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By A. H. Geisler, J. H. Keeler

Preferred orientations in rolled and annealed titanium sheets were determined by the Geiger counter spectrometer X-ray diffraction technique. Five annealing textures dependent upon the temperature range of annealing were found, and in order of increasing annealing temperature pendent upon the temperature range are: 1—a deformation like texture, 2—a rotated inorder a-recrystallization temperature texture, 3-a retained u-recrysraIlization texture, on annealing at lower temperatures of the ß-region, 4—a transformation texture based on recrystallized a and predicted by the Burgers' relationship, and 5—a ,ß-cube texture. These results are examined in terms of current theories of recrystallization textures. UMEROUS investigators have described the tex- ture obtained by cold rolling the hexagonal metals, titanium, zirconium, and beryllium, which have c/a ratios less than that of ideal packing, 1.633. The basal planes are rotated out of the rolling plane, about the rolling direction, so that the basal poles are tilted toward the transverse direction as shown schematically in Fig. la. In all instances but one,' it was also reported that the [1010] direction was parallel to the rolling direction (see Fig. lb). Hot rolling has been reported as causing a similar tilt of the basal poles in the transverse direction (see Fig. la) and causing the [1010] direction also to be parallel to the rolling direction as shown schematically in Fig. lb. Annealing after deformation does not appreciably change the tilt of the basal poles in the transverse direction." Beryllium2-7 continues to have the [1010] direction in the rolling direction after annealing, and similar observations for titanium and zirconium' . have been reported for annealing at fairly low temperatures, again as in Fig. lb. At higher annealing temperatures, however, the recrystallized grains of titanium" and zirconium have an orientation such that the [1120] direction is approximately in the rolling direction, although the basal poles are still inclined in the transverse direction. Figs. la and lc show the resulting orientations schematically. This change in orientation has been described as a nominally ±30° rotation of the hexagonal crystallites about the basal poles of the cold rolled texture and is apparent from the results which are summarized in Table I for investigations with the X-ray diffraction technique employing film. The angles y, , and ß are indicated in Fig. 2 which represents the stereographic projection of (1070) poles for the mean orientation of a pole figure. Texture determinations for titanium using the Geiger counter spectrometer have provided similar results except that in some instances additional components of the texture were proposed, as shown by the summary of data in the upper half of Table 11. On the other hand, the spectrometer technique, when applied to zirconium,* has revealed a splitting Recently completed studies of the textures of annealed zirconium", show zirconium to possess textures very similar to those reported here for titanium. Therefore, much of this discussion will include zirconium by virtue of its close similarity to titanium in pref erred orientations. of the intense areas of the pole figure for samples annealed at 600°C. This splitting could be described by a 7" rotation of the tilt axis about the normal to the rolling plane. Such a splitting for the annealed texture relative to the cold rolled texture was not observed in other determinations for either zirconium or titanium using the less sensitive film X-ray methoe and makes the relationship between the two types of texture more complex than the simple rotation about the (0001) pole based on film work. The more precise investigations on zirconium permit the descriptions in the lower part of Table 11, which show that the texture depends quantitatively on the temperature of annealing. When zirconium is annealed at temperatures up to 400°C, the texture is similar to the cold rolled texture, while annealing in the range 500" to 900°C produces a texture which is only approximately described as [11%] in the rolling direction. More precisely described results for zirconium show that the two types of splitting ( 1—about an axis in the rolling plane through an angle given in the second column in Table II and 2—about the normal to the rolling plane through an angle given in the third column of Table 11) depend on annealing temperature. The [1120 is the rolling direction only when the annealing temperature is in the vicinity of 900°C

Jan 1, 1957

By Harold Margalin, Elmars Ence

M. H. Mueller, M. V. Nevitt, and H. W. Knott (Argonne National Laboratory)—We have reported1 the crystal structure of Ti2CU as body centered tetragonal with a. = 2.944A and co = 10.786A, six atoms per unit cell, and space groupl4/mmm(MoSi2 type). This cell is larger but definitely related to the unit cell reported by the authors. It permits definite positions for the titanium and copper atoms in the cell located as follows: 2 Cu (a) 0 0 0; 1/2 1/2 1/2 4 Ti (e) 0 0 z; 1/2 1/2 1/2 + z; 0 0z; 1/2 1/2 1/2- z where z = 0.341 The face centered tetragonal cell reported by the authors can be transformed to a small body centered tetragonal cell with flo (small bet) = ao(fct)v2 Both unit cells have the same CO. Neither the face centered tetragonal cell with four atoms per unit cell nor the small body centered tetragonal cell with its two atoms per unit cell lend themselves conveniently to an orderly arrangment of the 2 to 1 ratio of titanium to copper atoms. When the co of this small body centered cell is tripled, however, a large body centered tetragonal cell results with six atoms per unit cell as described above. We had also noted that the X-ray patterns of Ti2Cu indicated that the structure could be approximately described by the face centered tetragonal cell as reported by the authors; how- ever, there was evidence for a few additional very weak lines whose positions indicated a larger unit cell. Since the X-ray scattering amplitudes of titanium and copper are nearly equal, it is evident that it is difficult to distinguish their positions especially from X-ray powder patterns. It was therefore decided to look at a powder pattern obtained by neutron diffraction since the scattering amplitudes of the two elements are considerably different in magnitude and opposite in sign. The sample used for neutron diffraction was selected from a group of three alloys prepared by arc melting using crystal bar titanium of 99.92 pet nominal purity and 99.999 pet pure Cu. The alloys designated as A, B, and C had the following respective compositions: Ti-32.8 at. pet Cu, Ti-33.3 at. pet Cu, and Ti-33.8 at. pet Cu. On the basis of the melting losses incurred, it was established that the actual concentration of either component in any of the alloys probably did not deviate from the intended value by as much as 0.1 at. pet. The alloys were annealed for 5 days at 700°C in evacuated Vycor capsules and quenched in tap water. The metallographic structures of these alloys are shown in Fig. 1. None of the alloys contained sufficient second phase to permit its positive identification. Since alloy B contained the least amount of second phase and since its composition placed it closest to the ideal stoichiometry, it was chosen for the neutron diffraction study. The oxygen content of alloy B was found by chemical analysis to be 0.06 at. pet. This particular intermetallic compound is especially suitable for investigation with neutron diffraction since if the titanium and copper atoms have a random statistical distribution, a near null-matrix would result in which there would be practically no coherent scattering of neutrons, and hence no Bragg diffraction peaks. Such a condition could come

