple operational procedure, and (5) ability to establish connate water, residual oil, or to obtain complete capillary pressure curve in one day or less. A commercially available centrifuge capable of speeds up to 3,800 rpm, and a high speed attachment providing a maximum rate of rotation of 18,000 rpm were used in this work in conjunction with core holding tubes designed specifically for this application. In view of the outstanding advantages associated with the use of the centrifuge the conclusion has been drawn that this method should be used in place of the more tedious, slower, and less reliable disc method for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. INTRODUCTION The need for accurate values of connate water, residual oil, and capillary pressure curves in reservoir engineering has been recognized for many years, and the extent of the effort devoted toward solving these problems is reflected in the large number of papers3-" which have appeared in the literature during the past decade. Most of the methods discussed in the recent literature employ a porous disc as a semi-permeable membrane to separate two immiscible phases and make pos-ible the application of an explicit difference in pressure between two phases in the core. Thus, in the determination of the capillary pressure curve the wetting phase (water) is displaced by the non-wetting phase (air or oil). Several investigators1,2 have used centrifugal forces to develop pressure differences between phases. As a result of the first work' in this field the conclusion was reached that "the more rapid centrifugal method for measuring irreducible saturation may have equal value, (compared to use of discs) but more work is required to establish this point." This work was followed in 1945 by a more detailed study2 in which the concepts of this experimental work were more clearly enunciated. A method for calculating saturation for any given speed of rotation based on the observed volume of water displaced was developed and a wider application of the method was suggested. The absence of any subsequent pertinent literature on this subject is interpreted as indicating that no additional work has been completed to substantiate or deny the earlier claims and suggestions of promise contained in the original papers on this subject. One purpose of this report is to provide evidence designed to establish the practical value of centrifugal methods in determining core properties such as connate water and capillary pressure curves. It is also our purpose to suggest a broadening of the scope of this tool to include determinations of residual oil by gas or water drives. THEORY AND PRACTICE IN USE OF CENTRIFUGE Hassler and Brunner2 have clearly presented the basic concepts involved in the use of the centrifuge by relating the performance of a small core in a field of high acceleration to the

Jan 1, 1951

By R. L. Slobod, W. L. Prehn, Adele Chambers

The centrifuge has been found to be an extremely useful tool for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. The use of the centrifuge for determining the properties of small core plugs has been discussed in the literature,',' but practically no experimental evidence has been presented justifying the use of this method in preference to other methods (mainly disc method) now in use. Data have been accumulated and are now presented demonstrating the advantages of the centrifugal method, some of which are: (1) rapid establishment of equilibrium, (2) excellent precision yielding very reproducible results, (3) availability of high pressure differences between phases, (4) simple operational procedure, and (5) ability to establish connate water, residual oil, or to obtain complete capillary pressure curve in one day or less. A commercially available centrifuge capable of speeds up to 3,800 rpm, and a high speed attachment providing a maximum rate of rotation of 18,000 rpm were used in this work in conjunction with core holding tubes designed specifically for this application. In view of the outstanding advantages associated with the use of the centrifuge the conclusion has been drawn that this method should be used in place of the more tedious, slower, and less reliable disc method for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. INTRODUCTION The need for accurate values of connate water, residual oil, and capillary pressure curves in reservoir engineering has been recognized for many years, and the extent of the effort devoted toward solving these problems is reflected in the large number of papers3-" which have appeared in the literature during the past decade. Most of the methods discussed in the recent literature employ a porous disc as a semi-permeable membrane to separate two immiscible phases and make pos-ible the application of an explicit difference in pressure between two phases in the core. Thus, in the determination of the capillary pressure curve the wetting phase (water) is displaced by the non-wetting phase (air or oil). Several investigators1,2 have used centrifugal forces to develop pressure differences between phases. As a result of the first work' in this field the conclusion was reached that "the more rapid centrifugal method for measuring irreducible saturation may have equal value, (compared to use of discs) but more work is required to establish this point." This work was followed in 1945 by a more detailed study2 in which the concepts of this experimental work were more clearly enunciated. A method for calculating saturation for any given speed of rotation based on the observed volume of water displaced was developed and a wider application of the method was suggested. The absence of any subsequent pertinent literature on this subject is interpreted as indicating that no additional work has been completed to substantiate or deny the earlier claims and suggestions of promise contained in the original papers on this subject. One purpose of this report is to provide evidence designed to establish the practical value of centrifugal methods in determining core properties such as connate water and capillary pressure curves. It is also our purpose to suggest a broadening of the scope of this tool to include determinations of residual oil by gas or water drives. THEORY AND PRACTICE IN USE OF CENTRIFUGE Hassler and Brunner2 have clearly presented the basic concepts involved in the use of the centrifuge by relating the performance of a small core in a field of high acceleration to the

