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By John Chipman, Wayne L. Worrell

Using recent thermodynamic data for the carbides and oxides of tantalum, columbium, and vanadium, the stable solid phases aboue 1300°K and at 1 atm CO(g) pressure in each M-C-O system have been determined. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures necessary to obtain these metals by carbothermic reduction under reduced pressures. TANTALUM, columbium, and vanadium react with carbon to form the M,C and MC carbide phases. The M,C carbides have narrow homogeneity ranges, but the MC phases possess considerable ranges of homogeneity.' The free energies of formation of the MC carbides were recently measured, and those of MC and M2Ccarbides have been estimated., (The notations MC and MC denote, respectively, the carbide compositions at the carbon-rich and at the metal-rich boundaries of the homogeneous MC phase.) In this paper, these carbide data are combined with thermodynamic data for the oxides to predict the stable phases in the Ta-C-O, Cb-C-O, and V-C-O systems at specified temperatures and oxygen pressures. M-C-O PHASE DIAGRAMS The solid phases in equilibrium above 1300°K for each M-C-0 system are shown in Figs. 1, 2, and 3. Above 1300°K, the vapor would consist entirely of carbon monoxide; and these phase diagrams were obtained by specifying the vapor pressure of CO(g) to be 1 atm. The temperature at which any two solid phases become unstable is specified along the two-phase equilibrium lines in each diagram. To simplify the diagrams, all solid phases in the Ta-C-O and Cb-C-O systems are represented as stoichiometric compounds. However, the homogeneity ranges of VO and VC are indicated, because they form a complete series of solid solutions.3 It also should be noted that the homogeneity range of

Jan 1, 1964

By Daniel R. Shawe

Ore deposits of the western U.S. are divisible broadly into two genetic groups, a smaller one that fits the plate tectonic model of subduction and a larger one that appears unrelated to subduction. Some of the middle Paleozoic and lower-middle Mesozoic ore deposits in the western U.S. are associated with eugeosynclinal rocks and lie a few hundred kilometers west of reconstructed continent margins. These deposits probably formed as a result of subduction beneath oceanic or thin continental crust that was analogous to subduction predicated for the Kuroko massive sulfide deposits of Japan. Some middle Mesozoic porphyry copper deposits may have formed east of the continental margin when subduction-generated magmas were emplaced high in continental crust in a manner analogous to subduction-generated magmas that formed the Andean porphyry copper deposits. Most Cretaceous-Cenozoic ore deposits lie in a broad region extending many hundreds of kilometers east of the continent margin and characterized by conjugate tectonic zones, high terrestial heat flow, and low seismic velocity in the upper mantle. The deposits likely were formed in relation to magmas generated along the conjugate tectonic zones during differential northwestward drift and internal wrenching of the continental plate.

Jan 1, 1978

By J. W. Freeman, J. P. Rowe, R. F. Decker

HEAT-to-heat variations in properties of an alloy of constant nominal chemical composition have been a perplexing problem to the metallurgist. These heat-to-heat differences have been especially baffling in high-temperature metallurgy. In order to establish fundamental reasons for these heat-to-heat variations, the National Advisory Committee for Aeronautics has sponsored and financially assisted an extended research program on heat-resistant alloys at the University of Michigan. As part of the program to find the contribution of processing variables, Frey, Freeman, and white' studied effects of heat treating on nickel-base alloys and Ewing and reeman' investigated effects of hot-working practice on N155 alloy. To extend the program to the study of effects of melting practice on high-temperature properties, a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 pct A1 composition was selected for experimentation. The objective of this program was to establish the melting-practice variables which influenced the hot-working characteristics and creep-rupture properties and, at the same time, establish the metallurgical mechanisms for the effects. During the course of the investigation of practices using vacuum melting, it became increasingly evident through chemical analyses supplied by industrial concerns that a major variable was melt reaction with the crucible. This paper is devoted to the results of this phase of the melting-practice study. EXPERIMENTAL PROCEDURES Experimental 10-lb heats were induction melted in the University of Michigan vacuum-melting unit with the melting practices outlined in Table I. Aim analysis for the basic alloy, in wt pct, for all heats was as follows: Cr Co Mo Ti Al 20.0 15.0 4.0 3.1 3.1 Mn Si C Ni 0.12 0.12 0.08-0.15 Bal. Small amounts of boron and zirconium were added to certain heats as listed in Table I. These additions