Jan 1, 1962

By Northcutt Ely, Charles F. Wheatley

This chapter deals with the systems of laws by which governments regulate the exploration for and production of the minerals within their jurisdictions. It is a summary, restricted by necessary space limitations, of material assembled by the author for a forthcoming publication of the United States Bureau of Mines, "Summary of Mining and Petroleum Laws of the World." (Information Circular, 1959.) The present study is organized in three parts, dealing with (1) the historical background of these legal systems, (2) laws of the United States, and (3) laws of other countries of the world. The reader's attention is invited to the acknowledgments at the end of the chapter, which inadequately express the appreciation due those who have assisted in the collection of this material. Part I. Historical Development of Major Western Systems of Land Tenancy with Respect to the Ownership and Control of Minerals The use of metals in primitive societies was largely confined to the manufacture of weapons for self-preservation. The ruler's control over copper, then brass, then iron, was essential to maintenance of his own ascendancy at home and his group's position against neighbors who had access to similar metals. Ancient societies were thus characterized by the ruling group's ownership of minerals and metals. The Egyptian civilization, which emerged in the fourth millenium B.C. upon the agricultural subjugation of the lower valley of the Nile, was responsible for extensive development of the upper valley as a source of mineral wealth. The production of gold during the height of that civilization has been estimated at $30,000,000 per year, thus equaling the early placers of California and Australia. The mines of Egypt were the property of the Pharaohs and were controlled at their direction. Greek mining developed a different scheme of land tenancy which more closely resembled modem concepts. Development of mineral resources was

Jan 1, 1959

By E. C. Carris

THE loading of bituminous coal mechan¬ically was recognized about the year 1900, but during the following 28 years less than 5 per cent of the bituminous pro¬duction in the United States was loaded by mechanical means. During the past i6 years, however, the usage of some form of mechanical loader has had a very rapid and accelerated growth, until at present production of bituminous coal by mechanical means has reached an all¬time high of approximately 46 per cent, and is still increasing. This rapid growth in the use of the mechanical loader has been supplemented by an increase in mechanical cleaning. The importance of mechanical cleaning of coal was recognized many years before the mechanical loader was introduced, because of the impossibility of cleaning manually the sizes below 2 in., and the increasing competition from other fuels. Utilization of mechanical loaders without mechanical cleaning on the surface for at least one or more sizes is the exception, rather than the rule. One exception is a mine that employs caterpillar-mounted mobile loaders exclusively, and mines the entire seam without any selectivity, and yet loads and ships six grades of coal of the very highest quality without mechanical cleaning. Such a fortunate situation can exist only where mining conditions are ideal, where top and bottom are exceptional and there are no impurity partings, and where there is loader height. The conversion from hand loading to mechanical loading has definitely intro¬duced many problems in the preparation plant of yesterday and in the modern streamline plant as well. Many of these problems have been solved by good, sound, conscientious initiative on the part of the plant personnel, with minor expendi¬tures; the solution taking the pattern of rearranging and improving the equipment at hand. Other problems have caused, and are causing, considerable concern and difficulty. LARGE IMPURITIES The removal of large quantities of large impurities from the lump coal, and their handling and disposal, is definitely a troublesome and costly problem. The cost of manually removing the impurities from the picking table alone, based on the actual recovered lump coal, can reach a cost of 42 cents per ton or more. In the design of future plants it would be wise to give this phase of preparation considerably more time and thought, particularly if the seam of coal contains one or more heavy partings and the mining procedure is all seam. This same caution applies to seams that may not contain heavy partings but have poor and heavy draw-slate top, which falls with the coal during the mining cycle. One of the more recent of the modern preparation plants has answered this problem by installing a rock crusher under the picking table in such a manner that the impurities can be diverted by gravity directly to the crusher. This reduces the

Jan 1, 1946

[NORTH AMERICA UNITED STATES ALABAMA Birmingham Cord, Richard H. Dlsmukes, Edward B. Hunter, Robert A. Citronelle Perrin, Huey P. Fairfield Pagel, Herbert Ervin Fairhope Ruffles, William R. Huntsville Eng, Harvard Kelley, Dean W. Waggoner, J. B. Weber, Thomas C. Mobile Hankins, James D. Horner, William L. Petroutson, Peter C. University Cudworth, James R. Jones, Walter B. Mason, William L.]

Jan 1, 1961

LOCAL SECTIONS (There are 70 Local Sections in the United States, 6 Foreign) ADIRONDACK Established June 18, 1952 Meets fourth Saturday monthly, April through October A L Hall, Chairman Malcolm V Lowry, Vice-Chairman Charles Dievendorf, Secretary-Treasurer International Talc Co Gouverneur, N Y R J Grant Fleck, '58, Section Delegate M V Lowry, '58, Alternate Section Delegate

Jan 1, 1957

By Howard R. Keil

Reactor at Carlton mill successfully calcines pyrite-telluride flotation concentrate for cyanidation. CARLTON mill in the Cripple Creek district, 45 miles southwest of Colorado Springs, Colo., has been in operation for approximately three years, treating the custom sulpho-telluride ores formerly handled by the Golden Cycle mill in Colorado Springs. At the new mill the pyrite-telluride flotation concentrates have been roasted, prior to cyani-dation, in a Dorrco FluoSolids reactor, which has proved capable of yielding calcine readily amenable to cyanidation. Incoming ores are crushed at Carlton to % in. and sampled in 30 to 75-ton lots before the individual lots are mixed in the fine ore bin. The composite ore then goes to the grinding circuit. Classifier overflow from the grinding circuit is treated by flotation to produce a concentrate containing approximately 85 pct of the values in 5 pct of the weight. The flotation concentrate goes to the FluoSolids reactor prior to cyanidation. Cyanide solution values are recovered by zinc dust precipitation. Flotation tailings are thickened and cyanided, the values from this part of the circuit being recovered from solution by activated carbon. Gold values in the flotation concentrates consist of a small amount of finely divided metallic gold; the tellurides, sylvanite and calaverite; and gold very intimately associated with the pyrite. The metallic gold and a part of the telluride values can be extracted from the concentrates by cyaniding without roasting. However, extraction on the tellurides by this method is not satisfactory, and the pyrite values are so intimately associated with the pyrite that very fine grinding and cyanidation for a prolonged period under ideal laboratory conditions does not yield good recovery. Upon roasting, the tellurides are oxidized to very finely divided metallic gold which is readily soluble in cyanide. The pyrite is oxidized mainly to a porous iron oxide which allows cyanide solution to penetrate to gold particles and take them into solution. Feeding the Reactor Flotation concentrates move by gravity to a thickener. Thickener underflow is discharged at approximately 60 pct solids, by means of a diaphragm pump, into a storage and blending agitator. From here the concentrates are pumped to a disc filter. The filter cake, at 84 to 88 pct solids, drops directly into a repulper where it is repulped into a slurry of 78 to 80 pct solids. The repulped filter cake flows into a 6x6-ft slurry agitator from which it is fed directly into the reactor by the Moyno pump. The Moyno pump has eliminated a large number of difficulties that were first encountered in feeding a wet concentrate to the reactor. On the original installation in Canada a screw feeder was used to introduce the filter cake directly into the reactor. Since the reactor is under a slight positive pressure it was necessary to have a suitable seal to prevent gas escaping from the reactor at this point. When the concentrates produced in flotation were coarse or granular they could be readily fed to the reactor but when fine-textured, clayey concentrates were produced a great deal of trouble was encountered.