Jan 1, 1951

By Lendall P. Warriner, Blandford C. Burgess

Jasper County lies just north of the geographical center of Georgia, bounded on the west and north by the Ocmulgee River. The county seat, Monticello, is approximately 65 miles east-southeast of Atlanta and 40 miles north of Macon. It is served by the Macon-Athens branch of the Central of Georgia Railway Co. and by five paved highways converging from adjoining county seats. Farming and lumbering are the principal local occupations. About half the county is covered with pine and mixed hardwoods; a large part of the forested land is owned by the Soil Conservation Service of the Department of Agriculture in its Piedmont Land Utilization Project. The topography is one of gently rolling field and forest with occasional hills rising 100 ft or: more above the creek beds. Though annual rainfall is in the neighborhood of 60 in., most of it falls in torrential downpours of short duration which tend rapidly to erode the red soil and convert the country roads to greasy tracks of red mud.

Jan 1, 1949

By C. W. Macgregor

The observation of the flow layers, or Luders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-st'eel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are ill reality traces of wedge-shaped flow layers and are formed by the inter-section of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45" to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ncr, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45" to the principal stress direct-tions at the point. As examples of the latter may be mentionecl the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subject,ed to internal pressure only, etc. IIencc if the flow layers are observed from an experiment, the shear-st'ress trajectories —the curves indicating the direct,ions of the maximum shearing stresses in the body—may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45" to the principal stress directions, the family of principal stress trajectories, or the curves irldicating the directions of the principal stresses, may be thus obtained Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowai~; in duralumin and other aluminum alloys, by Dawidenkow,~Elam,~ Fell4 an(l others; in copper and copper-alloy crystals, by Elam;~ in brass by Elam;3 in brass wires by deForest;" in higher carbon steels, tungsten steel, and

Jan 1, 1939

By C. W. MacGregor

The observation of the flow layers, or Luders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-st'eel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are ill reality traces of wedge-shaped flow layers and are formed by the inter-section of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45" to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ncr, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45" to the principal stress direct-tions at the point. As examples of the latter may be mentionecl the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subject,ed to internal pressure only, etc. IIencc if the flow layers are observed from an experiment, the shear-st'ress trajectories —the curves indicating the direct,ions of the maximum shearing stresses in the body—may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45" to the principal stress directions, the family of principal stress trajectories, or the curves irldicating the directions of the principal stresses, may be thus obtained Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowai~; in duralumin and other aluminum alloys, by Dawidenkow,~Elam,~ Fell4 an(l others; in copper and copper-alloy crystals, by Elam;~ in brass by Elam;3 in brass wires by deForest;" in higher carbon steels, tungsten steel, and

Jan 1, 1939

By E. E. Barker

Although flotation was known to be a successful process prior to 1312, Utah Copper Co.'s ores were not entirely treated by this process until 1923. Experiments had been conducted, of course, prior to that time, and in February, 1917, the first unit of the Arthur plant was changed over from gravity concentration to flotation. On May 16, 1918, the entire Arthur plant was on flotation, excepting the coarse concentrate which was tabled prior to fine grinding. The reasons for the delay in adopting flotation at these plants were, first, that it was decided to await the outcome of the litigation with the Butte & Superior Mining Co., which began with an injunction served on Oct. 3, 1911. This litigation continued for years. Then the demands on the plants in the war years 1916, 1917 and 1918, really precluded any further drastic changes during that period, as all efforts were bent on maximum tonnage, and the cry of tonnage, rather than of recovery, was the major issue. The postwar depression followed these years of intensive production, so that it was not until 1922 that the Magna plant was equipped to use this process. Excepting, then, the amount of coarse concentrate that was tabled, 1923 was the first year when the Utah Copper Co.'s ores were on a full flotation basis. Effect of Flotation on Ore Reserves The object of this paper is to point out the effect that flotation has had on the operations of the Utah Copper Co. In 1905, when D. C. Jackling began making history in copper, the ore reserves were 34,000,000 tons, with a grade of 2 per cent. copper and a mill capacity of 700 tons daily. The point of cut-off between nonprofitable and profitable grades was 1.2 per cent. A few years later the capacity was increased to 6000 tons, when 1.1 per cent. became the point of cut-off. Ore reserves had climbed to 80,000,000 tons, having a grade of 1.9 per cent. In 1911 there was an ore reserve of 300,000,000 tons, with a grade of 1.5 per cent. and a cut-off of 1 per cent.; in 1918 the ore reserve was approximately 400,000,000 tons, and a grade of 1.38 per cent., and point of cut-off 0.95 per cent., based on normal costs and prices. Up to this