Jan 1, 1959

By R. E. Reed-Hill

A simple accurate graphical method for orienting fcc crystals using (111) slip traces on a single surface is described. Solutions placing the pole of the surface in a unit stereographic triangle are obtained using a Wulffnet, a (111) standard projection showing the four (111) planes, and a (111) standard projection ruled into unit stereogmphic triangles. The multiplicity of solutions is described in relation to this method. AN accurate, rapid single-surface technique for orienting fcc crystals, using (111) slip or twin traces, has been a matter of continuing interest, as evidenced by the periodic appearance of papers on this subject.'-4 This note presents a new method possessing some advantages over those previously reported. It is an analog to the technique for hcp metals5 where the solution is based upon a stereographic rotation of the specimen surface on a (0002) standard projection that contains the planes of the possible features that might account for the observed traces. In the hexagonal solution, the axis of rotation is the basal-plane trace in the surface. In the fcc case, the axis of rotation is one of the observed ( 111) slip or twin traces. It has been observed that the solution is greatly facilitated if the indicated movements of the (111) traces during the rotation of the surface are plotted directly on a paper copy of a Wulff net as shown schematically in Fig. 1. The trace selected to represent the axis of rotation is assumed to fall at the north-south poles of the Wulff net. The directions of the other traces are then plotted as points at the proper angles around one-half of the basic circle of the net. The loci of points corresponding to the movements of these traces (directions) during a 90-deg rotation of the surface, about the polar axis of the net, are then easily and accurately drawn by following the appropriate small circles on the Wulff net. The solutions to the problem are obtained with the aid of a (111) standard projection of the (111) planes, see Fig. 2. This is normally a Xerox copy of a carefully drawn master made on high-quality tracing paper. The (111) standard projection is superimposed over the Wulff net and rotated about its center until the points of intersection of the loci of surface traces, drawn on the Wulff net, and the great circles representing the (111) traces, all lie along a common meridian of the Wulff net as demonstrated in Fig. 3. This latter great circle represents a possible position of the surface. The pole of this plane is then plotted on the (111) standard projection. Its location in a unit stereographic triangle may be readily obtained by superimposing (over the standard projection) another tracing paper (111) standard projection subdivided into unit stereographic triangles. The result of this last operation is shown in Fig. 4. MULTIPLICITY OF THE SOLUTIONS The maximum possible number of (111) traces on a single grain surface is four. Any one may be selected as the axis about which the surface is rotated. Corresponding to each such choice are three possible surface-pole orientations, related to each other by a simple 120-deg rotation about the pole of the (111) basic circle. This is a direct result of the threefold symmetry of the (111) standard projection. Since each of the four rotations will normally give a different set of three-pole positions, there are, accordingly, twelve possible solutions. Each of these twelve solutions places the surface pole in the same relative position in a stereographic triangle so that all are crystallo-graphically equivalent. Accordingly, only a single solution is required to obtain a basic orientation of the crystal. It should be noted, however, that the orientations obtained by reflecting* any of these twelve orien- *The reflected orientations may be obtained by a 90-deg rotation of the opposite sense to that shown in Fig. 1. This rotation places the correspond-ing trace loci in the lower hemisphere of the Wulff net rather than in the upper hemisphere. tations through the surface are also possible orientations that could account for the surface traces. Thus, a given set of four traces always corresponds to a pair of basic orientations related by reflection through the specimen surface. This ambiguity can only be re-

Jan 1, 1967

By Donald N. Rosenblatt

I would like to commend the author on his description of Pinto Valley's plant, and its interesting innovations. The author's discussion of 18 ft in diameter by 21 ft long primary ball mills (the largest wet ball mills made to date) is of considerable importance to those who have been engaged in the field of studying ball mill liner wear as it relates to various grinding installations. While it is stated that the mills have operated on a fixed tonnage and therefore it has been difficult to determine the best liner pattern, calculations from the data in the paper indicates that for mills 1, 2, 5, and 6, the tonnage per hour varies from a low of 223 for mill No. 1, up to a high of 314, for mill No. 2, while mills 5 and 6 calculate 285 and 246, respectively. Analysis of the wear patterns for the single wave liners used in mill No. 1 as compared to the double wave liners in mill No. 2, suggests that the author's data may tell more than he suspects about liner wear to be expected and thus what should be a best pattern selection from what may appear to be only limited hours of operation. [Fig. A] is a reproduction of author's [Fig. 10], to which wear forecast patterns [F-1 and F-2] have been added. Forecasts are based on many previous studies of large diameter ball mill operations over many years of field service. Calculations from the first-wear pattern provide an initial wear rate of only 13 lb of liner per 100 sq ft of shell liner surface per day, or 0.031 lb per to: ground. However, the second wear pattern is ac-