Jan 1, 1955

By L. A. Rapoport, W. J. Leas, C. W. Carpenter

A program of scaled flow model experiments has been undertaken to study the performance of five-spot water floods. The modeling procedures are discussed and the construction and operation of the flow models are described. The tests were specifically designed to investigate the effects of injection rate and of oil-to-water viscosity ratio on oil recovery. The areal sweep of five-spot water floods was also studied, and direct comparisons between five-spot and linear flooding behavior have been established to permir better utilizatfon of core analysis results for purposes of field waterflood evaluations. INTRODUCTION For a long time reservoir engineering procedures have been confined to the consideration of idealized, one-dimensional or linear systems.11* However, direct application of the linear waterflood mechanism to the evaluation of actual field performance is justifiable only for the purposes of rough approximation. To obtain a realistic analysis of field behavior, it is necessary to account for reservoir geometry and well distribution, and to take into consideration the configuration of the flow of fluids between injection and producing wells. In the past it has been attempted to account for the complex nature of the fluid movement in the reservoir by associating each well pattern with a certain "sweep-efficiency constant", e.g., a sweep efficiency of 72 per cent for the conventional five-spot pattern.' More recently, methods of waterflood evaluation have been improved by the introduction of variable sweep-efficiency factors, defining the areal coverage as a function of cumulative water injection and viscosity or "mobility" ' ratio.""' These variable sweep-efficiency factors, derived from miscible fluid displacement experiments, require the assumption of piston-like displacement of oil by water. This implies that only one fluid, either oil or water, is moving at any one point of the reservoir ht any moment. Such an assumption, however, is incompatible with the bulk of the experimental evidence and also theoretical considerations which indicate that usually in the area invaded by water, both oil and water are flowing in varying proportions, in accordance with the relative permeability characteristics of the porous medium. Another recent approach toward the evaluation of five-spot flooding behavior involves correlations of the areal sweep efficiency (observed in immiscible fluid experiments) with a "mobility ratio," based on the consideration of the "average" relative permeability to the displacing fluid. Combination of these correlations with a modification of the Buckley-Leverett frontal-drive equation leads to a computational procedure for predicting the recovery performance of areal water floods. While of considerable interest, this approach has no complete theoretical justification and, therefore, does not entirely clarify the features of five-spot water floods. Rigorous, theoretical treatment of waterflood behavior in two- or three-dimensional systems as encountered in the reservoir, including proper consideration of relative permeability and capillary-pressure functions, is as yet beyond the scope of analytical or computational methods. The, behavior of such water floods can, however, be studied by means of scaled flow model ekperiments, which is the approach followed in these investigations. The flow model experiments described in this paper simulate a uniform, horizontal formation of constant thickness with fully penetrating wells. The system under consideration is entirely liquid saturated and not influenced by compressibility effects, which is representative of the situation achieved after gas fill-up under practical conditions. Gravity segregation effects are assumed to be negligible, which implies a relatively thin reservoir formation and/or low vertical permeability. THEORETICAL CONSIDERATIONS For a flow system of uniform thickness with no appreciable effects of gravity segregation, the analysis of water-oil displacement can be confined to a two-dimensional treatment based on the consideration of a "slice" of unit thickness. Referring to previously established derivations," the displacement of oil by water in such a system can be described by the following, dimen-sionless equations:

By W. F. Flanagan, D. H. Polonis, S. D. Dahlgren

Rotation diffraction patterns of Cu-4.84 wt pct Si polymystalline samples were taken during the course of isothel-ma1 affing of the suPersaturated a phase, a diffraction spots were obserzled to streak during the initial stages of aging, and this streaking was similar to the streaking of a spots observed earlier by Barvett with deformed super saturated samples of the same composition. Although it was suggested that stacking faults were the sole cause of styeaking in the deformed samples, the present study has shown that plates with one small crystallite dimension can also contribute to the streaking when there is lattice coherency across close-packed planes. THE decomposition of the supersaturated a phase in Cu-Si alloys has been reported to occur by means of both thermal and stress activation.1-4 According to the Cu-Si phase diagram,3 Fig. 1, the supersaturated a phase (fcc) is expected to transform during aging by the precipitation of the y phase. The results of earlier studies2,4 have indicated that metastable k phase (hcp with nearly ideal close packing) forms initially at temperatures below the eutectoid temperature, after which the k transforms to the a and y phases. Hof-mann et al.4 have proposed a metastable version of the phase diagram, showing the approximate boundaries for k formation below the eutectoid temperature. In view of the close-packed nature of both the a and k phases, it is essential to consider the role assumed by stacking faults in the transformation. Streaking effects have been reported by Barrett 1 in the rotating crystal X-ray patterns of strained Cu-Si alloys and were attributed to stacking faults rather than particle size effects. This deduction was based on the observation that streaks in the diffraction patterns did not occur tangent to the 220fee Debye ring. It is known that the atom movements involved in faulting leave some X-ray reflections unaffected while others are broadened,' and, in particular, it has been shown that faulting will not cause streaking of 220fee reflections tangent to the 220fee Debye ring as would be expected if all the reflections were broadened.' The formation