Jan 1, 1928

By William Kent

ABOUT a year ago, the writer had occasion to assist Mr. John L. Gill, Jr., of the Pittsburgh. Car-wheel Works, in making a trial of his new testing machine. A piece of Bessemer steel, of about .34 carbon, was used as a test-piece, turned to a sectional area of one square inch for a length of five inches between shoulders, and pro¬vided with large round heads, which were fitted to what is called the " Wade grip." Measurements of elongation, accurate to , 1/10000 of an inch, were made by a special apparatus containing two micrometer screws, with electric contact attachment. The machine was operated by hand-power. Readings of elongation were taken at each increment of 2000 pounds stress per square inch, up to 44,000 pounds, the elongation corresponding to the latter figure being .0088 inch. The elongations up to this point remained almost exactly proportional to the stresses, the strain diagram, as shown on the Plate, from the origin to the point A, being a straight line (the deviation of no observation from the straight line being greater than .0002 inch). There being no indication of an approach to the elastic limit, the attendant at the hand-wheel and scale-beam was told to proceed as usual and move the poise forward 2000 pounds, or to 46,000, and turn the wheel until the beam was balanced. Noticing that the beam did not rise in the usual time, and that the elongation was increasing rapidly, the writer called to the attendant to stop turning the hand-wheel and to push the poise backwards until the scale-beam balanced. Instead of balancing at between 44,000 and 46,000 pounds, as was expected, it balanced at 40,000 pounds, and the elongation had increased to .0343 inch (or more than four times that recorded at 44,000 pounds), as plotted at the point B, the dotted line between A and B showing the supposed course of the strain diagram between these two points. Immediately upon recording the elongation the writer said to Mr. Gill, who was standing alongside: "This phenomena is without a parallel in my experience, and I know of but one way to account for it. The piece must actually be broken in its interior, through a flaw or weak portion of the metal. The test-piece is now equivalent to a tube, with

Jan 1, 1880

By William Kent

About a year ago, the writer had occasion to assist Mr. John L. Gill, Jr., of the Pittsburgh Car-wheel Works, in malting a trial of his new testing machine. A piece of Bessemer steel, of about .34 carbon, was used as a test-piece, turned to a sectional area of one square inch for a length of five inches between shoulders, and provided with large round heads, which were fitted to what is called the " Wade grip." Measurements of elongation, accurate to 1/10000 of an inch, were made by a special apparatus containing two micrometer screws, with electric contact attachment. The machine was operated by hand-power. Readings of elongation were taken at each increment of 2000 pounds stress per square inch, up to 44,000 pounds, the elongation corresponding to the latter figure being .0085 inch. The elongations up to this point remained almost exactly proportional to the stresses, the strain diagram, as shown on the Plate, from the origin to the point A, being a straight line (the deviation of no observation from the straight line being greater than .0002 inch). There being no indication of an approach to the elastic limit, the attendant at the hand-wheel and scale-beam wits told to proceed as usual and move the poise forward 2000 pounds, or to 46,000, and turn the wheel until the beam was balanced. Noticing that the beam did not rise in the usual time, and that the elongation was increasing rapidly, the writer called to the attendant to stop turning the hantl-wheel and to push the poise backwards until the scale-beam balanced. Instead of balancing at between 44,000 and 46,000 pounds, as was expected, it balanced at 40,000 pounds, and the elongation had increased to .0343 inch (or more than four times that recorded at 34,000 pounds), as plotted at the point B, the dotted line between A and B showing the supposed course of' the strain diagram between these two points. Immediately upon recording the elongation the writer said to Mr. Gill, who was standing alongside: "This phenomena is without a parallel in my experience, and I know of but one way to account for it. The piece. must actually be broken in its interior, through a flaw or weak portion of the metal. The test-piece is now equivalent to a tube, with