Jan 1, 1978

By S. A. Lever, R. Hultgren

The solidus is usually the least satisfactorily determined portion of a phase diagram. Cooling curves, which succeed well with the liquidus, show the solidus inaccurately or not at all because of segregation which occurs during freezing. Heating curves of carefully homogenized alloys might be expected to indicate accurately the solidus, but they are seldom used. Dynamic methods involving heating or cooling are never completely satisfactory because of uncertainty as to whether equilibrium is attained. A static method in which the specimen may be allowed hours, days, or even weeks to attain equilibrium is to be preferred. In a static method a solid solution, for example, is first made thoroughly homogeneous, then heated to successively higher temperatures. After sufficient time at each temperature to assure equilibrium, some property is measured which should alter strikingly when melting begins. Microscopic examination can be used to detect the beginning of melting, but the method is tedious since the specimen must be quenched, sectioned, polished, and etched before each examination. Of all the physical properties which change on melting, electrical resistance is probably the most satisfactory to measure. The measurement may be made while the specimen is at temperature without damage to the specimen. It may be repeated indefinitely to ascertain when equilibrium has been achieved. Measurements may be made on a single specimen over the whole range of temperature. Most metals approximately double their resistance on melting. Since an accuracy of a few tenths of a percent is easy to achieve, the method is highly sensitive to the beginning of melting. In spite of these advantages, which have been perceived for a long time,l,2 a reasonable search of the literature has failed to reveal a single case in which the method has been satisfactorily applied in practice to the determination of solidus temperatures. The use of electrical resistance measurements appears to have been confined in practice to changes in the solid state. In the work described in the following pages we have applied the electrical resistance method to the solidus of the lead-tin system. We have found the method to be convenient, reproducible, and highly sensitive. We chose the lead-tin system because it leads to few technical difficulties. Furthermore, a number of determinations of solidus have been made in this system by various methods and results could be checked against them. However, all published results are not in good agreement with one another, so this work should help in determining the solidus more precisely. The Lead-tin Diagram Because of its commercial importance, there have been numerous investigations of the lead-tin diagram. The results of the most recent work on the solidus are indicated in Fig 7, as well as the results of the present work. The works of Honda and Abe3 and of Stockdale4 agree fairly well with each other and with the present work. Jeffery's5 data indicate the solidus to be about 50°C lower. Honda and Abe3 used differential thermal analysis on both heating and cooling cycles. Stockdale4 used the microscopic method and also differential heating curves. Stockdale's results were about 4" higher than those of Honda and Abe at low tin contents and lower at higher tin contents. These results also agree with those of Rosen-hain and Tucker.= Jeffery5 used electrical resistance measurements of the alloy as it was being heated or cooled. Apparently he did not attain equilibrium as his results are about 40°C lower than those of Stockdale4 or Honda and Abe.3 MATERIALS AND METHODS The lead and tin used were of high purity. They were supplied by the American Smelting and Refining Co., who gave the following analyses: Lead: silver, 0.0016 oz per ton; copper, 0.0008 pct; cadmium, 0.0007 pct; zinc, 0.0002 pct; arsenic, 0.0003 pct; antimony, 0.0002 pct; bismuth, 0.0005 pct; tin, 0.0001 pct; iron, 0.0020 pct; lead (by difference), 99.995 pct. Tin: antimony, 0.037 pct; arsenic, 0.020 pct; bismuth, 0.004 pct; cadmium, trace; copper, 0.025 pct; iron, 0.004 pct; lead, 0.020 pct; nickel and cobalt, 0.005 pct; silver, 0.0005 pct; sulphur, 0.005 pct; tin (by .-difference). 99.88 pct. One hundred grams of metal with the desired proportions of lead and tin was weighed out to the nearest one-tenth of a milligram. The mixture was placed in a silica crucible, covered with charcoal, and melted in a reducing atmosphere in a gas-fired furnace. The alloy was well stirred. Chemical analysis of two of the alloys checked closely with the weighed portions. The compositions of the remainder of the alloys were taken directly from the weighings, without chemical analysis.