Jan 1, 1967

By H. J. Beach

This paper describes the properties and uses of cementitious mixtures containing 10 to 20 per cent bentonite and 2 per cent or more sodium chloride. Salt additions improve bentonite cement by increasing early strength and stabilizing viscosity without changing thickening time. The volume yield of cement is increased 20 per cent or more without lowered early strength. The unique properties of salt in this type of system make savings of more than 10 per cent possible where light-weight, low-strength cementitious material is adequate to fill behind pipe. The density range of these mixtures is 12 to 13 1b/gal and the filtration rates are medium-low, aiding the placement of long columns in primary cementing. Where available, sea water is an ideal salt source in preparing these slurries. INTRODUCTION Accelerators increase the rate of cement hydration. In speeding reaction with water, they can affect cement performance by reducing thickening time and increasing early strength after set. Accelerators that cause both effects can be considered "total", and those which produce only one effect can be called "partial". Materials that act conversely to accelerators are retarders. and they also can be total or partial. Partial retarders. make high-temperature cementing possible by prolonging thickening time while impairing early strength only slightly. Most known accelerators are total. A useful partial accelerator would increase strength without altering thickening time. This report concerns material combinations in which a normally total accelerator exerts unique partial properties. Utilizing these limited effects improves bentonite cement. SEPARATE EFFECTS OF SODIUM CHLORIDE AND BENTONITE ON CEMENT Sodium chloride and calcium chloride are commonly used in cement, and at low concentrations their effects are similar. Ludwig1 studied sodium chloride in API Class A and Class E cements.' Figs. 1 and 2 sum- marize his data taken at 140°F on slurry pumpability and early strength. Normal water-to-cement ratios are 0.46 and 0.40, respectively, for Class A and Class E cements. At saturation the salt content is 12 to 14 per cent of the weight of cement solids. The illustrations, therefore, cover the range of salt solubility in the mixing water. The data show that sodium chloride is a total accelerator of the Class E cement studied over the range of solubility. It is total in Class A cement to 6 per cent. Above this concentration salt becomes a retarder— partial from 6 to 10 per cent and total above. These results are general for different brands of Class A cement, although the shift from acceleration to retardation may occur at different salt concentrations for different temperatures. The results are specific for the Class E brand studied. In discussing his data, the investigator emphasized that different Class E cements might respond erratically to salt, depending on the brand chosen. Morgan and Dumbauld3 escribe the properties of bentonite cement in a paper that is a standard reference in using these systems. Bentonite functions in cement as an enabling agent; each bentonite addition equal to 1 per cent of the weight of dry cement makes possible the further addition of 4.5 per cent water.' Thus, 10 per cent bentonite in Class A cement, normally slurried neat with 46 per cent water, enables the slurry to contain another 45 per cent before settling. Water is one of the lightest and cheapest cement extenders; it reduces density and cost. Bentonite cements produce uniform slurries having low susceptibility to solids separation. After set, they offer low resistance to perforation.

By G. E. Johnson

E. D. HYMAN*—How much sorting of scrap is done ? G. E. JOHNSON (author's reply)—We do practically no sorting. We charge "run of mine" scrap to the furnace. The unmeltables, mostly iron, are in such demand today that there is no difficulty in disposing of them. It may soon be desirable to sort out from the unmeltables as much of the brass as possible. J. J. BRUGMAN†—We have somewhat similar problems in the secondary aluminum business. What is your method of removing the unmelted material from the furnaces? Why have you such an apparently small space in which to charge your materials? Do you find that you have to seal that opening, or can you have it open and continuously charge at one end and pull out the other ? G. E. JOHNSON—Our means of melting scrap is efficient only to the extent that we use the waste heat from the vaporizing chamber to do the job. It is a batch process. We open the charge door and place the scrap on the hearth by hand shoveling. The door is then closed during the melting down period. After the melting is complete, the opposite door is opened and the unmeltables are raked out. The doors are approximately 3½ X 4½ ft and are not sealed during the process only closed. They are nominally tight. Some metal is oxidized in the process. We have visualized a means of conveying the materials through this melting unit with the metals that are melted trickling out during its travel. T. H. WELDON‡—Mr. Johnson, in line with the last question, is it necessary to seal the furnace between the melting down and the vaporizing unit, or have you got an inverted syphon in the bottom of the chamber? G. E. JOHNSON—That was one of the first things we encountered. We had to have a sealed opening, and it is a molten metal seal. You have indirectly asked me another question, which was: "Do you have to seal up the melting unit?" I would say we should exclude as much air as possible, although we are not too efficient in doing that. We allow the melting unit doors to be open when we charge and when we remove unmeltables. You can readily see that that would lead to the idea of having a controlled atmosphere in the melting unit, and I think this would do a more efficient job of melting the scrap. T. H. WELDON—How often do you charge the furnace? G. E. JOHNSON—We charge the melting unit, and rake out the unmeltables, about every hour. H. R. HANLEY*—Are any provisions made for controlling the rate of oxidation for the production of various size particles for certain characteristics of the zinc oxide product? G. E. JOHNSON—Yes, there are many. You are getting pretty much into the fine points of zinc oxide manufacture. Some of us still think we have something to learn about that. In general, this muffle furnace as I have described it to you produces a rounded particle of zinc oxide which is generally formed by a rapid oxidation of the zinc vapor, followed by rapid cooling. We have gone to the other extreme in some of our experiments. We have changed the furnace to produce a type of zinc oxide, such as we thought was peculiar to American process zinc oxide, by controlling the temperature at the point of oxidation and maintaining that temperature for a much longer period of time than we do when we make the rounded shape. There are other relationships that this furnace readily provides. One of the important factors is the ratio of air to zinc vapors. We can vary that by varying the air supply to the baghouse, or vary the rate at which we are vaporizing the zinc by the simple expedient of regulating the temperature over the carborundum arch. We have a number of variables that permit us to produce all of the grades of French process zinc oxide from lead-free up through the highest grades of seal oxides. There are many controls that we can apply to the operation. What I have said is but a brief condensation. K. MORGAN*—Can Mr. Johnson give us some idea of the fuel consumption of the furnace ? How much oil does he use per ton of zinc distilled? I am also interested to know what sort of heat transmission he gets through the arch? What is the thickness of the tiles used to construct the arch? Some time ago we built a small furnace for a different purpose, using a carborundum arch, and we found that the reflectivity of the molten zinc surface was so great we had to use a very high arch temperature. We found we made an improvement by having a layer of carbon on the surface of the zinc. Has Mr. Johnson had any experience on these points ? Does he make any sort of insolu-bles which he leaves in the furnace which he cannot tap out ? G. E. JOHNSON—I believe your first question was the fuel consumption. If I recall, somewhere in this paper there is a test that I quote. I believe we used 800 gal in a given period of time. Offhand I cannot translate that into tons of metal. I might also state that we have this understanding; that the carborundum arch, as the temperature becomes higher, becomes more efficient in heat transmission. As a matter of fact, I believe it is at about 2600°F or higher that the highest efficiency of heat transmission becomes available. We have calculations that I cannot quote from memory which indicate that the carborundum arch does a really very fine job for this type of furnace. Another point that we had considered was the fact that this furnace could be readily constructed so as to furnish an ideal source of heat for waste heat boilers. If a carborundum arch was used over the melting unit, we would have no zinc vapors in the gases at all— just clean combustion gases from which we would have removed some of the heat. L. P. DAVIDSON†— The insolubles