Jan 1, 1880

By A. E. Bibb, F. W. Kunz

A platelet form of zirconium hydride was found in zirconium and ZY-1 wt pct U single crystals containing hydvogen in the range of 50 to 100 ppm. The habit planes for the hydride plateletg in the zirconium crystals were found to be {1012}, {1121}, and (1122) while the habit planes in the ZY-1 wt pct U crystals were {1121), {1123}, and (1.231). With the exception of the {1231} plane, these have been identified as the twin planes in zirconium. The different effect of hydridc on the mechanical puoperlies of zirconium at high and low strain rates has been explained in terms of the defornzation mechanism and the habit planes of the hydride. ZIRCONIUM and zirconium-base alloys are considered for many nuclear reactor applications, where the pick-up of hydrogen is a distinct possibility, if not an unavoidable occurrence. An excellent example of this is the absorption of hydrogen by zirconium and its alloys during aqueous corrosion, where as much as 30 pct of the hydrogen produced by the corrosion reaction is picked up by the metal. Under the proper conditions, the absorbed hydrogen would precipitate as zirconium hydride and consequently alter the mechanical and physical properties of the zirconium-base alloys. The knowledge obtained from a study of the crystallographic aspects of the hydride precipitation is necessary for the interpretation of the observed changes in the mechanical and physical properties. The deleterious effect of hydrogen on zirconium-base materials is not always observed in normal slow tensile loadings at or above room temperature, but becomes immediately obvious under impact loading, where the energy absorbed decreases with increasing hydrogen content,' and in notched specimens where triaxial loadings are attained.2 This effect is of serious consequence in the applications of Zr where shock loads or high strain rates are experienced. The purpose of this investigation was to determine the crystallographic planes of the Zr and Zr-1 wt pct U matrices upon which zirconium hydride will precipitate and to correlate these with the observed mechanical property data. PROCEDURE Crystal Growth—Single crystals of Zr and Zr-1 wt pct U alloy were used in this investigation. The Zr crystals were made from sponge that had a typical analysis as shown in Table I. Large grains were grown in this material by rapid cooling an arc-melted charge in a button furnace. This operation undoubtedly lowered the volatile impurity concentration below those listed in Table I. Back-reflection Laue patterns of these large grains showed the presence of considerable substructure and lattice distortion within each grain. It was found that an 18-day anneal in an argon atmosphere at 840°C (a high a heat-treatment) followed by furnace cooling, resulted in the further growth of the large grains and removed the detectable substructure ana lattice distortion. Equiaxed crystals with a cube edge of approximately 1/4 in. were produced in this manner. Large crystals of Zircaloy-2 (1.5 wt pct Sn, 0.15 wt pct Fe, 0.1 wt pct Cr, 0.05 wt pct Ni) also were produced by this technique but the large amount of substructure formed could not be removed by annealing. The Zr-1 wt pct U solid solution crystals were produced from an alloy rod consisting of Westing-house-Foote hafnium-free crystal bar zirconium and depleted uranium. The chemical analysis of the alloy is also given in Table I. Three-inch sections were cut from an 0.120-in.-diameter alloy rod and tapered to a fine point on each end. The samples were sealed in evacuated Vycor tubes, homogenized for 5 hr at 1000°C in the ß-phase field, and slowly lowered in a gradient furnace into the a phase (800°C), annealed for 60 hr at this temperature to produce grain growth and furnace cooled. This technique produced large grains approximately 1/2 to 3/4 in. long over the entire cross section of the rod, which were free of observable substructure. Metallographic examination up to X1000 did not show the existence of any second phase in these grains. Crystal Orientation—All crystals were abraded on fine emery paper to produce two flat surfaces 90 deg to each other. The crystals were analyzed by the standard Back-Reflection Laue technique to obtain the crystal orientation with respect to the abraded surfaces. The Back-Reflection Laue Photograms of all crystals used were clear and sharp indicating that the crystals were free from any substructure that could be detected by these means. Hydriding—Only samples containing four to five grains were used for hydriding. Samples that exhibited fine grained patches were discarded. The samples were hydrided using the following technique. After etching in 48 vol. pct HNO3, 48 vol. pct H2O, and 4 vol. pct HF (48 pct) solution, the specimens

Jan 1, 1961