Jan 1, 1950

By A. Y. Bethune, W. G. Woolf

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process' for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt's earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.'s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By W. G. Woolf, A. Y. Bethune

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process' for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt's earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.'s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By H. K. VAN POOLLEEN, W. Hurst, H. C. Bixel

In an earlier publication* I showed the development of the instantaneous point source solution for a well producing at a constant rate at the center of a system of two radial, adjoining sands of different permeabilities. I also showed how a wellbore radius could be incorporated if this were the development required. For the purpose of that paper and the point I wished to make, this solution served. It yielded a simplifying solution of sands in series identified by Eqs. VI-26 and VI-27. (These equations are reproduced in part by Bixel and van Poollen as their Eq. 3, Page 302.) I am well aware that the simplified solutions are approximations. The facts that these Ei-functions satisfy the diffusivity equation and meet the boundary conditions both at the well and at the interface between sands, and that the earliest time considerations yield zero pressure drop, are evidence that the solutions are good approximations. This was the purpose for these formulas, which I interpret that where the permeabilities are of finite order of magnitudes in the respective media, the relations give satisfactory answers. However, from the authors' point of view there are reservations, which leads me to consider their entire generalization as illustrated in their Figs. 1 through 14. What I understand from their storage capacity, relationship Fs, which is the ratio of the product of porosity and compressibility of Sand II to Sand I, that is employed here by the authors as a correlative means of identifying one figure from another, there is nothing in the exact mathematics that supports such a term as a means of correlation. This is taken out of context, unsustained that this applies. Here the mathematics are known, where the true correlation is the diffusivity term of one sand to another. This entails permeability that refers back again to the term M in their paper for the transmis-sibility of fluid from one sand to the other that should have also been a part of this storage capacity. In Figs. 8 through 14, which purported to show the simplified equation following this correlation, there are apparent discontinuities for M equal to or less than 0.1000 that differ from the trends for greater values of M. In this connection there is no reference radius given for this cumulative pressure drop in the paper that would permit me to make these calculations. However, what is clear for M equal to 0.1000 or less we are treated to almost a closed barrier at the interface; a condition entered by the writers without qualification. This across-the-board treatment of these simplified formulas, whatever the motive of the authors, enters into a range of permeabilities that even I as the contributor would have reservations that such could apply. Under comparable conditions I would be looking at a closed reservoir or some facsimile for such. The extent to which the approximation or the exact equations pertain is not evident in the generality offered by Bixel and van Poollen in their paper. Only when they or other writers show the comparison of the pressure distributions within the formations can one be able to judge the rational limits to subscribe to the simplified formulas.

Jan 1, 1969

Discussion of the paper of Leonard Waldo, presented at the New York meeting, February, 1911, and printed in Bulletin No. 76, April, 1913, pp. 555 to 559. HERBERT HAAS, San Francisco, Cal. (communication to the Secretary*):-Referring to Leonard Waldo's paper on Temperature Conversion Tables, I believe the following formulas can be easily remembered, and by reference to the thermomter scales of Fahrenheit (F.), Celsius (C.), and Réaumur (R.), their derivation and relation are at once understood n° F. = 4/9 (n°-32) R. = (n°-32) C. n° C.=(9/5 n° + 32) F. = 4/5 n° R. n° R.=(9/4 n° + 32) F. = 5/4 n° C. As the freezing point of water is at 32° F., corresponding to 0° C. and 0° R., 32 must be deducted from the Fahrenheit degrees when these are converted into C. or R. degrees. Likewise, to C. or R. degrees converted into F. degrees 32 must be added. The fractions 4/9 and 5/9 and their reciprocals are obtained thus:

Jan 5, 1913

L50 Adirondack L1 Alaska L2 Arizona L58 Arkansas L66 Billings Petroleum L3 Black Hills L4 Boston L5 Carlsbad Potash L6 Central Appalachian L60 Central New Mexico L7 Chicago L8 Cleveland L9 Colorado L57 Colorado Plateau L10 Columbia LII Connecticut L55 Dallas L12 Delta L65 Denver Petroleum L13 Detroit L14 East Texas L15 El Paso Metals L71 Evangeline L45 Florida L54 Fort Worth L16 Gulf Coast L61 Hobbs L62 Hugoton L68 Illinois Pet Basin L17 Kansas L18 Lehigh Valley L52 Lou-Ark L47 Mexico L19 Mid-Continent L20 Minnesota L56 Mississippi L21 Montana L22 Nevada L64 Niagara Frontier L23 New York L67 New York Petroleum L25 North Pacific L24 North Texas L26 Ohio Valley L27 Oklahoma City L28 Oregon L63 Panhandle L29 Penn -Anthracite L30 Permian Basin L51 Peru L31 Philadelphia L32 Pittsburgh L33 St Louis L34 San Francisco L59 San Joaquin L35 Southeast L36 Southern Calif L69 Southern Calif Pet L53 South Plains L37 Southwest Texas L48 Southwest Alaska L38 Southwest N Mex L44 Spindletop L39 Tri-State L40 Upper Peninsula L41 Utah L70 Venezuela L42 Washington, D C L43 Wyoming L49 West Central Texas L46 Philippine