Jan 1, 1950

By A. L. Pranatis, G. M. Pound

Changes in length of copper foils of varying thickness and grain size were measured under such conditions of low stress and high temperature that it is believed that creep was predominately the result of interboundary diffusion of the type recently discussed by Conyers Herring. The surface tension of copper was calculated and results confirmed previous work within the limits of experimental error. Under the assumption of viscous flow, viscosities were calculated as a function of temperature and grain size. Predictions of the Nabarro Herring theory of surface grain boundary flow were borne out fully and the Herring theory of diffusional viscosity is strongly supported. ONLY a relatively few techniques for obtaining the surface tension of solids are presently available. Of these, the simplest and most straight forward is the direct measurement of surface tension by the application of a balancing counterforce. Thin wires or foils are lightly loaded and strain rates (either positive due to the downward force of the applied load or negative if the contracting tendency of surface tension is sufficiently greater than the applied stress) are observed. By plotting strain rates against stress, the load which exactly balances the upward pull is found and a simple calculation yields a value for the surface tension. The technique is of comparative antiquity, and solid surface tension values were reported by Chapman and Porter,' Schottky; and Berggren" in the early part of the century. Later, the filament technique became fairly well established as a method for determining the surface tension of viscous liquids, and Tammann and coworkers,'. " Sawai and co-worker and Mackh howed good agreement between the values of surface tension for glasses and tars obtained by the filament technique and by more conventional methods. With the increased confidence in the technique gained in these experiments, the method was applied to solid metals and the first reliable values of surface tension of solid metals were reported by Sawai and coworkers10' " and by Tammann and Boehme." More recently, Udin and coworkersu-'" have reported the results of experiments with gold, silver, and copper wires. Similar experiments with gold wires were carried out by Alexander, Dawson, and Kling.'" The excellent review articles of Fisher and Dunn" and of Udinl@ should be referred to for detailed criticism of the foregoing work and for discussion of underlying theory. In all the foregoing calculations, it is assumed implicitly that the material contracts or extends uni- formly along the length of the specimen and also that it flows in a viscous fashion, i.e., that strain rates are proportional to stress. For an amorphous material, such as glass, tar, or pitch, the assumptions are quite valid and good agreement is obtained with values of surface tension measured by other techniques. The values reported for metals, however, are occasionally regarded with misgiving, since it can be argued that, because of their crystalline nature, true solids can not deform in a viscous fashion. If this is true, then the results reported for solid metals over a long period of years are of only doubtful value. Thus it is clearly necessary that a mechanism be established that would explain both the viscous flow and the uniform deformation that has been assumed. Such a mechanism has been proposed by Herring."' Briefly, he suggests that, under the conditions of the experiment, deformation takes place by means of a flow of vacancies between grain boundaries and surfaces. This is a direct but independent extension of the theory proposed by Nabarro" in an attempt to explain the microcreep observed by Chalmer~.In a condensed form the Herring viscosity equation is TRL there 7 is the viscosity, T the absolute temperature, R and L grain dimensions, and D the self-diffusion coefficient. In its complete form, all constants are calculable and it includes such factors as grain shape, specimen shape, and degree of grain boundary flow. When applied to existing data, good agreement was obtained between predicted and observed flow rates. The theory received provisional confirmation from the work of Buttner, Funk, and Udin" who observed viscosities in 5 mil Au wire much higher than those in the 1 mil wire used by Alexander, Dawson, and Kling.'" More significant were the completely negligible strain rates found by Greenough" in silver single crystals. Opposed to these observations were those of Udin, Shaler, and Wulff'" who found indications of viscosity decreasing as grain size increased. Thus, complete confirmation of the theory was lacking in that the data to which it could be applied contained only a limited number of grain sizes. Hence, it was proposed that a series of experiments be carried out with thin foils of varying grain size up to and including single crystals, where, according to the Herring theory, deformation would occur only at almost infinitely slow rates.

Jan 1, 1956

By Ralph Hultgren, Prodyot Roy

Manganese vapor pressures from 1250° to 1500°K were measured by conventional Knudsen and torsion-effusion methods in twelve Fe-Mn alloys with compositions from 9 to 80 at. pct Mn. The Knudsen re-sults agveed approximately with previous measurements found in the literature which indicated the solutions were nearly ideal. However, except for the higher manganese compositions, the initial torsion readings indicated much (up to 50 pct) higher vapor presszcres than the Knudsen method. These high readings decreased steadily with time. The results are interpreted as due to depletion of surface concentration of manganese during evaporation. Thus the initial torsion readings are the most nearly correct and Knudsen methods on alloys are to be regarded with suspicion unless it can be demonstrated that diffusion rates are rapid enough to replenish surface concentrations depleted by evaporation. For the lowest manganese contents and highest temperatures, depletion causes initial torsion readings to be too low. FEW thermodynamic data are available for alloys of the high-melting transition metals due primarily to experimental difficulties at the high temperatures involved. Measurement of vapor pressure is one of the most promising techniques to be applied to this problem. From the vapor pressure of a component of an alloy phase, its activity or its partial molar Gibbs energy can be directly calculated. From measurements over a sufficient range of temperatures and compositions the partial and integral Gibbs energies, enthalpies, and entropies may be determined through Gibbs-Duhem integration. For solid phases of variable composition, which commonly are found in alloys, measured vapor pressures are low because of depletion of the surface concentration of the more volatile component as it is selectively vaporized. Diffusion from the interior tends to restore the depleted concentration. The seriousness of the effect depends on the relative rates of diffusion and vaporization. Although depletion has been recognized as a factor,' direct measurements of its rate are lacking and quantitative estimates of its effect on measurements are uncertain. In the present work the vapor pressures above a series of Fe-Mn alloys have been measured by the torsion-effusion method. This method permits a measurement of the vapor pressure of manganese as soon as the sample comes to temperature and continuously throughout the run. The rate of decline of the apparent vapor pressure measures the rate of depletion and the torsion reading at zero time should be correct. At high manganese concentrations (70 and 80 at. pct Mn), the torsion reading remained nearly constant; surface depletion was negligible. There was a slow drop in measured pressure due to bulk loss of manganese from the sample. However, for lower manganese contents, especially at high temperatures, the depletion effect was considerable and the apparent vapor pressure decreased steadily with time. For these alloys the Knudsen method should give pressures which are too low. The measurement of pressure in the Knudsen method cannot be made until enough manganese has been vaporized to be weighable. The Knudsen result is therefore an integrated average between the initial and final vapor pressures. To verify this, conventional Knudsen measurements were also made with results in approximate agreement with previously published Knudsen measurements for these alloys. As expected, for the lower manganese contents the initial torsion readings of pressure were as much as 50 pct higher than the Knudsen. THE APPARATUS The apparatus, shown in Fig. 1, is capable of operating to temperatures up to 2000°K. A vacuum of 5 x 10"6 mm Hg can be maintained. Temperatures were measured to +3° by a W-Re thermocouple placed in the dummy cell, N. The torsion cell consisted of two alumina crucibles with holes in their covers. They were placed in the molybdenum holder shown suspended from the torsion wire. Rectangular torsion wires (1 by 4 mm) were found to have superior sensitivity and less residual distortion than circular (2-mm-diameter) wires. The precision of angular measurement was found to be *0.025 deg; the variation is no doubt due to temperature fluctuation and vibration. For the Knudsen experiments the alumina cell was set on the support, N. SAMPLE PREPARATION 800-g samples were prepared by melting together electrolytic iron and electrolytic manganese and pouring the melt into a water-cooled copper mold. Melting and pouring were done under a helium at-

Jan 1, 1965

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature microhardness of as-grown and annealed MoaC single crystals was measured on the (0001), {2110), and1012) planes using Knoop and Vickevs indenters at loads ranging front 25 to 1000 g. The orientatimz dependence of hardness with respect to crystal axes was also studied. The average random hardness of as-grown crystals was determined to be 1520 kg per sq nm. Annealing to 2000°C decreased. the average hardness by 150 units. An increase in hardness after annealing at 2200 ;C was noted. Optical and electron microscopy revealed slip and twin traces on all planes studied, as produced by mi-cvohavdness indentations. Basal (0001)(2i10) slip was determined to be the primary slip system and was substantiated by electron transmission microscopy. A secondary {1010)(2110) slip was produced by mi-crohardness indentations. The lattev also produced twinning- of the {10i2)[0001] type, as proven by electron diffraction. Electrical resistivity and elastic-modulus anisotropy were found and correlated with hardness anisotropy and Mo2C crystal structure. Elastic-modulus values were obtained by microhard-uess and ullrasonic methods. Bonding mechanism of Mo2C is discussed. ROOM-TEMPERATURE microhardness indentations are useful for studying hardness anisotropy, slip, and twinning in brittle materials. Slip has previously been produced in this manner in and WS~~.~ Recently, the authors5 reported slip of the {10i0)(11~0) type produced by high pressure and microhardness indentations on hexagonal TiBz (c/a = 1.066) single and polycrystals. This slip system was also reported by French and ~homas' and Taka-hashi and ~reise~ for hexagonal WC (c/a = 0.976) crystals. These results suggest that prismatic rather than basal slip is favored in hexagonal nonmetallic materials having a c/a ratio considerably less than the ideal (1.633). Buerger precession and cylindrical X-ray rotation patterns were previously' taken on cleaved sections of the Mo2C single crystals studied in this work. Th~y were found to be hexagonal MoaC with a. = 3.0233A, co = 4.7344A, and C/O = 1.5660. The latter ratio is close to that of the beryllium metal (c/a = 1.57), which slips primarily on the (0001) plane: but also slips on the (1010) planes.'0 ~irconium" (c/u = 1.59) and titanium12 (c/o = 1.59) deform mainly by slip on nonbasal planes which contain a close-packed direction. This is due to the fact that for these two metals the initial resolved shear stress for slip on the (10i0) prismatic planes is lower than that on the (0001) plane. The prominence of basal rather than prismatic slip in metals of high c/o ratios is shown by cadmium (c/a = 1.89), zinc (c/a = 1.86), and magnesium (c/a = 1.62) which deform mainly by basal slip. However, in case of the latter, by stressing magnesium crystals in tension or compression parallel to the basal plane, slip on (10i0) planes can also be produced.13 Several hardness values for polycrystalline Mo2C are reported in the literature: Biickle ' and Samsonov'~ give a value of 1800 and 1479 kg per sq mm, respectively, at a 100-g load; and Kieffer and Benesovsk~'~ report a value of 1950 kg per sq mm at a 50-g load. ~ott'~ reports a Vickers hardness value of 2000 kg per sq mm, with the load unspecified. A Rockwell A hardness value of RA = 88 has also been reported.'' In the present work, for comparison with single-crystal Mo2C hardness values, a Khnloo value of 1600 It 150 kg per sq mm was found on 99.6 pct pure and 99 pct dense hot-pressed Mo2C. This work was undertaken partly to explain the considerable differences in hardness values reported for polycrystalline Mo2C. EXPERIMENTAL The Mo2C single crystals investigated were prepared by a Verneuil-type process using an electric arc by the Linde Co. of the Union Carbide Corp.lg The largest specimens grown were boules 7 mm in diam by 40 mm in length. The crystals had an average density of 9.04 g per cu cm, with a Mo + C content of 99.8 wt pct. The major impurities were: 100 ppm each Na, Zr, and Ca; 85 ppm 0, 55 ppm Fe, and 10 ppm each Cr and Ta. The crystals were found to be carbon-poor, the average carbon content being 5.73 wt pct (stoichiometric value is 5.89 pct). The molybdenum content was found to be 94.08 pct, which is nearly stoichiometric. Electron-microprobe traverses of selected specimens were done with a Phillips-AMR microanalyzer. Thin-film and carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to optical and electron-optical studies, specimens were mounted in Lucite and polished on a vibratory polisher using diamond-paste grades ranging from 9-1 p and Linde A powder for up to 48 hr. Dilute nitric acid was used for thin-section polishing and chemical etching for 1-15 min. Electrical-resistivity measurements at room temperature were taken with a Rubicon bridge, using gold contacts. For hardness measurements, a Tukon Microhardness Tester Type FB with Knoop and Vickers indenters was used. Measurements were taken at loads ranging from 25 to 1000 g; however, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Indentations of cracking classes 1 and 2 only were considered for hardness determinations.20)21 (There are six cracking classes, ranging from "class 1" for a perfect inden-