Jan 1, 1956

By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.' More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.' This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.' These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer's6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By John E. Conley

THE slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5 ¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. USE OF WASTE SLATES FOR MAKING AGGREGATES The lightweight-aggregate industry has been discussed elsewhere4.5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. REQUIREMENTS FOR RAW MATERIALS As pointed out by Hughes,4 the light-weight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of any low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig. I illustrates the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200'K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:'4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3'7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

INTERNATIONAL ENGINEERING CONGRESS This Congress will be held under the auspices of five National Engineering Societies, of whi h the Institute is one. The sessions will be held in 11 sections and the proceedings will be published in 10 volumes of 500 pages each, of which Volume 8 will contain the papers and proceedings on Mining Engineering and Metallurgy. The membership fee of $5 will entitle the holder to the volume of General Proceedings and Index, and, in addition thereto, any other single volume chosen. Other volumes may be subscribed for according to a sliding scale depending upon the number of volumes taken. The Institute will have a meeting in San Francisco during 1915, and it is desirable for our members to join the International Engineering Congress at in early date in order that their support of the enterprise may be given in its early stages, when it is most needed.

Jan 2, 1914

By Michael Perch, Charles C. Russell

Nearly 75 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank' standardized by the American Society for Testing Materials. Although this method of classification has been an American stand¬ard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1944

By O. E. Palasvirta

Close examination of most so-called new processes in mineral dressing reveals that they were conceived and developed a long time ago. High-intensity magnetic separation is no exception. Although its application in iron ore beneficiation seems new, in Germany the process has been commercially successful for almost two decades. High-intensity separators have long been standard equipment in the glass sand industry; they have also been used in concentrating some of the more unusual paramagnetic minerals. The basic features of an induced-rotor, high-intensity magnetic separator were described by Désiré Korda in Paris in 1905,1 and many patents have since been issued for improvements on the original design. Fig. 1 shows the basic design of an induced-rotor separator. Several U. S. manufacturers have been supplying induced-rotor separators for many years, but these are all devices of relatively low capacity, not suitable for treating such low-cost commodities as iron ore. On the other hand, two German manufacturers are offering induced-rotor separators of high capacity, both proven in the field.

Jan 12, 1959

By R. Maddin, R. Pond

THERE have been many recent studies of nonequi-librium alloy structures using specimens which have been formed by rapid solidification.' The general methods for achieving nonequilibrium structure utilize high velocity impingement of a liquid metallic droplet(s) and one or more substrates of relatively high heat conductivity. Specimens formed by current popular techniques are small and have various forms of irregular geometry which severely limit their use for many measurements of physical or mechanical properties. As a result of geometric limitations most research has been restricted to X-ray diffraction, electron microscopy, and to a small degree, electrical resistivity. Recently several attempts in mechanical property evaluation have been reported.2,3 A technique for casting large quantities of regular, rectilinear, continuous metallic fibers has existed for a number of years.4 We have utilized this technique with some slight modifications to produce nonequi- librium alloy structures. The apparatus is composed of a small open tube furnace, a pneumatic cage which raises and lowers a graphite ejection mold, and a