Jan 1, 1967

By B. L. Averbach, Morris Cohen, L. L. Seigle

Free energies, enthalpies, and entropies of mixing of Ni-Au solid solutions containing 5 to 95 atomic pct Ni have been determined by the electromotive force method at 700° to 900°C. The thermodynamic activities exhibit large positive deviations from Raoult's law, and the entropies of mixing are almost twice those of ideal solutions. The enthalpies of mixing are positive (heat is absorbed) and are attributable to the lattice distortional energy resulting from the size difference between the nickel and gold atoms. This factor appears to be responsible for the miscibility gap at lower temperatures. IN the thermodynamic study of metallic solid solutions, most interest has been directed toward systems with negative deviation from Raoult's law, namely, those exhibiting superlattice or compound formation. The results of previous investigations are summarized in recent publications.'-' Relatively little experimental work has been carried out on solid solutions which manifest a positive deviation, possibly because the range of solubility in such cases is usually quite limited. Nevertheless, the relationship of the thermodynamic properties of these solutions to diffusion, nucleation, and precipitation in the solid state are of considerable importance. The binary Ni-Au alloys are particularly suited to an investigation of these relationships. Despite the presence of a miscibility gap at lower temperatures, Fig. 1, indicating a large positive deviation from Raoult's law, complete solid solubility is found above 840°C. Moreover, the difference in the atomic scattering powers of nickel and gold is sufficiently great to permit X-ray diffraction studies of atomic arrangements and pre-precipitation phenomena. Radioisotopes of both nickel and gold are available for diffusion work, and finally, a large difference in nobility between the two elements facilitates measurement of the thermodynamic properties. The present paper describes the experimental determination of the free energies, enthalpies, and entropies of mixing of solid Ni-Au alloys. Table I gives a list of the symbols used in the paper. Experimental Method The stability of nickel chloride relative to gold chloride" indicated that the galvanic cell method could be used for determining the thermodynamic properties of Ni-Au alloys. An electrolytic cell (Fig. 2) was constructed, similar to that of Weibke and Matthes,7 in which the electrodes were solid nickel and Ni-Au alloys, and the electrolyte was a fused mixture of alkali chlorides containing NiCl,. The cell electrodes were made from fine gold granules and carbonyl nickel shot melted together under argon, chill cast, swaged to 1/16 in. diam rod, and annealed for one week at 850°C. Commercial reagent and chemically pure grade salts, purified by dehydration, were used for the electrolyte. The cell, operating in an atmosphere of purified argon, was heated in a resistance-wound cylindrical furnace whose temperature was controlled to within ±0.5ºC. The potential developed between the pure nickel and the alloy electrodes, which is related to the thermodynamic properties of the alloys by standard equations to be presented later, was measured with a potentiometer and a mirror galvanometer sensitive to 10-7 v. Dehydration of the electrolyte was carried out in the assembled cell by evacuating at 100°C for about

Jan 1, 1953

By C. E. Lundin, M. Hansen, D. J. McPherson

PRIOR work on the Zr-Cu phase diagram by Alli-bone and Sykes,' Pogodin, Shumova, and KUGU cheva,' and Raub and EngeL3 as confined largely to copper-rich alloys. The investigations of Raub and Engel were the most recent and seemingly the most complete of these. Alloys from 0 to 68.3 pct Zr were studied principally by thermal analysis and microscopic examination. These authors reported an inter metallic compound ZrCu, (1116°C melting point) and two eutectics, one at 86.3 pct Cu (977°C mp) and the other at 49 pct Cu (877°C mp). The solubility of zirconium in copper was reported to be less than 0.1 pct at 940°C. The zirconium melting stock consisted of Westing-house "Grade 3" iodide crystal bar (nominally 99.8 pct pure). It was treated by sand blasting and pickling (HF-HNO, solution) to remove the surface film of corrosion product, resulting from grade designation tests. The crystal bar was cold rolled to strip, lightly pickled again, and cut into pieces approximately 1/32 in. thick and 1/4 in. square. These were cleaned in acetone, dried, and stored for charging. The high-purity copper (spectrographic grade) was supplied by the American Smelting and Refining Co. with a nominal purity of 99.99 pct. These copper rods were rolled to strip, cut into squares the same size as the zirconium platelets, cleaned in acetone, dried, and stored. Equipment and Procedures The equipment used for melting and annealing the zirconium binary alloys and for the determination of solidus curves has been described in connection with previous work on the Ti-Si system' and in recent papers in this series describing the studies on eight binary zirconium systems.5-' Techniques employed for preparing and processing the alloys were also similar to those used in the above references. Ingots of 20 g were melted under a protective atmosphere of helium on water-cooled copper blocks in a nonconsumable electrode (tungsten) arc furnace. The ingots were homogenized and cold-worked prior to isothermal annealing to aid in the attainment of equilibrium. The specimens were heat-treated in Vycor bulbs sealed in vacuo or under argon, depending on the temperature of the anneal. Quenching was accomplished by breaking the Vycor bulbs under cold water. Temperature control was within ±3OC of reported temperatures. Thermal analysis was primarily relied on to determine eutectic levels, peritectic levels, and compound melting points. The induction furnace incipient melting technique was also used but did not provide the accuracy obtained by thermal analysis in this system, which involves much lower solidus temperatures than the other zirconium systems. A special technique for the determination of characteristic temperatures was employed in the case of several intermediate phases and their eutectics which displayed very small differences in melting temperatures. Specimens were sealed in Vycor bulbs and annealed at a series of very accurately controlled temperatures. Metallographic examination was then employed to reveal incipient melting. Furnaces and techniques in general were described previously.' The echant used was 20 pct HF plus 20 pct HNO3 in glycerine unless otherwise stated. Results and Discussion The chemical analyses of the majority of alloys prepared for the determination of phase relationships in this system are given in Table I and a brief summary of the equilibrium anneals employed is given in Table 11. In a preliminary program, alloys containing 1, 4, and 7 pct Cu were annealed for three different times at each of the temperatures 700°, 800°, and 900°C. No change in the relative amounts of phases present was detected after 350, 150, and 75 hr at the above temperatures, respectively. The times listed in Table II were accordingly chosen as a result of these preliminary tests. Zirconium-rich alloys containing from 0.1 to 10 pct CU were reduced by cold pressing from 58 to 8 pct, depending upon thk alloy content, homogenized for 7 hr at 900°C, and then reduced 80 to 13 pct by cold rolling, again depending upon copper content. Other alloys were studied in the cast, or cast and annealed conditions. The contracted scope of investigation for this system included the range 0 to 50 atomic pct Cu. This approximate region is shown in Fig. 1. Due to evidence of phase relationships departing considerably from those proposed by Raub and Engel" in the 50 to 100 atomic pct range, the investigation was extended to cover this composition area rather thoroughly also. Fig. 2 is a drawing of the entire diagram. The labeling of some phase fields was omitted in Fig. 2 for the sake of clarity. An expanded view of the zirconium-rich region, with the experimental points necessary for its construction, is given in Fig. 3. The generally accepted value of Vogel and Tonn8 or the allotropic transformation a + 862' ±5OC, was employed in the construction of these diagrams. A careful study revealed that the "Grade 3" crystal bar used in this investigation actually transforms over the approximate range 850" to 870°C, due to impurities. It must be expected that this two-phase field in unalloyed zirconium will cause some departures from binary ideality in the very dilute alloys. Zirconium-rich Alloys: The a + ß transformation temperature is decreased from 862" to about 822°C by increasing amounts of copper. Thus, a eutectoid reaction, fi ß a+ Zr,Cu, occurs at a composition of about 1.6 pct Cu. The eutectoid level was determined to lie between the alloy series annealed at 815" and 830°C. The placement of this eutectoid temperature

Jan 1, 1954

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

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

Jan 1, 1963

By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By D. S. Eppelsheimer, D. N. Williams

The cold rolled textures of iodide titanium and of three samples of commercial titanium were examined using the Schulz-Decker Geiger counter technique. The iodide titanium and two of the three samples of commercial titanium showed a (0001) [1010] texture rotated 30' toward the transverse direction about an axis in the rolling direction. The third sample of commercial titanium showed a double texture. THE metals of the hexagonal system tend to deform similarly if the c/a ratios are similar. Thus titanium, zirconium, and beryllium, with c/a ratios of 1.601, 1.590, and 1.570, respectively,l should have similar cold rolled textures. The cold rolled texture of high purity iodide titanium has been described as (0001) [1010] rotated 30" toward the transverse direction about an axis in the rolling direction.' The texture of zirconium has also been reported as (0001) [1010] with a transverse rotation from the ideal position of approximately 30" about an axis in the rolling direction." This texture differs from that reported for titanium however since a continuous spread of (0001) poles toward the transverse direction was reported rather than distinct (0001) maxima 30" from the rolling plane normal. Beryllium has a texture similar to that of zirconium although the angle of transverse rotation of the (0001) poles is much less.' These three metals thus show a common type of cold rolled texture, as yet unexplained, which can be described as (0001) [1010] with various degrees of rotation toward the transverse direction about an axis in the rolling direction. Since titanium showed the greatest degree of rotation from the (0001) [1010] position, the cold rolled texture of titanium was re-examined using a semiquantitative Geiger counter X-ray technique to obtain more accurate experimental data from which a theoretical interpretation of this new type of hex- agonal rolling texture could be developed. The cold rolled textures of iodide titanium and of three samples of commercial titanium were determined. Table 1 gives the analyses of the titanium samples. Experimental Procedure Preparation of Samples: Prior to the final rolling operation each of the samples was given an initial reduction of approximately 50 pct and annealed to remove the gross effects of any previous treatments. Samples were annealed in vacuum, high purity helium, and air to determine whether annealing atmosphere had any effect on the cold rolled textures developed. All samples were annealed 1 hr at 800°C. Grain size determinations were made using the formula, 1.075 in which n is the number of grains counted in an area A (in sq mm) and M is the magnification of the area counted.' This formula gives the diameter between opposite flats assuming hexagonal grains. At least three areas containing more than sixty grains each were counted in each grain size determination. Rockwell B hardness readings were made on the annealed samples. The results of the measurements of

Jan 1, 1954

By Peter Greenfield, Paul A. Beck

Thirty binary systems of vanadium and chromium group transition elements with second and third long period transition elements were explored in regard to the intermediate phases formed. It was found that the phases predominating in these systems are s, AB type with ordered a-tungsten or C8 structure, close-packed-hexagonal with small unit cell dimensions and, finally, phases isomorphous with 1-manganese. IN recent years, considerable information has become available concerning the intermediate phases in binary systems of the transition elements. Thus, the s phase has been found to occur in most of the binary systems of vanadium, chromium, and molybdenum with the group of elements manganese, iron, cobalt, and nickel.' It was observed that, while the rr phases formed by chromium with manganese, iron, or cobalt possess a considerable temperature range of stability, particularly in the Cr-Co system, the corresponding s phases with molybdenum are limited to a temperature range of less than 400" above about 1200°C. Goldschmidt' reported v phases of tungsten with iron and cobalt, and these are apparently stable only at (and above?) 1400°C." Exploratory work in this laboratory with Fe-W and Co-W alloys of approximately 60 atomic pct W annealed at 1300°C did not produce X-ray patterns suggesting the presence of a phase. It appears then that the phases of iron and cobalt with the chromium group elements decrease in stability as the two components are chosen from long periods further removed from each other. From the available information, it might be concluded that the controlling factor is the increasing difference in atomic radii between the components. In contrast to the a phase, the phases formed by iron and cobalt with chromium group elements' are stable only when the latter have large atomic radii (molybdenum and tungsten); the corresponding phases with chromium do not occur. When the difference in atomic size becomes still larger (r,/r,, approaching the ideal value of 1.225), the u and p phases are replaced by Laves phases (AB,), as in the alloys of iron and cobalt with columbium," tantalum." and titanium."-" However, atomic size certainly cannot be the sole determining factor, since, for instance, in contrast to the very stable (Mo, Co)p phase, no such phase occurs in the Mo-Ni system even though the atomic diameters of cobalt and nickel are nearly the same. Similarly, chromium and cobalt form a a phase in a wide temperature range," but the corresponding s phase in the Cr-Ni system is missing. It has been shown that the composition of the u phase in various binary and ternary systems of transition elements in the first long period may be correlated in a fairly quantitative manner with the number of electron vacancies. The influence of electronic structure is probably present also in binary and ternary phases' and to some extent, apparently, even in Laves phases." " Although the absence of phases in the Cr-Ni and Mo-Ni systems has not as yet been explained on the basis of electronic structure, it appears reasonable to suspect a connection. One of the great difficulties in arriving at well founded rules in regard to the alloying behavior of transition elements lies in the lack of reliable information concerning the details of their electronic structure in the metallic and alloy form. The theoretical penetration of this field appears to be beset by very considerable difficulties, even when the complications due to alloy formation are disregarded. Another great source of uncertainty is the scarcity of phase diagram information even for binary systems of the transition elements so that only a very limited basis is provided for generalizations as to the occurrence of intermediate phases. For instance, very few binary phase diagrams of second and third long period transition element systems have so far been published. The present work was undertaken in order to survey the various types of intermediate phases occurring in 30 binary systems of elements of the group vanadium, columbium, tantalum, chromium, molybdenum, and tungsten with the elements rhenium, ruthenium, rhodium, palladium, and platinum. For most of these binary systems phase diagrams are very incompletely or not at all known, as will be further reviewed.*

Jan 1, 1957