Jan 1, 1970

By C. R. Kuzell

ALTHOUGH furnaces constructed of refractory brick have been oper-ated for many decades, there has always been an unfulfilled desire by the operators for a less arduous and more satisfactory method of patching weak spots and burned-out zones in order to postpone and to effectively extend the termination of a furnace campaign. Not only has this desire frequently arisen when small spots have approached incipient failure while the furnace structure as a whole was still in good condition, but also when larger areas showed signs of needing replacement. The availa-ble methods have been arduous, sometimes dangerous, inefficient with respect to the life of new refractory material used, and nearly always have necessitated interruption of the continuity of the furnace operations and therefore reduction in furnace production during the period of time required for the repair work. Most of these older methods have involved the replacement of masonry by refractory shapes in the weakened areas. Many attempts have been made to develop a method of patching the burned-out areas by spraying granular refractory material upon old surfaces. While some success has been attained in attempts to renew the grooved, corroded side walls and fettling, and the edges of hearths, there have been no known successful applications of the spraying method in patching the underside of arches of operating furnaces. The method developed recently at the Clarkdale smelter of the United Verde Branch of Phelps Dodge Corporation, at Clarkdale, Ariz., and described in this paper, has been found to be not only convenient and successful with respect to patching vertical or inclined surfaces, but has met with a marked degree of success in patching the parts of furnace arches that are exposed to flame, the successful result being obtained with-out interruption or interference with the continuity of furnace operations. ? It may be described as a method of renewing the interior refractory sur-faces of operating furnaces by pneumatic spraying of an aqueous suspen-sion of finely divided particles of refractory material. It has been used

Jan 1, 1939

By E. S. Bumps, H. D. Kessler, M. Hansen

The titanium-rich end of the Ti-AI phase diagram has been determined to the compound TiAI3 (62.7 pct Al), thus joining the aluminum-rich portion previously investigated by others and completing the diagram. Micrographic analysis and X-ray diffraction were the chief methods used to determine the phase relationships. THE Ti-Al phase diagram has been investigated as part of a program on titanium phase diagrams for the Wright Air Development Center. Included in the available information concerning the phase relationships in titanium-rich Ti-A1 alloys is a brief statement by Brown' that: "aluminum raises the transformation temperature to 1000°C (183Z°F)." This observation is interesting in that it is the first example of a metallic alloying component raising the transformation temperature of titanium, and consequently widening the field of the a solid solution. Busch and Freyer' presented resistivity data which indicated the formation of titanium-rich solid solutions of 1 and 3 pct A1 alloys prepared by powder metallurgy methods. Duweza found that there is only one other intermediate phase other than the known compound TiA1, (62.7 pct Al). This phase, designated as y, is of variable composition; its crystal structure is of the AuCu type and is therefore based on the composition TiAl (36.02 pct Al). Earlier work on the constitution of the aluminum-rich alloys has been reviewed by Hansen, and need not be discussed here. The tetragonal crystal lattice of TiAl,, as found by Fink, Van Horn, and Budge," was confirmed by Brauer." Recently, Schubert7 has reported that TiA1, is homogeneous within a limited composition range; however, the solubility limits were not given. The Ti-A1 phase diagram as presented in. this paper was determined by micrographic analysis of alloys containing from 1 to 62 pct Al, annealed at and quenched from temperatures between 700" and 1400°C. The phases and phase ranges investigated extend to the compound TiA1, (62.7 pct Al) to join the aluminum-rich end of the system determined by other investigators, thus completing the diagram. Methods of Investigation Preparation of Alloys: Iodide titanium, 99.9+ pct pure, obtained from the New Jersey Zinc Co., and high-purity (99.99+ pct) aluminum sheet from the Aluminum Co. of America were used to make up alloy ingots weighing 10 to 20 g. Detailed descriptions of melting techniques have been presented previously for work on the Ti-Mo and Ti-Cb> nd Ti-Si" phase diagrams. Briefly, the melting practice consisted of arc melting an accurately weighed charge in a copper block crucible insert in a non-consumable tungsten electrode furnace, under helium at atmospheric pressure. All ingots were carefully weighed after melting to detect possible losses. Comparison of weight before and after melting showed no appreciable weight changes. Also, chemical analyses were in close agreement with nominal compositions, Table I. The diagram as presented is, therefore, based on nominal compositions. Alloys were prepared having the following nominal aluminum contents: 1 ... 36 (1 pct increments), 38, 40, 41, 42.5, 44, 45, 46, 47.5, 49 . . . 64 (1 pct increments), 67, 70, 80, and 90. Ingots with up to 14 pct A1 were cold-pressed various amounts in order to increase the rate of attaining equilibrium structures on heat treatment. The amount of cold deformation that could be applied decreased with increasing aluminum content, until alloys containing 12 pct A1 or more cracked after only a few percent deformation. Annealing Treatments: Samples annealed at temperatures of 700" to 1000°C were sealed in

Jan 1, 1953